CN114618307A - Mixed matrix membrane for acid diffusion dialysis and preparation method and application thereof - Google Patents
Mixed matrix membrane for acid diffusion dialysis and preparation method and application thereof Download PDFInfo
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- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 46
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000009792 diffusion process Methods 0.000 title claims abstract description 37
- 238000000502 dialysis Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 21
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 5
- DJLHXXNSHHGFLB-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C(C)=C DJLHXXNSHHGFLB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract 11
- 238000003756 stirring Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000012621 metal-organic framework Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WPDXAMRGYMDTOV-UHFFFAOYSA-N 3-bromo-2-methylphenol Chemical compound CC1=C(O)C=CC=C1Br WPDXAMRGYMDTOV-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
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- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/243—Dialysis
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A mixed matrix membrane for acid type diffusion dialysis and a preparation method and application thereof are disclosed, wherein the method comprises the following steps: dissolving pyromellitic acid, 2-amino terephthalic acid and sodium hydroxide in water to form a solution A, dissolving zirconium oxychloride octahydrate and acetic acid in water to form a solution B, mixing the solutions A, B for reaction, washing and drying to prepare UiO-66- (COOH) taking Zr metal as the center2MOF nanoparticles; mixing dimethylamine ethyl methacrylate as a quaternization reagent with brominated polyphenyl ether for quaternization reaction to prepare a quaternization QPPO film matrix with the quaternization degree of 75 percent; mixing UiO-66- (COOH)2The MOF nanoparticles are dispersed in a solvent and stirredAnd mixing the membrane with a quaternized QPPO membrane matrix to obtain membrane liquid, coating the membrane liquid on a glass plate, and drying to obtain a mixed matrix membrane. The mixed matrix membrane prepared by the preparation method of the invention is used for H+/Fe2+The selective separation of the acid can obtain high selective separation performance under the condition of low filler amount, thereby greatly improving the recovery efficiency of the acid in the acid wastewater.
Description
Technical Field
The invention relates to the technical field of mixed matrix separation membranes, in particular to a mixed matrix membrane for acid diffusion dialysis and a preparation method and application thereof.
Background
A large amount of acidic waste water comes from metallurgy, printing and dyeing, chemical production, mineral resource exploitation and the like, and the acidic waste water is discharged into the environment, which poses serious threat to the health of human beings and animals. If the acid can be recovered from the acid waste liquid, the resources can be saved, and the effect of protecting the environment can be achieved. The emerging Diffusion Dialysis (DD) membrane separation technology driven by osmotic pressure has high selectivity on recovered acid, large and controllable effective area of the membrane, and generates no by-product in the acid recovery process, thereby not only saving the cost, but also being more environment-friendly.
However, ion transport of conventional anion exchange membranes for acid diffusion dialysis forms nanoscale interconnected water primarily by microphase separation of hydrophobic main chains and hydrophilic side chainsIt is difficult to improve both selectivity and permeability of the ion exchange membrane. Thus, how to increase H by constructing ion transport channels+/Fe2+Selective separation selectivity of (2), thereby producing a catalyst having a higher H+/Fe2+The selection of an acid recovery membrane having separation performance is an important subject of current research.
Disclosure of Invention
Therefore, the invention provides a mixed matrix membrane for acid type diffusion dialysis and a preparation method and application thereof, which aim to solve the technical problems in the prior art.
In order to achieve the aim, the invention provides a mixed matrix membrane for acid type diffusion dialysis, a preparation method and application thereof, wherein the mixed matrix membrane is prepared by using UiO-66- (COOH)2The MOF nano particles are used as fillers and are obtained by adding the fillers into a quaternized QPPO film matrix and then blending.
As a further preferred embodiment of the present invention, UiO-66- (COOH) in the mixed matrix membrane2The weight of the nano particles is 0.01-20 wt%.
