CN112999888A - Ultrathin PTMSP composite nanofiltration membrane and preparation method thereof - Google Patents
Ultrathin PTMSP composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN112999888A CN112999888A CN202110342741.8A CN202110342741A CN112999888A CN 112999888 A CN112999888 A CN 112999888A CN 202110342741 A CN202110342741 A CN 202110342741A CN 112999888 A CN112999888 A CN 112999888A
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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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
The invention belongs to the technical field of membrane separation, and relates to an ultrathin PTMSP composite membrane and a preparation method thereof. The ultrathin PTMSP composite nanofiltration membrane comprises a support layer and a PTMSP separation layer, wherein the pore diameter of the support layer is less than 200nm, the thickness of the PTMSP separation layer is less than 600nm, the PTMSP separation layer contains trimethyl silicon-1-propyne and an additive, and the additive is selected from p-DCX, PAFs and SiO2At least one of (1). The ultrathin PTMSP composite nanofiltration membrane provided by the invention has higher Bengal Red (RB) rejection rate and methanol flux, high stability and great industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to an ultrathin PTMSP composite nanofiltration membrane and a preparation method thereof.
Background
The nanofiltration membrane is a membrane material with the aperture of less than 0.5-2 nm and selective permeability. Substances with the molecular weight of 200-1000 daltons can be screened by applying proper pressure to one side of the nanofiltration membrane. The nanofiltration technology for realizing material separation by using the nanofiltration membrane has wide application prospects in the aspects of environmental protection, water resource regeneration, organic solvent recovery and the like.
The polytrimethyl silicon-1-propyne (PTMSP) is a porous polymer material with ultrahigh free volume fraction (20-26%) and pore diameter of about 1nm, has good chemical stability, heat resistance and mechanical stability, and shows excellent membrane separation performance in the aspect of separation and purification of materials in recent years. The material is mainly used in the fields of gas separation and alcohol/water separation, and has less application reports in the organic solvent nanofiltration technology. The preparation of PTMSP separation membrane usually adopts casting mode at present, however, the thickness of PTMSP membrane prepared by this method is mostly several micrometers to several tens micrometers, and can not reach nanometer level, which greatly limits the improvement of solvent permeation efficiency in the application of PTMSP nanofiltration technology. In addition, the existing PTMSP nanofiltration membrane also has the problem of operation stability under service conditions, the permeation efficiency or rejection rate is obviously reduced after the membrane is operated for a period of time, the service life is short, and the popularization and the application of the membrane are limited.
Disclosure of Invention
The invention aims to solve the problem that the existing PTMSP membrane preparation process is difficult to produce the ultrathin PTMSP nanofiltration membrane with higher permeation efficiency and running stability by a simple and easily-amplified method, adopts the idea of blending PTMSP and an additive and then scraping the mixture into a membrane on a base membrane material with a smaller aperture by a scraping mode, and provides the nanofiltration membrane with the ultrathin PTMSP composite separation layer and the preparation method thereof so as to improve the separation performance and the running stability of the PTMSP composite nanofiltration membrane.
The thickness of the PTMSP nanofiltration membrane formed by the existing mode (such as casting) is mostly between several micrometers and tens of micrometers, and the thickness is difficult to achieve thinner. The defect-free PTMSP separation layer with nanometer-scale thickness and high separation efficiency is difficult to obtain due to the problems that the casting solution is easy to permeate into the base film and the like in the conventional physical modes (such as spin coating, blade coating and the like). However, after intensive research, the inventors of the present invention found that the catalyst comprises 1 to 10 parts by weight of polytrimethylsilicon-1-propyne and 0.1 to 10 parts by weight of additives (p-DCX, PAFs, MoS)2、O-MoS2And SiO2At least one of the above) and 80-99 parts by weight of organic solvent, wherein the casting solution has a specific viscosity, and a PTMSP separation layer with a pore diameter of less than 200nm can be formed when the casting solution is subjected to a membrane scraping operation with a thin coating thickness on a base membrane with a pore diameter of less than 200nm, so that the obtained ultrathin PTMSP composite nanofiltration membrane has high permeation efficiency (particularly methanol flux) and Bengal Red (RB) rejection rate. Based on this, the present invention has been completed.
The ultrathin PTMSP composite nanofiltration membrane comprises a supporting layer and a PTMSP separation layer, wherein the pore diameter of the supporting layer is less than 200nm, the thickness of the PTMSP separation layer is less than 600nm, the PTMSP separation layer contains polytrimethyl silicon-1-propyne and an additive, and the additive is selected from poly-1, 4-p-dichlorobenzyl (p-DCX), porous aromatic skeleton compounds (PAFs) and molybdenum disulfide (MoS)2) Molybdenum disulfide oxide (O-MoS)2) And SiO2At least one of (1). The PAFs may specifically be at least one selected from the group consisting of PAF-1, PAF-2, PAF-3, PAF-4, and PAF-5.
