CN108031304B - Flat plate type mixed matrix forward osmosis membrane based on metal organic framework MIL-101(Cr) and preparation method - Google Patents
Flat plate type mixed matrix forward osmosis membrane based on metal organic framework MIL-101(Cr) and preparation method Download PDFInfo
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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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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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
- B01D61/002—Forward osmosis or direct osmosis
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- 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
- B01D67/0002—Organic membrane manufacture
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- 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
- B01D69/06—Flat membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
Abstract
The invention discloses a flat plate type mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr) and a preparation method thereof, belonging to the field of membrane separation. Uniformly dispersing 0.05-1.5% (w/w) MIL-101(Cr) in 66.5-90.95% (w/w) mixed solvent by ultrasonic, adding the mixture and 8.0-20.0% (w/w) cellulose acetate into a three-mouth round-bottom flask in a certain order, stirring to completely dissolve the cellulose acetate, adding 1.0-12.0% (w/w) polyvinylpyrrolidone or polyethylene glycol, stirring at 15-90 ℃ to completely dissolve for 2-16 h, standing and defoaming for 3-16 h, and preparing forward osmosis membrane casting solution; scraping the support material to form a film, and performing heat treatment on the film for 5-60 mins in deionized water at the temperature of 30-90 ℃ to obtain the flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr). The forward osmosis membrane prepared by the invention utilizes 1M NaCl as a driving liquid and deionized water as a raw material liquid, and the pure water flux of the forward osmosis membrane is more than 45.0L/M within 1h of test time2H, reverse salt flux less than 2.5g/m2•h。
Description
Technical Field
The invention relates to a high-molecular flat forward osmosis membrane and a preparation method thereof, in particular to a flat mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr) and a preparation method thereof.
Background
The shortage of water resources and the increasingly serious water pollution become bottlenecks that restrict social progress and economic development, and the development of new water sources and the resource utilization of waste sewage also become global common concerns. Because the seawater resources on the earth are extremely rich and a large amount of waste sewage is generated, seawater desalination and sewage recycling become strategic choices for solving the water resource crisis. Among many seawater desalination and sewage recycling technologies, membrane separation technology is one of the best choices. The forward osmosis technology with low energy consumption and high water recovery rate, which is produced as a solution to the key problem, becomes a research focus and a hotspot in the fields of seawater desalination and sewage recycling, and has important strategic significance for solving the problem of water resource shortage.
Forward Osmosis (FO) is a membrane separation technology driven by osmotic pressure on two sides of a membrane, and is increasingly emphasized, and related theories and application researches have made great progress and are successfully applied to the fields of seawater desalination, wastewater treatment, food and medicine, energy and the like. At present, common forward osmosis membranes mainly comprise cellulose acetate membranes, polybenzimidazole membranes, polyamide composite membranes and the like, and the forward osmosis membranes with low commercialization degree mainly lack good forward osmosis membranes and proper driving liquid, and are the key points of the whole forward osmosis process. The high-performance forward osmosis membrane is closely related to the material property and the structure of the membrane, and the membrane material with excellent visible performance and the preparation method of the forward osmosis membrane are particularly important. Common preparation methods of the forward osmosis membrane include an interface polymerization method, a double-selection layer membrane preparation method and a nanofiltration membrane modification method. The concentration polarization in the forward osmosis composite membrane prepared by the interfacial polymerization method is serious; the double-selection layer film effectively reduces the internal concentration polarization, but the preparation process is more complex; the rejection rate and water flux of the nanofiltration membrane modified membrane to monovalent salt are both low; therefore, it is required to develop a new forward osmosis membrane preparation process to improve the separation performance of the forward osmosis membrane and the feasibility of industrialization.
In the last 60 years, the research on forward osmosis technology began abroad, and the application research on forward osmosis is carried out by adopting commercial reverse osmosis membranes or nanofiltration membranes, and the result proves that the existing reverse osmosis membranes or nanofiltration membranes are difficult to use in the forward osmosis process, but the performance of the forward osmosis membranes is closely related to membrane materials and membrane structures; subsequently, a number of membrane scientists have begun fundamental research on the preparation of forward osmosis membranes, and research results show that forward osmosis membranes with excellent performance can be prepared by selecting appropriate membrane materials and membrane forming processes. The research on forward osmosis technology in China starts late, and the research on forward osmosis technology in China is still in the exploration stage no matter the film preparation or the film process research is carried out at present. Some membrane researchers have explored the preparation conditions of cellulose forward osmosis membranes and studied the influence of various factors on the performance of the forward osmosis membranes, but have not prepared the forward osmosis membranes with good performance which can be commercialized; the research on the preparation and application of forward osmosis membranes is still of great importance. The early researches show that the water flux, the salt rejection rate, the mechanical property and the pollution resistance of the forward osmosis membrane are hopeful to be improved by modifying the membrane material by using the blending technology, and the industrialization is easy to realize. According to the invention, the flat-plate type and hollow fiber forward osmosis membranes are prepared by respectively blending nano titanium dioxide, graphene and cellulose acetate in patent ZL201410770001.4, 201510245514.8, ZL201410769752.4 and 201510245504.4, and the separation performance and the permeability of the prepared forward osmosis membranes are greatly improved; the invention patents 2017100954795, 2017100954780 and 2017100954846 adopt the blending of the functionalized carbon nano tube and the cellulose acetate to prepare the forward osmosis membrane with better performance; but the separation performance and the permeability of the prepared forward osmosis membrane can be further improved by selecting proper auxiliary materials, so that the requirements of commercial production and application are met.