According to another aspect of the present invention, there is also provided a method for producing a mixed matrix membrane for acid diffusion dialysis, characterized by comprising the steps of:
1) dissolving pyromellitic acid, 2-amino terephthalic acid and sodium hydroxide in water to form a solution A, dissolving zirconium oxychloride octahydrate and acetic acid in water to form a solution B, mixing the solutions A, B for reaction, washing and drying to prepare UiO-66- (COOH) taking Zr metal as the center2MOF nanoparticles;
2) mixing dimethylaminoethyl methacrylate as a quaternization reagent with brominated polyphenyl ether for quaternization reaction at the temperature of 35-45 ℃ to prepare a quaternization QPPO film matrix with the quaternization degree of 70-80%;
3) mixing UiO-66- (COOH)2And dispersing the MOF nano particles in a solvent, mixing the MOF nano particles with a quaternized QPPO membrane matrix under a stirring condition to obtain membrane liquid, coating the membrane liquid on a glass plate, and drying to obtain the mixed matrix membrane for acid diffusion dialysis.
In a further preferred embodiment of the present invention, in step 1), a mixture of pyromellitic acid and 2-aminoterephthalic acid is used as an organic ligand, the molar amount of pyromellitic acid is 0 to 80% of the total amount of organic ligands, and the molar ratio of the organic ligand to the zirconium oxychloride octahydrate is 1: 1.
as a further preferred technical solution of the present invention, the step 1) specifically comprises: dissolving pyromellitic acid, 2-amino terephthalic acid and sodium hydroxide in water at the temperature of 30-60 ℃ for 5-15 min to form a solution A; dissolving zirconium oxychloride octahydrate and acetic acid in water at the temperature of 45-60 ℃ for 1-2.5 hours to form a solution B; mixing the solutions A, B for reaction at 70-80 ℃ for 9-12 h, washing and drying to obtain UiO-66- (COOH) with Zr metal as the center2MOF nanoparticles.
As a further preferable technical solution of the present invention, the step 2) specifically includes: firstly, dissolving brominated polyphenyl ether by using N-methyl pyrrolidone at normal temperature, then adding dimethylamine ethyl methacrylate for quaternization reaction, wherein the quaternization temperature is 40 ℃, the time is 24 hours, and the quaternization degree is 75%, so as to prepare the quaternization QPPO film matrix.
In a further preferred embodiment of the present invention, in step 3), N-methylpyrrolidone is used as a solvent.
As a further preferable technical solution of the present invention, the step 3) specifically includes: mixing UiO-66- (COOH)2Dispersing the MOF nanoparticles in N-methylpyrrolidone by ultrasound for 1.5-2 h; stirring the dispersed UiO-66- (COOH)2Adding the MOF nano particles into a quaternized QPPO membrane matrix at normal temperature, and stirring for 10-12 h to obtain a membrane liquid; and coating the membrane liquid on a glass plate by a tape casting method, and drying at 60-80 ℃ to finally obtain the mixed matrix membrane.
As a further preferred embodiment of the present invention, in step 3), UiO-66- (COOH) is controlled2The addition amount of the MOF nano particles can prepare mixed matrix membranes with different MOF loading amounts, wherein UiO-66- (COOH)2The addition amount of the MOF nano-particles is 0.01-20 wt%。
According to another aspect of the invention, the invention also provides application of the mixed matrix membrane for acid type diffusion dialysis, which is characterized in that the mixed matrix membrane is applied to acid waste liquid for acid recovery treatment by utilizing the principle of acid type diffusion dialysis.
The mixed matrix membrane for acid diffusion dialysis and the preparation method and the application thereof can achieve the following beneficial effects by adopting the technical scheme:
1) in the preparation method, water is used as a solvent, and a green chemical synthesis method is used for successfully synthesizing UiO-66- (COOH)2The MOF nano particles obviously reduce the harm of the synthetic process to the environment, simultaneously reduce the economic cost and improve the economic benefit;
2) the preparation method of the invention has simple process of constructing the mixed matrix membrane by the blending method and high repeatability;
3) the mixed matrix membrane prepared by the preparation method of the invention is used for H+/Fe2+The selective separation of the acid can obtain high selective separation performance under the condition of low filler amount, thereby greatly improving the recovery efficiency of the acid in the acid wastewater.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows UiO-66- (COOH) synthesized in example 1 of the present invention2XRD patterns of MOF nanoparticles;
FIG. 2 is a SEM cross-sectional morphology characterization of the products prepared in examples 1-4 of the present invention and comparative example 1;
FIG. 3 is IEC performance test data for products prepared in examples 1-4 of the present invention and comparative example 1;
FIG. 4 is data of the separation performance test of the products prepared in examples 1 to 4 of the present invention and comparative example 1.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
The invention provides a mixed matrix membrane for acid diffusion dialysis, which passes through UiO-66- (COOH)2The MOF nano-particles are blended with a quaternized QPPO film matrix, and UiO-66- (COOH) is added into the mixed matrix film2The mass fraction of the nano particles is 0.01-20 wt%.