In the present invention, the pore diameter of the support layer is 200nm or less, preferably 2nm to 150nm, and more preferably 2nm to 100 nm. The thickness of the PTMSP separation layer is 600nm or less, and may be, for example, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, or the like.
In a preferred embodiment of the present invention, the material of the support layer is at least one selected from polysulfone, polyethersulfone, polyetheretherketone, polyacrylonitrile, polyimide, polyvinylidene fluoride, and polytetrafluoroethylene.
In a preferred embodiment of the present invention, the mass ratio of the polytrimethylsilicon-1-propyne to the additive is (5-15): 1.
The preparation method of the ultrathin PTMSP composite nanofiltration membrane provided by the invention comprises the following steps:
s1, preparing a casting solution: uniformly mixing 1-10 parts by weight of polytrimethyl silicon-1-propyne, 0.1-10 parts by weight of additive and 80-99 parts by weight of organic solvent, and standing and defoaming to obtain a membrane casting solution; the additive is selected from p-DCX, PAFs and SiO2At least one of;
s2, scraping, curing and drying the membrane casting solution on a support layer with the aperture of less than 200nm to form a PTMSP separation layer with the thickness of less than 600nm, thereby obtaining the ultrathin PTMSP composite nanofiltration membrane comprising the support layer and the PTMSP separation layer.
In the present invention, in step S1, the amount of the polytrimethylsilicon-1-propyne in the casting solution is 1 to 10 parts by weight, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight; the additive is used in an amount of 0.1 to 10 parts by weight, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight; the organic solvent is used in an amount of 80 to 99 parts by weight, for example, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 parts by weight. In addition, in a preferred embodiment, the mass ratio of the polytrimethylsilicon-1-propyne to the additive is (5-15): 1, and the obtained nanofiltration membrane has higher separation efficiency.
In the present invention, the mixing method in step S1 is not particularly limited, and for example, the additive and the organic solvent may be first mixed to obtain a mixed solution, and the mixed solution and PTMSP may be second mixed. The temperature of the first mixing and the second mixing is not particularly limited as long as the mixing is performed at a stable temperature of the raw materials, and both of them are preferably room temperature. The first mixing and the second mixing are preferably performed under stirring conditions, and the rate of stirring is not particularly limited as long as uniform dispersion of each material can be achieved.
In the present invention, in step S1, the organic solvent may be any of various inert liquid substances capable of dissolving or dispersing the polytrimethylsilicon-1-propyne and the additives, and is preferably at least one selected from tetrahydrofuran, chloroform and cyclohexane, and more preferably chloroform and/or cyclohexane.
In the present invention, in step S1, the standing defoaming is preferably performed under a sealed condition. The standing and defoaming time is preferably 1-48 h, more preferably 2-36 h, and most preferably 4-24 h.
In a preferred embodiment of the present invention, in step S2, the material of the support layer is at least one selected from polysulfone, polyethersulfone, polyetheretherketone, polyacrylonitrile, polyimide, polyvinylidene fluoride, and polytetrafluoroethylene.
In a preferred embodiment of the present invention, in step S2, the thickness of the doctor blade coating or slit extrusion used for the doctor film is 1 to 50 μm, and more preferably 2 to 20 μm.
In a preferred embodiment of the present invention, in step S2, the curing temperature is 20 to 40 ℃ and the curing time is 5min to 12 h. The purpose of the curing was to allow the majority of the organic solvent to evaporate, forming a dense PTMSP separation layer.
In a preferred embodiment of the present invention, in step S2, the drying temperature is 30 to 80 ℃ and the drying time is 4 to 24 hours. The purpose of the drying was to completely volatilize the remaining organic solvent in the PTMSP separation layer.
The invention also provides the ultrathin PTMSP composite nanofiltration membrane prepared by the method.
The ultrathin PTMSP composite nanofiltration membrane provided by the invention has higher Bengal Red (RB) rejection rate and methanol flux and high stability. Test results show that the interception rate of the ultrathin PTMSP composite nanofiltration membrane on RB provided by the invention can be up to 90% -97%, and the methanol flux can be up to 60Lm-2h-1The above.
Detailed Description
In order to better understand the present invention, the technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, adding 0.4 part by weight of p-DCX into 96 parts by weight of cyclohexane, stirring at room temperature until the p-DCX is completely dispersed, then adding 4 parts by weight of PTMSP, stirring at room temperature for 12 hours to form a homogeneous solution, and then standing and defoaming in a closed environment for 24 hours to obtain the casting solution.
