CN113559708A - MIL-68 (Al)/alpha-iron oxide mixed matrix-based forward osmosis membrane and preparation method thereof - Google Patents
MIL-68 (Al)/alpha-iron oxide mixed matrix-based forward osmosis membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 130
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 75
- 239000013216 MIL-68 Substances 0.000 title claims abstract description 48
- 239000011159 matrix material Substances 0.000 title claims abstract description 43
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000000654 additive Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
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- 230000004907 flux Effects 0.000 abstract description 29
- 239000007788 liquid Substances 0.000 abstract description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 15
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- 238000005265 energy consumption Methods 0.000 description 4
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- 230000035699 permeability Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000013178 MIL-101(Cr) Substances 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000013144 Fe-MIL-100 Substances 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
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- 239000002096 quantum dot Substances 0.000 description 1
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- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
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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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a metal organic framework compound MIL-68 (Al)/alpha-iron oxide (alpha-Fe)2O3) A mixed matrix forward osmosis membrane and a preparation method thereof belong to the field of membrane separation. 0.2 to 1.0 percent (w/w) of MIL-68 (Al)/alpha-Fe2O3Adding 53.0-82.8% (w/w) of organic solvent, 2.0-10.0% (w/w) of 1, 4-dioxane or acetone, 2.0-10.0% (w/w) of pore-forming agent lactic acid or polyethylene glycol, 2.0-10.0% (w/w) of auxiliary pore-forming agent methanol and 11.0-16.0% (w/w) of cellulose acetate into a three-neck round-bottom flask according to a certain sequence, stirring for 8-16 h at 40-80 ℃ until complete dissolution, standing for 20-24 h, and preparing into casting solution; scraping on supporting materialsForming a film, immersing the film in a constant-temperature coagulating bath at 30-50 ℃, soaking the film in deionized water at normal temperature for 20-48 h after forming, and performing heat treatment on the film for 5-60 min in deionized water at 40-80 ℃ to obtain the film based on MIL-68 (Al)/alpha-Fe2O3A mixed matrix forward osmosis membrane. The forward osmosis membrane prepared by the invention uses 1M NaCl as a driving liquid and deionized water as a raw material liquid, and tests for 1h show that the pure water flux is more than 61.9L/(M)2H) reverse salt flux of less than 2.85 g/(m)2·h)。
Description
Technical Field
The invention belongs to the technical field of membranes, relates to a polymer mixed matrix forward osmosis membrane and a preparation method thereof, and particularly relates to a metal-organic framework compound MIL-68 (Al)/alpha-Fe-based forward osmosis membrane2O3A mixed matrix forward osmosis membrane and a preparation method thereof.
Background
With the rapid growth of global population and the continuous development of industry, the shortage of fresh water resources and the treatment of polluted water sources become global problems to be solved urgently. The seawater occupying two thirds of the surface area of the earth is desalted to prepare fresh water and the fresh water is obtained by purifying a polluted water source, which is an important means for solving the crisis of fresh water resources at present. In the past half century or more, many water treatment technologies have been developed worldwide to perform desalination processes such as desalination of sea water, and these technologies can be classified into two categories, thermal desalination and membrane desalination, according to the separation principle.
Thermal desalination, also called distillation, can realize effective separation of multi-component solution by traditional techniques including multi-stage flash distillation, vapor compression distillation, multi-stage evaporation and the like, but the development of the method is limited by the problems of high energy consumption, high operation cost and the like. Membrane separation is a technique in which a component of a fluid is selectively passed through a membrane to be concentrated, fractionated or purified, driven by the pressure difference of the fluid across the membrane material.
In recent years, membrane separation techniques have been widely used in the fields of water treatment, desalination, and the like. However, the traditional membrane separation technologies such as microfiltration, ultrafiltration, nanofiltration and reverse osmosis need to use extra pressure as the driving force for water molecule transmission across membranes, and the operation energy consumption and the cost are high. Therefore, reducing energy consumption is critical to whether the technology can be applied on a large scale.