The mixed matrix membrane has a high H content+/Fe2+Selecting separation performance to load Metal Organic Framework (MOF) material on quaternary QPPO membrane matrix, wherein the metal organic framework is UiO-66- (COOH)2Nanoparticles having the following characteristics: uniform controllable nanochannels on the order of angstroms; a rigid structure having permanent pores; the surface has abundant functional groups and is easy to functionalize.
In order to make those skilled in the art further understand the technical solution of the present invention, the technical solution of the present invention is further described in detail by the following specific embodiments.
Example 1
The preparation method of the mixed matrix membrane for acid diffusion dialysis in this example is specifically as follows:
(1)UiO-66-(COOH)2preparation of MOF nanoparticles: weighing 0.322g (1mmol) of zirconium oxychloride octahydrate in a 20mL glass bottle, adding 3mL of deionized water to completely dissolve the zirconium oxychloride, then adding 1.23mL of glacial acetic acid, and heating and stirring at 60 ℃ for 2h to form a precursor metal central ion solution; weighing 0.091g (0.5mmol) of 2-aminoterephthalic acid and 0.127g (0.5mmol) of pyromellitic acid in a 20mL glass bottle, adding 5mL of deionized water, then adding 0.12g (3mmol) of sodium hydroxide, heating and stirring at 60 ℃ for 10min to completely dissolve the mixture to form a brownish red ligand solution, and cooling to room temperature for later use; finally adding the ligand solution into the metal central ion solution to form yellow solid immediately, heating and stirring the mixture at 80 DEG C12 h; centrifuging and washing with deionized water and ethanol at 8000rpm for 3 times to remove unreacted substances, and collecting the obtained UiO-66- (COOH)2Drying the crystals in a high-temperature drying oven at 80 deg.C for 12h to obtain UiO-66- (COOH) as light yellow solid powder2MOF nanoparticles.
(2) Preparation of quaternized QPPO membrane matrix: firstly, weighing 10g of brominated polyphenylene oxide (BPPO) in a 100mL container, adding 35mL of N-methylpyrrolidone (NMP) into the BPPO to fully dissolve the BPPO into an orange yellow transparent solution; 3.467g of dimethylamine ethyl methacrylate is weighed and dropwise added into the brominated polyphenylene ether solution to carry out quaternization reaction, and the solution is heated and stirred for 24 hours at 40 ℃ to form a brownish yellow quaternized brominated polyphenylene ether (QPPO) film matrix, namely the quaternized QPPO film matrix.
(3) Preparation of mixed matrix membrane: the quaternized QPPO film matrix was weighed 4.95g, 3.5mL of N-methylpyrrolidone (NMP) was measured, and 0.067g of UiO-66- (COOH) was added2Adding MOF nanoparticles into the matrix of QPPO film, stirring for 12 hr, coating the obtained film solution on 6 × 10cm glass plate by casting, transferring to a heating table, and drying at 80 deg.C for 6 hr to obtain UiO-66- (COOH)2The MOF nano-particle added amount is 5 wt% of the mixed matrix membrane, also called UiO-66- (COOH)2/QPPO mixed matrix membrane (hereinafter referred to as membrane in the test).