Metal-Organic Frameworks (MOFs) are a new material developed recently, also called Metal-Organic complex polymers, which are porous materials with infinite network structures assembled by Organic ligands containing oxygen, nitrogen, etc. and Metal ions through coordination. Compared with the traditional inorganic porous materials, the MOFs material has incomparable excellent performance of inorganic porous materials such as zeolite, activated carbon, carbon nano tubes and the like, has the micropore volume which is several times higher than that of the porous materials, and has the characteristics of variable pore channels, stable chemical structure and the like. The excellent characteristics enable the MOFs material to have huge application prospects in the aspects of gas storage, water body pollutant adsorption and separation, gas catalysis and the like. The metal organic framework is used as a novel organic-inorganic hybrid material, and the organic ligand in the structure of the metal organic framework is helpful for improving the affinity between MOFs particles and a polymer matrix, so that the metal organic framework is an ideal mixed matrix membrane disperse phase. Therefore, if a mixed matrix forward osmosis membrane is prepared by blending a proper MOFs material and cellulose acetate, the forward osmosis membrane is expected to have pollution resistance while high water flux and salt rejection rate are obtained, and a new thought is provided for research, development, application and popularization of a forward osmosis membrane material.
How to make the forward osmosis membrane have the pollution resistance and the stability of keeping the water flux while obtaining the hydrophilic property is a difficult problem which is continuously thought and researched by membrane technologists in recent years. The research of improving the structure, the permeability and the separation performance of the mixed matrix forward osmosis membrane by adopting MIL-101(Cr) has not been reported in documents at home and abroad.
Disclosure of Invention
The invention aims to provide a flat mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr), and the invention also aims to provide a preparation method of the mixed matrix forward osmosis membrane.
In order to achieve the purpose, the invention adopts the technical scheme that:
a flat mixed matrix forward osmosis membrane based on MIL-101(Cr) is composed of the following substances in percentage by mass: 8.0-20.0% (w/w) of polymer film material, 1.0-12.0% (w/w) of pore-foaming agent, 0.05-1.5% (w/w) of MIL-101(Cr) and 66.5-90.95% (w/w) of solvent;
the polymer film material is one or two of cellulose diacetate and cellulose triacetate, and the content is 8.0-20.0% (w/w);
the metal organic framework MIL-101(Cr) is a self-made metal organic framework material, has regular and uniform appearance, uniform particle size, smooth and flat crystal surface and octahedral crystal shape, and the content is 0.05-1.5% (w/w);
the pore-foaming agent is one of polyvinylpyrrolidone and polyethylene glycol-400, and the content is 1.0-12.0% (w/w);
the solvent is a mixed solvent of N-methyl pyrrolidone and acetone, the volume ratio of N-methyl pyrrolidone to acetone =1: 0.1-7.0, and the content is 66.5% -90.95% (w/w).
A preparation method of a flat plate type mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr) comprises the following steps:
(1) adding a certain amount of MIL-101(Cr) into a mixed solvent, fully and uniformly dispersing the MIL-101(Cr) in the mixed solvent by using ultrasound, adding the mixture into a three-neck round-bottom flask after the dispersion is finished, adding a certain amount of polymer film material, and uniformly stirring;
(2) adding a certain amount of pore-forming agent into a three-neck round-bottom flask, stirring and dissolving at the temperature of 15-90 ℃ for 2-16 hours until the pore-forming agent is completely dissolved, and preparing an initial casting solution of a flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr); standing the obtained casting solution for 3-16 hours at the stirring and dissolving temperature, and removing bubbles remained in the casting solution;
(3) spreading the support layer on a cleaned and dried glass plate, pouring a certain amount of casting solution on the glass plate, and scraping the casting solution into a film by using a flat film scraper; evaporating the formed nascent membrane for 1-30 seconds at room temperature, immersing the nascent membrane into a constant-temperature solidification bath water tank at 15-60 ℃ for solidification and formation, automatically separating the formed nascent membrane from a glass plate, taking out the nascent membrane, soaking the nascent membrane in normal-temperature deionized water for 12-48 hours, and then carrying out heat treatment on the nascent membrane in the deionized water at 30-90 ℃ for 5-60 minutes to obtain the flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr).