S2, placing the membrane casting solution in a trough, pumping the membrane casting solution into a slit extrusion cutter head through a precision metering pump, scraping the membrane on a polysulfone ultrafiltration membrane supporting layer (the aperture is less than or equal to 100nm) by using a scraper with the coating layer thickness of 4 microns to form a membrane, curing the membrane for 6 hours at 25 ℃ in an air atmosphere, and then placing the membrane into an oven at 40 ℃ to dry the membrane for 8 hours to obtain the ultrathin PTMSP composite nanofiltration membrane. The thickness of the PTMSP separation layer in the ultrathin PTMSP composite nanofiltration membrane is 270 +/-20 nm.
Example 2
S1, adding 0.1 part by weight of PAF-1 into 99 parts by weight of cyclohexane, stirring at room temperature until the PAF-1 is completely dispersed, then adding 1 part by weight of PTMSP, stirring at room temperature for 12 hours to form a homogeneous solution, and then standing and defoaming in a closed environment for 10 hours to obtain the casting solution.
S2, placing the membrane casting solution in a trough, pumping the membrane casting solution into a slit extrusion cutter head through a precision metering pump, scraping the membrane on a polysulfone ultrafiltration membrane supporting layer (the aperture is less than or equal to 100nm) by using a scraper with the coating layer thickness of 4 microns to form a membrane, curing the membrane for 2 hours at 25 ℃ in an air atmosphere, and then placing the membrane into an oven at 40 ℃ for drying for 4 hours to obtain the ultrathin PTMSP composite nanofiltration membrane. The thickness of the PTMSP separating layer in the ultrathin PTMSP composite nanofiltration membrane is 0-200 nm.
Example 3
S1, adding 5 parts by weight of PTMSP into 95 parts by weight of cyclohexane, stirring at room temperature for 24 hours to form a homogeneous solution, and then standing and defoaming in a closed environment for 24 hours to obtain a casting solution.
S2, placing the casting solution in a trough, pumping the casting solution into a slit extrusion cutter head through a precision metering pump, scraping the casting solution on a polyvinylidene fluoride base membrane (the aperture is less than or equal to 100nm) by using a scraper with the coating layer thickness of 4 microns to form a membrane, curing the membrane for 4 hours at 25 ℃ in an air atmosphere, and then placing the membrane in an oven at 60 ℃ for drying for 6 hours to obtain the ultrathin PTMSP composite nanofiltration membrane. The thickness of the PTMSP separation layer in the ultrathin PTMSP composite nanofiltration membrane is 340 +/-20 nm.
Comparative example 1
An ultrathin PTMSP composite nanofiltration membrane is prepared according to the method in the embodiment 1, except that the p-DCX is replaced by the same weight part of organic solvent, and the rest conditions are the same as those in the embodiment 1, so that the reference ultrathin PTMSP composite nanofiltration membrane is obtained. The thickness of the PTMSP separation layer in the reference ultrathin PTMSP nanofiltration membrane is 270 +/-20 nm.
Comparative example 2
An ultrathin PTMSP composite nanofiltration membrane is prepared according to the method in the embodiment 1, except that the aperture of the adopted polysulfone-based membrane is 450nm, and the rest conditions are the same as those in the embodiment 1, so that the reference ultrathin PTMSP composite nanofiltration membrane is obtained. The thickness of the PTMSP separating layer in the reference ultrathin PTMSP composite nanofiltration membrane is 0-300 nm.
Comparative example 3
An ultra-thin PTMSP composite nanofiltration membrane was prepared according to the method of example 1, except that the thickness of the scraped film was 50 μm, and the rest of the conditions were the same as those of example 1, to obtain a reference ultra-thin PTMSP composite nanofiltration membrane. The thickness of the PTMSP separation layer in the reference ultrathin PTMSP composite nanofiltration membrane is 3600 +/-50 nm.
Test example
(1) Methanol flux: respectively loading the ultrathin PTMSP composite nanofiltration membranes obtained in the embodiments and the comparative examples into a membrane pool, measuring the methanol permeation amount of the membrane after 0.5h of operation under the conditions of 0.4MPa of pressure and 25 ℃, and calculating the methanol flux by the following formula:
j ═ Q/(a · t), where J is methanol flux, Q is methanol flux (L), and a is effective membrane area of the nanofiltration membrane (m ═ t)2) And t is time (h). The results are shown in Table 1.
