CN115722213A - Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater - Google Patents
Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater Download PDFInfo
- Publication number
- CN115722213A CN115722213A CN202211510769.9A CN202211510769A CN115722213A CN 115722213 A CN115722213 A CN 115722213A CN 202211510769 A CN202211510769 A CN 202211510769A CN 115722213 A CN115722213 A CN 115722213A
- Authority
- CN
- China
- Prior art keywords
- organic phosphorus
- organic
- amino
- mofs material
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000011574 phosphorus Substances 0.000 title claims abstract description 131
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000013183 functionalized metal-organic framework Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 title claims description 11
- 239000010865 sewage Substances 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 46
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 10
- 239000012498 ultrapure water Substances 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000002779 inactivation Effects 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000003754 zirconium Chemical class 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- -1 pentamethylene methylene Chemical group 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 229940120146 EDTMP Drugs 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract 1
- 230000002860 competitive effect Effects 0.000 abstract 1
- 239000011975 tartaric acid Substances 0.000 abstract 1
- 235000002906 tartaric acid Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 235000011007 phosphoric acid Nutrition 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000003016 phosphoric acids Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000004021 humic acid Substances 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000013356 anionic metal-organic framework Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses an amino-functionalized MOFs material, a preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewaterThe application method for removing the organic phosphorus in the sewage comprises the following steps: adjusting the pH value of the water body containing the organic phosphorus, and enabling the water body to pass through an adsorption column filled with MOFs materials; and after adsorption inactivation, soaking the filling material by using alkali liquor, then washing the filling material to be neutral by using ultrapure water, then washing and soaking the filling material by using acid liquor to carry out activation regeneration, washing the filling material by using the ultrapure water to be neutral, and drying the filling material at a low temperature. The invention uses amino-functionalized MOFs material to treat different organic phosphorus, when the pH value of water is 5.0 +/-0.1, and high-concentration SO coexists 4 2‑ Under the condition of competitive substances such as citric acid, tartaric acid, organic matters and the like, the content of organic phosphorus in the effluent can be reduced from 1mg/L to below 0.02 mg/L (counted by P), and no metal zirconium is detected in the effluent.
Description
Technical Field
The invention belongs to the technical field of phosphorus-polluted water body remediation, and particularly relates to an amino-functionalized MOFs material, a preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater.
Background
Phosphorus is a limiting nutrient element of primary productivity of aquatic ecosystems, and its background value in natural water is low, but various forms of phosphorus are input into water as population grows and industrialization progresses. Among various input sources, the large-scale discharge of sewage and wastewater is the main source of phosphorus in water, such as some artificially synthesized functional phosphorus compounds added in the production process. Excessive phosphorus discharge can cause eutrophication of water bodies and other water quality problems, thereby causing serious threats to human health and ecological safety. Removal of phosphorus from wastewater by a wastewater treatment plant (WWTP) is an effective way to alleviate such environmental problems. Currently, the global limits of phosphorus emissions are gradually decreasing. For example, some areas of Europe specify total phosphorus emissions as low as 50 μ g/L; the U.S. environmental protection agency stipulates that the phosphorus content in WWTP effluent should be less than 0.1 mg/L. This requires WWTPs to have higher phosphorus removal capacity to meet increasingly stringent phosphorus emission standards.
Phosphorus has various forms and properties in water, and is classified into two major classes, inorganic phosphorus and organic phosphorus, according to chemical bond characteristics. In recent years, the commonly used phosphorus removal methods for WWTPs mainly include biological methods, chemical precipitation methods and the like. Biological phosphorus removal depends on excessive absorption of phosphorus in water by phosphorus accumulating bacteria in an anaerobic-aerobic environment and storage of the phosphorus in the form of polyphosphate in cells, and phosphorus is removed from sewage by discharging excess sludge; the chemical phosphorus removal is to add multivalent metal salt and inorganic phosphorus to form metal phosphate precipitate, and then remove the phosphorus through solid-liquid separation. Generally, these conventional phosphorus removal methods focus on removing inorganic phosphorus such as orthophosphate, but have poor effect on removing organic phosphorus. It has been reported that Dissolved Organic Phosphorus (DOP) accounts for 26-81% of dissolved Total phosphorus (TDP) in WWTP effluent from Boston, USA where both biological and chemical phosphorus removal processes are used (Science of the Total environmental 2015, 511, 47-53); furthermore, liu et al studied the removal effect of different phosphorus components by WWTP treatment processes, and the results showed that DOP removal rate by biological treatment was relatively low, DOP was hardly removed by chemical precipitation dephosphorization, and the ratio of organic phosphorus in total phosphorus gradually increased during Water treatment (Water Science and Technology 2011, 63 (4), 804-810). Therefore, the removal efficiency of phosphorus depends on the morphological composition of phosphorus in the wastewater effluent, and the removal of organic phosphorus must be a concern to achieve lower concentrations of total phosphorus emissions. Therefore, scientists have developed various methods for enhancing the removal of organic phosphorus, such as photocatalytic oxidation, ozone oxidation, microfiltration, ultrafiltration and the like, but the methods are not widely applied to WWTPs, so that various forms of organic phosphorus are discharged into water environment along with the effluent of sewage treatment plants (WWTPs), and become important contributors to eutrophication of water bodies, and part of the organic phosphorus can even be used as a micro-pollutant to cause health risks of ecosystems and human beings. Therefore, the development of the deep purification technology of the organic phosphorus in the sewage and the wastewater has fundamental significance.