The obtained film is taken down and soaked in deionized water for standby application to be tested, and the specific performance test is as follows:
(1) ion Exchange Capacity (IEC) test: the ion exchange capacity is expressed in terms of the number of exchange groups per gram of dry film (mmol/g). A sample of the membrane having a size of 4X 4cm was immersed in a 1mol/L NaCl solution for 24 hours according to the Mohr method to make H in the membrane+Is Na in the solution+And completely exchanging out. Then soaking the membrane in deionized water, replacing fresh deionized water every 2h, repeating the process for more than 10 times to completely clean NaCl solution remained on the surface of the membrane to obtain a chlorine QPPO membrane, drying the membrane at 80 ℃ to constant weight, recording the mass of the dry membrane at the moment, and recording as Wdry. Then the film was placed in a volume of 100mL of 0.5mol/L Na2SO4Soaking in the solution for 8h to remove C in the membranel-Is completely released. With K2CrO40.1mol/L AgNO as indicator3Titrating the solution as a titrant, wherein the titration end point is the brick red color converted from the white turbidity, and recording the consumed AgNO3Volume of solution, noted as VAgNO3. The calculation method of IEC is as follows:
(2) ion separation performance test: the diffusion dialysis device consists of two compartments and an ion exchange membrane, wherein the anion exchange membrane is fixed between the two compartments and divides the compartments into a feeding chamber and a diffusion chamber. The effective area of the ion exchange membrane is 4.9cm2. Firstly, soaking the membrane in simulated waste acid liquor (feed liquor: 1 mol. L)-1HCl and 0.2 mol. L-1FeCl2) The pretreatment is carried out for 12h, and then the surface of the product is sufficiently cleaned by deionized water before beginning diffusion dialysis so as to remove residual acid on the surface. During the experiment, 40mL of the feed solution and 40mL of deionized water were injected into the feed chamber and the diffusion chamber, respectively, and magnetons were placed on both sides of the chamber for uniform and vigorous stirring to eliminate concentration polarization. The diffusion dialysis test was performed for 1h at a temperature of 25 ℃ on each membrane. Then using 0.01 mol.L-1The NaOH solution takes methyl red and bromocresol green as a mixed indicator (V)Methyl Red:VBromocresol green1:3) titration H+The concentration of (3) is the titration end point when the solution changes from red to blue-green. Simultaneous determination of Fe by inductively coupled plasma mass spectrometer (ICP)2+The concentration of (2). HCl and FeCl2The diffusion coefficient (U) of (a) can be calculated using the following equation:
in the formula, M represents a single component (HCl or FeCl)2) The molar amount of diffusion, S, represents the effective membrane area, and t represents the diffusion time. Δ C represents the log mean of the concentration difference between the two chambers and is defined by the following formula:
in the formula (I), the compound is shown in the specification,
and
the individual components (HCl or FeCl) in the feed at times 0 and t, respectively2) The concentration of (2).
Represents the individual components (HCl or FeCl) of the dialysate at time t2) The concentration of (c).
HCl(UHCl) And FeCl2(UFeCl2) The separation factor (S) is the ratio of diffusion coefficients of (a):
through the above tests, the performance parameters of the mixed matrix membrane obtained in this example are: ion exchange capacity 1.69mmol/g, H+Dialysis coefficient (U)H +) Is 0.0104 m.h-1Coefficient of separation (S)H+/Fe 2+) Is 254.
Example 2
The method of preparing the mixed matrix film and the performance test in this example were the same as those in example 1 except that UiO-66- (COOH) was added to the film2The mass of the MOF nanoparticles was 0.094g, resulting in a membrane with a 7 wt% filler amount.
The performance parameters of the mixed matrix membrane obtained in this example were tested as follows: ion exchange capacity of 1.65mmol/g, H+Dialysis coefficient (U)H +) Is 0.0084 m.h-1Coefficient of separation (S)H+/Fe 2+) Is 492.
Example 3
Mixing base in this examplePreparation method and Performance test of the plasma Membrane were the same as example 1 except that UiO-66- (COOH) was added in this example2The mass of the MOF nanoparticles was 0.135g, resulting in a membrane with a 10 wt% filler amount.
The performance parameters of the mixed matrix membrane obtained in this example were tested as follows: ion exchange capacity 1.618mmol/g, H+Dialysis coefficient (U)H +) Is 0.0083 m.h-1Coefficient of separation (S)H+/Fe 2+) 539.