The forward osmosis process is a process in which water flows from a low-concentration raw material solution to a high-concentration draw solution by utilizing the permselectivity of a membrane with the osmotic pressure difference between both sides of the membrane as a driving force. In this process, water on the raw material liquid side enters the drawing liquid side by diffusion. Thus, the raw material solution is concentrated, and the draw solution is diluted. The diluted drawing agent of the drawing liquid is subjected to a series of treatments such as thermal decomposition, thermal volatilization and the like to obtain purified water. Forward osmosis is a membrane separation technology which spontaneously realizes water molecule transfer by taking osmotic pressure difference on two sides of a selective osmosis membrane as a driving force, so that the forward osmosis has the characteristics of low energy consumption, low pollution, strong pollutant interception capability and the like, and has attracted much attention in recent years.
Because the forward osmosis membrane has certain interception to can make the solute in the raw materials liquid gather at the surface of membrane in the permeation process, and the opposite side is because there is water to pass through and makes the boundary concentration far less than the driving liquid main part, so raw materials liquid side membrane surface near concentration is too high, and main solution concentration is less than the membrane surface region, and driving liquid side solution is diluted to lead to the reduction of membrane both sides osmotic pressure difference, finally makes the water flux in this permeation process reduce. Therefore, in order to improve the separation performance of the forward osmosis membrane, researchers continuously search for and improve a preparation method of the separation membrane, optimize a structure of a support layer, and practically and greatly improve the separation performance of the forward osmosis membrane. How to obtain high-performance forward osmosis membranes is also a current research hotspot. 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. The invention patents CN201711475700.6, CN201711480321.6, CN201711484518.7 and CN201711476031.4 respectively adopt MIL-53(Fe), MIL-101(Cr), MIL-100(Fe), MIL-101(Cr)/GO and cellulose acetate to be blended to prepare the flat-plate type and hollow fiber forward osmosis membrane, and the separation performance and the permeability of the prepared forward osmosis membrane are greatly improved. But also has the problems of complex material preparation process, higher cost, easy pollution generation and the like. Therefore, proper auxiliary materials are selected, so that the separation performance and permeability of the prepared forward osmosis membrane can be further improved, and the commercial production and application requirements can be met.
The metal organic framework material is a hybrid crystal material which is self-assembled by taking an organic ligand as a bridging molecule, and metal ions or metal clusters through coordination and coordination bonds and the interaction between the molecules and has a one-dimensional, two-dimensional or three-dimensional ordered network structure. Metal-organic frameworks have many advantages over other porous materials. The pore diameter of the porous material can be changed, the porosity is large, and the chemical structure is stable. In the field of membrane separation, a metal organic framework with high porosity is beneficial to water molecules to pass through; meanwhile, the window has adjustable window size, and is favorable for molecular selection. The two advantages are organically combined, so that the selectivity and the salt interception capability of the membrane are enhanced, and the defects of the forward osmosis membrane are overcome.
The metal organic framework composite is a two-phase or multi-phase composite material which takes a metal organic framework as a matrix or a reinforcement and takes polymer whole, microspheres, fibers, metal, magnetic nano particles, graphite oxide, carbon nano tubes, quantum dots, photonic crystals, inorganic matters and the like with different properties as the matrix or the reinforcement. The metal-organic framework composite maintains the excellent performance of each phase, and simultaneously compensates the limitation of any single phase in application.
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 invention adopts metal organic framework compound MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane is prepared, the structure and the hydrophilicity of the forward osmosis membrane are improved, and no literature report is found at home and abroad.
Disclosure of Invention
The invention aims to provide a metal-organic framework compound MIL-68 (Al)/alpha-Fe based on2O3The present invention also provides a method for preparing the mixed matrix forward osmosis membrane.