The adsorption method for removing the organic phosphorus has the advantages of high speed and efficiency, simple process, convenient operation and the like, and the adsorbed organic phosphorus can be desorbed and recovered through ion exchange, thereby retaining potential economic value. At present, researches on phosphorus removal by an adsorption method at home and abroad mainly focus on modifying a porous material to improve the adsorption performance on organic phosphorus. The common adsorbing materials include natural adsorbents (such as slag, fly ash, zeolite, sepiolite and the like) and synthetic adsorbents (such as activated carbon, metal oxide and salt modified materials thereof and the like), but the traditional adsorbing materials have the adsorbing capacity to organic phosphorusThe ideal level is difficult to achieve, and the energy absorption performance is easily interfered by coexisting matrixes (such as natural organic matters, sulfate radicals, micromolecular carboxylic acid and the like), so that the efficiency of selectively adsorbing organic phosphorus is poor. Metal-Organic Frameworks (MOFs) are a class of porous crystalline materials with periodic multidimensional network structures formed by self-assembly of Metal ions or Metal cluster units and Organic ligands through coordination. The highly developed pore structure and the ultrahigh specific surface area of the MOFs material provide rich active sites, and trace toxic and harmful pollutants in water can be effectively removed. Hitherto, MOFs materials are mostly used for adsorption removal of dyes, heavy metal ions and inorganic phosphorus, for example, cationic MOFs developed by Fang et al (inorg. Chem., 2010) can effectively remove cationic pollutants (Hg) in water 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ Etc.); anionic MOFs developed by Fei et al (J. Am. Chem. Soc., 2011) can effectively adsorb and remove anionic pollutants (ClO) in water body 4 - 、MnO 4 - 、NO 3 - 、ReO 4 - Etc.). Chinese patent application No. CN104707569A discloses a MOFs material for adsorbing phosphate radical ions, and the patent relates to several protected MOFs materials (ZIF-8, MOF-5, MIL-125, fe-MIL-101, cu-MOF, al-MOF, cr-MOF) which have large specific surface area, high adsorption capacity and high phosphate radical ion removal efficiency. However, no article or patent for removing organic phosphorus from the MOFs material exists at present, and the patent successfully performs functional modification on the MOFs material and innovatively applies the functional modification to the organic phosphorus in a water body. In addition, the process also has the advantages of low equipment installation and maintenance cost and the like. The material of the invention can be used for smoothly treating the water body only by adding the material into a stirring tank with a water inlet and a water outlet and a feeder, and the maintenance cost is low because no equipment is required to be installed.
Disclosure of Invention
Aiming at the current application situation of the MOFs material in the phosphorus pollution control, the invention aims to provide an amino-functionalized MOFs material, a preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater, and further discloses a method for removing organic phosphorus in sewage and wastewater by adsorption by using the amino-functionalized MOFs material, so as to solve the problems in the technology of treating water bodies polluted by organic phosphorus.
The preparation method of the amino-functionalized MOFs material comprises the following steps of:
1) Mixing and dissolving zirconium salt and 2-amino terephthalic acid in an organic solvent according to a molar ratio of 1.5 to 1.5, adding hydrochloric acid as a regulator, performing ultrasonic treatment until the zirconium salt and the 2-amino terephthalic acid are completely dissolved, placing the mixture into a closed reaction kettle, and then transferring the reaction kettle into an oven to react for 20-30 hours at 100-150 ℃;
2) And step 1) after the reaction is finished, carrying out centrifugal filtration on the reaction liquid to obtain a solid product, and washing and drying to obtain the amino functionalized MOFs material.
The preparation method of the amino-functionalized MOFs material is characterized in that in the step 1), the dissolving concentrations of zirconium salt and 2-amino terephthalic acid in an organic solvent are respectively 12-15mM, and the molar ratio of the zirconium salt to the 2-amino terephthalic acid is 1.
The preparation method of the amino-functionalized MOFs material is characterized in that in the step 1), zirconium salt is zirconium chloride, and an organic solvent is DMF.