Example 4
The method of preparing the mixed matrix film and the performance test in this example were the same as those in example 1 except that UiO-66- (COOH) was added to the film2The mass of the MOF nanoparticles was 0.269g, resulting in a film with a 20 wt% filler content.
The performance parameters of the mixed matrix membrane obtained in this example were tested as follows: ion exchange capacity 1.47mmol/g, H+Dialysis coefficient (U)H +) Is 0.0064 m.h-1Coefficient of separation (S)H+/Fe 2+) Is 399.
Comparative example 1
This comparative example was conducted in the same manner as example 1 except that UiO-66- (COOH) in comparative example 1 was used2The addition amount of MOF nanoparticles was 0 wt%, resulting in a blank QPPO membrane.
The performance parameters of the blank QPPO membrane obtained for this ratio were tested to be: ion exchange capacity 1.76mmol/g, H+Dialysis coefficient (U)H +) Is 0.0111 m.h-1Coefficient of separation (S)H+/Fe 2+) Is 0.
FIG. 1 shows UiO-66- (COOH) prepared in example 1 of the present invention2XRD pattern of MOF nanoparticles, synthetic UiO-66- (COOH) can be seen2The MOF nanoparticles showed clear and intense diffraction peaks at the 6 positions 2 θ ═ 7.4 °, 8.5 °, 14.8 °, 17.1 °, 25.8 ° and 30.8 °, respectively, corresponding to the (111), (200), (222), (400), (442) and (711) crystal planes. And no visible peak shift compared to the XRD of standard UiO-66, confirming that UiO-66- (COOH)2MOF nanoparticles have a highly crystalline structure.
FIG. 2 is a SEM cross-sectional topographical representation of the products of each of examples 1-4 of the present invention and comparative example 1, wherein the products were prepared according to UiO-66- (COOH)2The amount of the filler of the MOF nanoparticles varies, and a to e in fig. 2 correspond to 0 wt% to 20 wt% of the filler in sequence. When the amount of the filler is 5% by weight or 7% by weight, UiO-66- (COOH)2The MOF nano-particles are dispersed uniformly in the membrane, the cross section structure of the membrane is uniform and continuous, and no obvious membrane gap exists. While 10 wt% of UiO-66- (COOH) is added2After MOF nano particles, the cross section roughness of the mixed matrix membrane is slightly increased, and MOF is slightly agglomerated. With UiO-66- (COOH)2When the addition amount of the MOF nano particles reaches 20 wt%, the MOF is obviously agglomerated inside the membrane, and the SEM shows that the cross section of the membrane is honeycomb-shaped.
FIG. 3 is an IEC performance test of the products prepared in each of examples 1-4 and comparative example 1: as can be seen from FIG. 3, the IEC value of the blank QPPO membrane was 1.759mmol/g, and the IEC value of the mixed matrix membrane gradually decreased with the increase in the amount of the filler, as compared with the blank QPPO membrane.
FIG. 4 is a further test of the separation performance of the products prepared in each of examples 1-4 and comparative example 1: with UiO-66- (COOH)2The increase of the filler amount of the MOF nanoparticles, which is 10 wt%, leads to a gradual increase of the separation coefficient, H+/Fe2+Up to 565.
From the above, example 3 is the best mode of the present invention.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. A mixed matrix membrane for acid diffusion dialysis, characterized in that the mixed matrix membrane is prepared by reacting UiO-66- (COOH)2The MOF nano-particles are used as fillers and are added into a quaternized QPPO film matrixMixing to obtain the final product.
2. The mixed matrix membrane for acid diffusion dialysis as claimed in claim 2, wherein UiO-66- (COOH) in the mixed matrix membrane2The addition amount of the nano particles is 0.01-20 wt%.