(2) Bengal red rejection: respectively loading the ultrathin PTMSP composite nanofiltration membranes obtained in the examples and the comparative examples into membrane tanks, wherein the filtrate is 20ppm of Bengal/methanol solution, collecting Bengal/methanol permeate after the membrane runs for 0.5h under the conditions of 0.4MPa of pressure and 25 ℃, and calculating the Bengal rejection rate according to the following formula:
R＝(Cp-Cf)/Cpx 100%, wherein R is the Bengal rejection rate, CpIs the concentration of Bengal in the stock solution, CfThe concentration of bengal in the permeate is given. CpAnd CfAll measurements were performed using an ultraviolet-visible spectrophotometer (model UV-7502PC, from Shanghai Xinmao instruments Co., Ltd.). The results are shown in Table 1.
TABLE 1
The comparison between the example 1 and the comparative example 1 shows that the nano additive can improve the separation effect and the operation stability of the ultrathin PTMSP separation layer, greatly improve the methanol flux and keep a higher RB retention rate; the comparison between example 2 and comparative example 2 shows that the appropriate pore size of the base membrane can enable the PTMSP to form a relatively complete PTMSP composite separation layer at a lower wiped film thickness, and when the pore size of the base membrane is too large, the continuous complete separation layer is difficult to form, so that the membrane shows poor rejection rate; comparing example 3 with comparative example 3, it can be seen that by using a smaller scraped membrane thickness to scrape an ultra-thin PTMSP separation layer, the permeation flux of the membrane can be greatly increased on the basis of a substantially constant menglan rejection. Therefore, the ultrathin PTMSP nanofiltration membrane obtained by the method provided by the invention not only has higher methanol flux, but also shows good interception performance for Bengal (RB).
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. The ultrathin PTMSP composite nanofiltration membrane is characterized by comprising a supporting layer and a PTMSP separation layer, wherein the pore diameter of the supporting layer is less than 200nm, the thickness of the PTMSP separation layer is less than 600nm, the PTMSP separation layer contains trimethyl silicon-1-propyne and an additive, and the additive is selected from p-DCX, PAFs and MoS2、O-MoS2And SiO2At least one of (1).
2. The ultra-thin PTMSP composite nanofiltration membrane of claim 1, wherein the material of the support layer is at least one selected from polysulfone, polyethersulfone, polyetheretherketone, polyacrylonitrile, polyimide, polyvinylidene fluoride and polytetrafluoroethylene.
3. The ultrathin PTMSP composite nanofiltration membrane according to claim 1, wherein the mass ratio of the polytrimethylsilicon-1-propyne to the additive is (5-15): 1.
4. A preparation method of an ultrathin PTMSP composite nanofiltration membrane is characterized by comprising the following steps:
s1, preparing a casting solution: uniformly mixing 1-10 parts by weight of polytrimethyl silicon-1-propyne, 0.1-10 parts by weight of additive and 80-99 parts by weight of organic solvent, and standing and defoaming to obtain a membrane casting solution; the additive is selected from p-DCX, PAFs, MoS2、O-MoS2And SiO2At least one of;
s2, scraping, curing and drying the membrane casting solution on a support layer with the aperture of less than 200nm to form a PTMSP separation layer with the thickness of less than 600nm, thereby obtaining the ultrathin PTMSP composite nanofiltration membrane comprising the support layer and the PTMSP separation layer.
5. The method for preparing the ultrathin PTMSP composite nanofiltration membrane according to claim 4, wherein in the step S1, the mass ratio of the polytrimethylsilicon-1-propyne to the additive is (5-15): 1.
6. The method for preparing an ultrathin PTMSP composite nanofiltration membrane according to claim 4, wherein in step S1, the organic solvent is at least one selected from tetrahydrofuran, chloroform and cyclohexane.
7. The method for preparing an ultrathin PTMSP composite nanofiltration membrane according to claim 4, wherein in step S2, the material of the support layer is at least one selected from polysulfone, polyethersulfone, polyetheretherketone, polyacrylonitrile, polyimide, polyvinylidene fluoride and polytetrafluoroethylene.
8. The method for preparing an ultrathin PTMSP composite nanofiltration membrane according to any one of claims 4 to 7, wherein in the step S2, the scraping process is a doctor blade coating process or a slit extrusion process, and the thickness is 1 to 50 μm.
9. The method for preparing the ultrathin PTMSP composite nanofiltration membrane according to any one of claims 4 to 7, wherein in the step S2, the curing temperature is 20-40 ℃, and the curing time is 5 min-12 h; the drying temperature is 30-80 ℃, and the drying time is 4-24 hours.
10. An ultrathin PTMSP composite nanofiltration membrane prepared by the method of any one of claims 4 to 9.
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