The supporting layer is one of a polyester screen, a non-woven fabric, a cotton yarn filter cloth, filter paper and nylon cloth, and the aperture of the supporting layer is 60-280 meshes;
the evaporation time of the nascent membrane at normal temperature refers to the retention time of the prepared flat forward osmosis membrane in the air after the membrane scraping is finished, and the evaporation time is 1-30 seconds;
the heat treatment temperature and time refer to the deionized water temperature and the treatment time for carrying out heat treatment on the prepared flat forward osmosis membrane, the heat treatment temperature is 30-90 ℃, and the heat treatment time is 5-60 minutes;
the coagulating bath is deionized water.
The invention provides a flat mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr) and a preparation method thereof, wherein the MIL-101(Cr) is introduced into a polymer to prepare the mixed matrix forward osmosis membrane, and the mixed matrix forward osmosis membrane is endowed with good permeability, separation performance and pollution resistance, which is an innovative point of the invention. The test result shows that the pure water flux and the reverse salt flux of the prepared forward osmosis membrane are greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the MIL-101(Cr) provided by the invention solves the problem of collapse of the traditional metal organic framework, and compared with the traditional cellulose acetate forward osmosis membrane and the carbon nanotube-based blending forward osmosis membrane, the pure water flux and the reverse salt flux of the flat plate type mixed matrix forward osmosis membrane prepared by blending modification are obviously improved.
(2) The method for preparing the flat plate type mixed matrix forward osmosis membrane by blending and modifying MIL-101(Cr) has the advantages of simple and easily-controlled equipment and simple membrane preparation process, endows the prepared forward osmosis membrane with good permeability, separation performance and pollution resistance while forming the membrane, and is easy to realize industrialization.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
0.5% (w/w) of MIL-101(Cr) was added to a mixed solvent of 54.5% (w/w) N-methylpyrrolidone and 25.0% (w/w) acetone, and sufficiently and uniformly dispersed therein by using ultrasonic waves, and after completion of the dispersion, the mixture was added to a three-necked round-bottomed flask, and 13.0% (w/w) of cellulose acetate was added thereto and uniformly stirred. Adding 7.0% (w/w) of polyethylene glycol-400 pore-foaming agent into a three-neck round-bottom flask, stirring and dissolving at 65 ℃ for 8 hours until the pore-foaming agent is completely dissolved, and preparing an initial membrane casting solution of the flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr); then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 9 hours to remove air bubbles remaining in the casting solution. Spreading a 180-mesh polyester screen on a cleaned and dried glass plate, pouring a certain amount of casting solution on the glass plate, and scraping the casting solution into a film by using a flat film scraper; evaporating the nascent film at room temperature for 10 s, and soaking in 25 deg.C constant temperature coagulationAnd (3) solidifying and forming in a solid bath water tank, automatically separating the formed film from the glass plate, taking out the film, soaking the film in deionized water at normal temperature for 24 hours, and then performing heat treatment on the film in the deionized water at 65 ℃ for 15 minutes to obtain the flat mixed matrix forward osmosis film based on MIL-101 (Cr). 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 45.0L/m within 1h of test time2H or more, reverse salt flux is less than 2.5g/m2•h。
Example 2:
the contents of MIL-101(Cr) and N-methylpyrrolidone were adjusted to 0.05% (w/w) and 54.95% (w/w), respectively, and the rest was the same as in example 1. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 31.0L/m within 1h of test time2H or more, reverse salt flux is less than 3.5g/m2•h。
Example 3:
MIL-101(Cr) and N-methylpyrrolidone were adjusted to 1.5% (w/w) and 53.5% (w/w), respectively, and the rest was the same as in example 1. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 43.0L/m within 1h of test time2H or more, reverse salt flux is less than 3.0g/m2•h。
Example 4:
the procedure of example 1 was repeated except that polyethylene glycol-400 in the porogen was replaced with polyvinylpyrrolidone. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 36.0L/m within 1h of test time2H or more, reverse salt flux is less than 2.5g/m2•h。
Example 5:
the temperature of the coagulation bath was adjusted from 25 ℃ to 60 ℃ in the same manner as in the previous example1. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 49.0L/m within 1h of test time2H or more, reverse salt flux is less than 3.5g/m2•h。
Example 6:
the heat treatment temperature was adjusted from 65 ℃ to 90 ℃ and the rest was the same as in example 1. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 39.0L/m within 1h of test time2H or more, reverse salt flux is less than 3.0g/m2•h。
Example 7:
the heat treatment time was adjusted from 15 minutes to 60 minutes, and the rest was the same as in example 1. The properties of the prepared flat mixed matrix forward osmosis membrane based on MIL-101(Cr) are as follows: 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 41.0L/m within 1h of test time2H or more, reverse salt flux is less than 2.5g/m2•h。
Comparative example 1:
a mixed solvent composed of 55.0% (w/w) N-methyl pyrrolidone and 25.0% (w/w) acetone was added to a three-necked round-bottomed flask, and then 13.0% (w/w) cellulose acetate was added thereto and stirred uniformly. Adding 7.0% (w/w) of polyethylene glycol-400 pore-forming agent into a three-neck round-bottom flask, stirring and dissolving at 65 ℃ for 8 hours until the pore-forming agent is completely dissolved, and preparing initial membrane casting solution of the flat-plate cellulose acetate mixed matrix forward osmosis membrane; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 9 hours to remove air bubbles remaining in the casting solution. Spreading a 180-mesh polyester screen on a cleaned and dried glass plate, pouring a certain amount of casting solution on the glass plate, and scraping the casting solution into a film by using a flat film scraper; evaporating the nascent film at room temperature for 10 s, soaking in 25 deg.C constant temperature coagulating bath water tank for coagulating and forming, and automatically separating the formed filmAnd (3) taking the membrane out, soaking the membrane in deionized water at normal temperature for 24 hours, and then performing heat treatment on the membrane in deionized water at 65 ℃ for 15 minutes to obtain the flat plate type cellulose acetate mixed matrix forward osmosis membrane. 1MNaCl is used as a driving liquid, deionized water is used as a raw material liquid, and the pure water flux of the prepared forward osmosis membrane reaches 33.0L/m within 1h of test time2H or more, reverse salt flux is less than 4.0g/m2•h。
Claims (4)
1. A flat plate type mixed matrix forward osmosis membrane based on a metal organic framework MIL-101(Cr) is characterized in that a casting solution contains the metal organic framework MIL-101(Cr) and influences the structure and the performance of the forward osmosis membrane; the casting solution consists of the following substances in percentage by mass: polymer film material 8.0-20.0% (w/w), pore-forming agent 1.0-12.0% (w/w), MIL-101(Cr) 0.5-1.5% (w/w), solvent 66.5-90.95% (w/w);
the pore-foaming agent is polyethylene glycol-400;
the polymer membrane material is one or two of cellulose diacetate and cellulose triacetate;
the solvent is a mixed solvent of N-methyl pyrrolidone and acetone, and the volume ratio of the mixed solvent to the solvent is N-methyl pyrrolidone: acetone =1: 0.1-7.0, content 66.5% -90.95% (w/w);
the preparation method of the flat plate type mixed matrix forward osmosis membrane based on the metal organic framework MIL-101(Cr) comprises the following steps:
(1) adding a certain amount of MIL-101(Cr) into a mixed solvent, fully and uniformly dispersing the MIL-101(Cr) in the mixed solvent by using ultrasound, adding the mixture into a three-neck round-bottom flask after the dispersion is finished, adding a certain amount of polymer film material, and uniformly stirring;
(2) adding a certain amount of pore-forming agent into a three-neck round-bottom flask, stirring and dissolving at the temperature of 15-90 ℃ for 2-16 hours until the pore-forming agent is completely dissolved, and preparing an initial casting solution of a flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr); standing the obtained casting solution for 3-16 hours at the stirring and dissolving temperature, and removing bubbles remained in the casting solution;
(3) spreading the support layer on a cleaned and dried glass plate, pouring a certain amount of casting solution on the glass plate, and scraping the casting solution into a film by using a flat film scraper; evaporating the formed nascent membrane for 1-30 seconds at room temperature, immersing the nascent membrane into a constant-temperature solidification bath water tank at 15-60 ℃ for solidification and formation, automatically separating the formed nascent membrane from a glass plate, taking out the nascent membrane, soaking the nascent membrane in normal-temperature deionized water for 12-48 hours, and then carrying out heat treatment on the nascent membrane in the deionized water at 30-90 ℃ for 5-60 minutes to obtain the flat plate type mixed matrix forward osmosis membrane based on MIL-101 (Cr).
2. The MIL-101(Cr) -based flat mixed matrix forward osmosis membrane according to claim 1, wherein: the forward osmosis membrane is prepared by adopting a traditional phase inversion method, namely a dry-wet method.
3. The MIL-101(Cr) -based flat mixed matrix forward osmosis membrane according to claim 1, wherein: the MIL-101(Cr) is a self-made metal organic framework material, is octahedral crystal particles and has the content of 0.5-1.5% (w/w).
4. The MIL-101(Cr) -based flat mixed matrix forward osmosis membrane according to claim 1, wherein: the supporting layer is one of a polyester screen, a non-woven fabric, a cotton yarn filter cloth, filter paper and nylon cloth, and the aperture of the supporting layer is 60-280 meshes; the coagulating bath is deionized water.
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