3. A method for preparing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 1 or 2, characterized by comprising the steps of:
1) dissolving pyromellitic acid, 2-amino terephthalic acid and sodium hydroxide in water to form a solution A, dissolving zirconium oxychloride octahydrate and acetic acid in water to form a solution B, mixing the solutions A, B for reaction, washing and drying to prepare UiO-66- (COOH) taking Zr metal as the center2MOF nanoparticles;
2) mixing dimethylaminoethyl methacrylate as a quaternization reagent with brominated polyphenyl ether for quaternization reaction at the temperature of 35-45 ℃ to prepare a quaternization QPPO film matrix with the quaternization degree of 70-80%;
3) mixing UiO-66- (COOH)2And dispersing the MOF nano particles in a solvent, mixing the MOF nano particles with a quaternized QPPO membrane matrix under a stirring condition to obtain membrane liquid, coating the membrane liquid on a glass plate, and drying to obtain the mixed matrix membrane for acid diffusion dialysis.
4. The method for preparing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 3, wherein in step 1), a mixture of pyromellitic acid and 2-aminoterephthalic acid is used as the organic ligand, the molar amount of pyromellitic acid is 0 to 80 percent of the total amount of the organic ligand, and the molar ratio of the organic ligand to the zirconium oxychloride octahydrate is 1: 1.
5. the method for producing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 4, wherein the step 1) specifically comprises: dissolving pyromellitic acid, 2-amino terephthalic acid and sodium hydroxide in water at the temperature of 30-60 ℃ for 5-15 min to form a solution A;dissolving zirconium oxychloride octahydrate and acetic acid in water at the temperature of 45-60 ℃ for 1-2.5 hours to form a solution B; mixing the solutions A, B for reaction at 70-80 ℃ for 9-12 h, washing and drying to obtain UiO-66- (COOH) with Zr metal as the center2MOF nanoparticles.
6. The method for producing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 3, wherein the step 2) specifically comprises: firstly, dissolving brominated polyphenyl ether by using N-methyl pyrrolidone at normal temperature, then adding dimethylamine ethyl methacrylate for quaternization reaction, wherein the quaternization temperature is 40 ℃, the time is 24 hours, and the quaternization degree is 75%, so as to prepare the quaternization QPPO film matrix.
7. The method for producing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 6, wherein in step 3), N-methylpyrrolidone is used as a solvent.
8. The method for preparing a mixed matrix membrane for acid diffusion dialysis as claimed in claim 7, wherein step 3) specifically comprises: mixing UiO-66- (COOH)2Dispersing the MOF nanoparticles in N-methyl pyrrolidone by ultrasonic for 1.5-2 h; stirring the dispersed UiO-66- (COOH)2Adding the MOF nano particles into a quaternized QPPO membrane matrix at normal temperature, and stirring for 10-12 h to obtain a membrane liquid; and coating the film liquid on a glass plate by a tape casting method, and drying at 60-80 ℃ to finally obtain the mixed matrix film for acid diffusion dialysis.
9. The method for producing a mixed matrix membrane for acid diffusion dialysis as claimed in any one of claims 3 to 8, wherein in step 3), by controlling UiO-66- (COOH)2The addition amount of the MOF nano particles can prepare mixed matrix membranes with different MOF loading amounts, wherein UiO-66- (COOH)2The addition amount of the MOF nanoparticles is 0.01-20 wt%.
10. The use of the mixed matrix membrane for acid diffusion dialysis as claimed in claim 1 or 2, wherein the mixed matrix membrane is applied to an acidic waste liquid by the principle of acid diffusion dialysis to recover an acid.
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| CN102698616A (en) * | 2012-06-21 | 2012-10-03 | 盐城师范学院 | Preparation method of BPPO and PVA-based organic-inorganic hybrid anion exchange membrane |
| CN106380614A (en) * | 2016-09-05 | 2017-02-08 | 复旦大学 | Functionalized metal-organic framework synergistically modified polymer hybrid proton exchange membrane and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102698616A (en) * | 2012-06-21 | 2012-10-03 | 盐城师范学院 | Preparation method of BPPO and PVA-based organic-inorganic hybrid anion exchange membrane |
| CN106380614A (en) * | 2016-09-05 | 2017-02-08 | 复旦大学 | Functionalized metal-organic framework synergistically modified polymer hybrid proton exchange membrane and production method thereof |
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