In order to achieve the purpose, the invention adopts the technical scheme that:
metal organic framework compound MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane consists of the following substances in percentage by mass: 11.0-16.0 percent (w/w) of polymer film material, 2.0-10.0 percent (w/w) of additive, 2.0-10.0 percent (w/w) of pore-foaming agent, 2.0-10.0 percent (w/w) of auxiliary pore-foaming agent, 53.0-82.8 percent (w/w) of organic solvent and MIL-68 (Al)/alpha-Fe2O3 0.2%～1.0% (w/w)。
The polymer film material is one or two of cellulose diacetate and cellulose triacetate, and the content is 11.0-16.0% (w/w);
the additive is one of 1, 4-dioxane or acetone, and the content is 2.0-10.0% (w/w);
the pore-foaming agent is one of lactic acid or polyethylene glycol, and the content is 2.0-10.0% (w/w);
the auxiliary pore-foaming agent is methanol with the content of 2.0-10.0% (w/w);
the organic solvent is one of N, N-dimethylformamide or N, N-dimethylacetamide, and the content is 53.0-82.8% (w/w);
the MIL-68 (Al)/alpha-Fe2O3The self-made metal organic framework compound is a porous polyhedral structure, and the content of the porous polyhedral structure is 0.2-1.0% (w/w).
Metal organic framework compound MIL-68 (Al)/alpha-Fe2O3 The method for preparing a mixed matrix forward osmosis membrane of (1), comprising the steps of:
(1) mixing a certain amount of MIL-68 (Al)/alpha-Fe2O3Adding the mixture into an organic solvent, fully and uniformly dispersing the mixture in the organic solvent by utilizing 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 an additive, and uniformly stirring;
(2) adding a certain amount of pore-forming agent and auxiliary pore-forming agent into a three-neck round-bottom flask, stirring and dissolving at 40-80 ℃ for 8-16 hours until the pore-forming agent and the auxiliary pore-forming agent are completely dissolved, and preparing the MIL-68 (Al)/alpha-Fe-based material2O3The mixed matrix forward osmosis membrane of (1) initial membrane casting solution; then, will getStanding the obtained casting solution for 20-24 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-state membrane for 1-30 seconds at room temperature, immersing the nascent-state membrane into a constant-temperature solidification bath water tank at the temperature of 30-50 ℃ for solidification and forming, automatically separating the formed nascent-state membrane from a glass plate, taking out the nascent-state membrane, soaking the nascent-state membrane in normal-temperature deionized water for 12-48 hours, and then carrying out heat treatment on the nascent-state membrane in deionized water at the temperature of 40-80 ℃ for 5-60 minutes to obtain the nascent-state membrane based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix of (3) is a forward osmosis membrane.
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 state membrane at normal temperature refers to the retention time of the prepared 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 temperature of deionized water and the treatment time for carrying out heat treatment on the prepared forward osmosis membrane, the heat treatment temperature is 40-80 ℃, and the heat treatment time is 5-60 minutes;
the coagulating bath is deionized water.
The invention provides a metal-organic framework compound MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane is prepared by mixing MIL-68 (Al)/alpha-Fe2O3The composite material is added into a polymer to prepare a mixed matrix forward osmosis membrane, and the mixed matrix forward osmosis membrane is endowed with good permeability, separation performance and pollution resistance, which is the innovation 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-68 (Al)/alpha-Fe provided by the invention2O3Solves the problem of collapse of the traditional metal organic framework, and the mixture prepared by blending and modifying the traditional metal organic frameworkCompared with the traditional cellulose acetate forward osmosis membrane and the carbon nanotube-based blended forward osmosis membrane, the pure water flux and the reverse salt flux of the composite-matrix forward osmosis membrane are obviously improved.
(2) The MIL-68 (Al)/alpha-Fe provided by the invention2O3The method for preparing the mixed matrix forward osmosis membrane by blending modification 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:
mixing 0.6% (w/w) of MIL-68 (Al)/alpha-Fe2O3Adding into 65.4% (w/w) N, N-dimethylacetamide solvent, dispersing uniformly therein by using ultrasonic wave, adding into a three-neck round-bottom flask after the dispersion is completed, adding 8.0% (w/w) 1, 4-dioxane and 12.0% (w/w) cellulose acetate, and stirring uniformly. Adding 6.0% (w/w) of pore-forming agent lactic acid and 8.0% (w/w) of auxiliary pore-forming agent methanol into a three-neck round-bottom flask, stirring and dissolving at 60 ℃ for 8 hours to prepare the MIL-68 (Al)/alpha-Fe-based porous material2O3The mixed matrix forward osmosis membrane of (1) initial membrane casting solution; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 20 hours to remove air bubbles remaining in the casting solution. Spreading a 100-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 formed nascent-state membrane for 30 seconds at room temperature, immersing the nascent-state membrane into a constant-temperature coagulation bath water tank at 35 ℃ for coagulation forming, automatically separating the membrane from a glass plate, taking out the membrane, immersing the membrane in normal-temperature deionized water for 24 hours, and then carrying out heat treatment on the membrane for 15 minutes in deionized water at 50 ℃ to obtain the membrane based on MIL-68 (Al)/alpha-Fe2O3A mixed matrix forward osmosis membrane. The pure water flux of the prepared forward osmosis membrane is measured within 1 hour of test time by using 1M NaCl as a driving liquid and deionized water as a raw material liquidReach 61.9L/(m)2H) or more, reverse salt flux less than 2.85 g/(m)2·h)。
Example 2:
mixing MIL-68 (Al)/alpha-Fe2O3The contents of N, N-dimethylacetamide and N, N-dimethylacetamide solvents were adjusted to 0.2% (w/w) and 65.8% (w/w), respectively, and the rest was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 46.9L/(M) within 1 hour of test time2H) or more, reverse salt flux of less than 2.64 g/(m)2·h)。
Example 3:
mixing MIL-68 (Al)/alpha-Fe2O3The contents of N, N-dimethylacetamide and N, N-dimethylacetamide solvents were adjusted to 1.0% (w/w) and 65.0% (w/w), respectively, and the rest was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 41.3L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 2.57 g/(m)2·h)。
Example 4:
the 1, 4-dioxane in the additive was replaced with acetone, and the rest was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 56.2L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 2.77 g/(m)2·h)。
Example 5:
the lactic acid in the porogen was replaced with polyethylene glycol, the rest of the procedure was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: the pure water flux of the forward osmosis membrane is prepared by using 1M NaCl as a driving liquid and deionized water as a raw material liquid within the test time of 1 hourThe amount reaches 54.6L/(m)2H) or more, reverse salt flux of less than 2.71 g/(m)2·h)。
Example 6:
the temperature of the coagulation bath was adjusted from 35 ℃ to 50 ℃ in the same manner as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 49.9L/(M) within 1 hour of test time2H) or more, reverse salt flux of less than 2.45 g/(m)2·h)。
Example 7:
the stirring temperature was adjusted from 50 ℃ to 80 ℃ and the rest was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 53.9L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 2.38 g/(m)2·h)。
Example 8:
the heat treatment temperature was adjusted from 50 ℃ to 80 ℃ in the same manner as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 55.2L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 2.66 g/(m)2·h)。
Example 9:
the heat treatment time was adjusted from 15 minutes to 60 minutes, and the rest was the same as in example 1. Then the obtained product is based on MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane has the following properties: 1M NaCl 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 63.9L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 2.95 g/(m)2·h)。
Comparative example 1:
66.0% (w/w) of N, N-dimethylacetamide as an organic solvent was added to a three-necked round-bottomed flask, followed by 8.0% (w/w) of 1, 4-dioxane and 12.0% (w/w) of cellulose acetate, and the mixture was stirred to homogeneity. Adding 6.0% (w/w) of pore-forming agent lactic acid and 8.0% (w/w) of auxiliary pore-forming agent methanol into a three-neck round-bottom flask, stirring and dissolving at 60 ℃ for 8 hours until the pore-forming agent methanol is completely dissolved, and preparing an initial membrane casting solution of the cellulose acetate mixed matrix forward osmosis membrane; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 12 hours, and bubbles remaining in the casting solution were removed. Spreading a 100-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 formed nascent-state membrane for 30 seconds at room temperature, immersing the nascent-state membrane into a constant-temperature coagulation bath water tank at 35 ℃ for coagulation forming, automatically separating the membrane from a glass plate, taking out the membrane, immersing the membrane in normal-temperature deionized water for 24 hours, and then carrying out heat treatment on the membrane in the deionized water at 50 ℃ for 15 minutes to obtain the cellulose acetate mixed matrix forward osmosis membrane. 1M NaCl 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 45.4L/(M) within 1 hour of test time2H) or more, reverse salt flux less than 3.29 g/(m)2·h)。
Claims (10)
1. Metal organic framework compound MIL-68 (Al)/alpha-Fe2O3The mixed matrix forward osmosis membrane is characterized in that the membrane casting solution contains a metal organic framework compound MIL-68 (Al)/alpha-Fe2O3And affect the structure and performance of forward osmosis membranes; the casting solution consists of the following substances in percentage by mass: polymer film material 11.0-16.0% (w/w), 0.2-1.0% (w/w) MIL-68 (Al)/alpha-Fe2O32.0 to 10.0 percent (w/w) of additive, 2.0 to 10.0 percent (w/w) of pore-forming agent, 2.0 to 10.0 percent (w/w) of auxiliary pore-forming agent and 53.0 to 82.8 percent (w/w) of organic solvent.
2. The MIL-68(Al)/α -Fe-based of claim 12O3Mixed matrix forward osmosis membranes, characterised byThe method comprises the following steps: the forward osmosis membrane is prepared by adopting a traditional phase inversion method, namely a dry-wet method.
3. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the cellulose acetate is one or two of cellulose diacetate and cellulose triacetate.
4. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the additive is 1, 4-dioxane or acetone, and the content is 2.0-10.0% (w/w).
5. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the pore-foaming agent is lactic acid or polyethylene glycol, and the content is 2.0-10.0% (w/w).
6. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the auxiliary pore-foaming agent is methanol with the content of 2.0-10.0% (w/w).
7. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide, and the content is 53.0-82.8% (w/w).
8. The MIL-68(Al)/α -Fe-based of claim 12O3A mixed matrix forward osmosis membrane characterized by: the MIL-68 (Al)/alpha-Fe2O3The self-made metal organic framework compound is a porous polyhedral structure, and the content of the porous polyhedral structure is 0.2-1.0% (w/w).
9. Metal organic framework compound MIL-68 (Al)/alpha-Fe2O3A method for preparing a mixed matrix forward osmosis membrane, characterized in that it comprises:
(1) mixing a certain amount of MIL-68 (Al)/alpha-Fe2O3Adding the mixture into an organic solvent, fully and uniformly dispersing the mixture in the organic solvent by utilizing ultrasound, adding the mixture into a three-neck round-bottom flask after the dispersion is finished, adding a certain amount of additives and polymer film materials, and uniformly stirring;
(2) adding a certain amount of pore-forming agent and auxiliary pore-forming agent into a three-neck round-bottom flask, stirring and dissolving at 40-80 ℃ for 8-16 hours until the pore-forming agent and the auxiliary pore-forming agent are completely dissolved, and preparing the MIL-68 (Al)/alpha-Fe-based material2O3Mixing the initial membrane casting solution of the matrix forward osmosis membrane; standing the obtained casting solution at a stirring and dissolving temperature for 20-24 hours, 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-state membrane for 1-30 seconds at room temperature, immersing the nascent-state membrane into a constant-temperature solidification bath water tank at the temperature of 30-50 ℃ for solidification and forming, automatically separating the formed nascent-state membrane from a glass plate, taking out the nascent-state membrane, soaking the nascent-state membrane in normal-temperature deionized water for 20-48 hours, and then carrying out heat treatment on the nascent-state membrane in deionized water at the temperature of 40-80 ℃ for 5-60 minutes to obtain the nascent-state membrane based on MIL-68 (Al)/alpha-Fe2O3A mixed matrix forward osmosis membrane.
10. The MIL-68(Al)/α -Fe-based of claim 92O3The preparation method of the mixed matrix forward osmosis membrane is characterized by comprising the following steps: 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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