The amino-functionalized MOFs material provided by the invention can be well applied to deep removal of organic phosphorus in sewage and wastewater, and the application method comprises the following steps:
s1: adjusting the pH value of the water body containing the organic phosphorus to 5.0 +/-0.1;
s2: filling the amino functionalized MOFs material into an adsorption column, and then introducing the organic phosphorus-containing water body with the pH adjusted in the step S1 into the adsorption column;
s3: and (3) after the adsorption inactivation in the step (S2), disassembling the MOFs material in the adsorption column, soaking the MOFs material in alkali liquor, washing the MOFs material to be neutral by using ultrapure water, soaking the MOFs material in acid liquor for activation regeneration, washing the MOFs material to be neutral by using the ultrapure water, drying the MOFs material, namely completing the activation regeneration, and then repeatedly applying the MOFs material in the step (S2).
Further, in the step S1, the organic phosphorus is one or two of organic phosphoric acid and organic phosphate, the organic phosphoric acid is at least one of 2-phosphoric acid-1, 2, 4-butane tricarboxylate, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, 1, 6-hexamethylene diamine tetramethylene phosphonic acid, and diethylenetriamine pentamethylene methylene phosphonic acid, and the organic phosphate includes dibutyl phosphate.
Further, in the step S3, the alkali liquor is 5 to 20mmol/L sodium hydroxide solution, and the washing and soaking time is 20 to 40min; the acid solution is a hydrochloric acid solution of 5 to 20mmol/L, and the washing and soaking time is 20 to 40min.
Furthermore, the concentration of the organic phosphorus-containing water body in terms of P is less than 5mg/L, preferably less than 1mg/mL, and the flow rate of the organic phosphorus-containing water body passing through the MOFs material bed layer with amino functionalized in the adsorption column is 0.5-2BV/h, preferably 1BV/h. When the concentration of the effluent P is more than 0.01 mg/L, the adsorption inactivation is recorded.
Compared with the prior art, the invention has the following beneficial effects:
(1) The MOFs material has low production cost and wide sources;
(2) The MOFs material has large specific surface area and high adsorption capacity, and has high removal rate of low-content organic phosphorus in water, which can reach more than 90%, so that the efficiency of the whole device is greatly improved;
(3) The material of the invention can be used for smoothly treating the water body only by adding the material into a stirring tank with a water inlet and a water outlet and a charging machine, and the maintenance cost is low because no equipment is required to be installed;
(4) The material adopted by the method has no phosphorus resolving phenomenon, and no metal zirconium is dissolved out, so that secondary treatment and secondary pollution are avoided, and the method has good economic benefit and social benefit.
Drawings
FIG. 1 shows Uio-66 and NH 2 Comparison of adsorption Effect of HCL-Uio-66 on six organic phosphoric acids, the left graph is Uio-66, and the right graph is NH 2 -HCL-Uio-66；
FIG. 2 shows NH at different pH 2 -zirconium ion elution diagram of HCL-Uio-66.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
First, it should be noted that Uio-66 refers to a MOFs material with Zr as the metal center and terephthalic acid as the organic ligand, NH 2 -HCl-Uio-66 refers to amino-functionalized Uio-66 after adjustment with hydrochloric acid.
Blank example 1:
an amino-functionalized MOFs material is prepared by the following specific steps:
1) Uniformly mixing 13mmol of zirconium chloride and 13mmol of amino terephthalic acid, dissolving in 160mL of DMF, adding 6% by volume of hydrochloric acid as a regulator (the hydrochloric acid is added to improve the solubility of the zirconium chloride and accelerate the connection among metal clusters), performing ultrasonic treatment until the zirconium chloride and the amino terephthalic acid are completely dissolved, placing the mixture into a reaction kettle, and placing the reaction kettle into an oven to react for 24 hours at 120 ℃;
2) Centrifuging and filtering the reacted suspension in a centrifuge to obtain a product, alternately cleaning the product with DMF and methanol for 3 times, centrifuging and collecting the product after cleaning, putting the product in a vacuum drying oven, and drying the product in vacuum at the temperature of 80 ℃ to obtain the material, wherein the material is marked as NH 2 -HCl-Uio-66; wherein the centrifugal speed of the centrifugal machine is 7000-10000rpm, and the centrifugal time is 3-5min. The specific surface area of the MOFs material prepared in blank example 1 is about 1400 m 2 /g。
The MOFs mentioned in the following examples 1-22 were amino-functionalized MOFs prepared in blank example 1.
Blank example 2:
a process for the preparation of MOFs material by repeating the blank 1 except that the amino terephthalic acid is replaced by an equimolar amount of terephthalic acid, the final material obtained is designated as Uio-66.
Example 1
A treatment method for removing common organic phosphorus in water by using amino functionalized MOFs materials comprises the following specific steps:
1) Adjusting pH = 5.0 + -0.1 for aqueous solutions of six organic phosphoric acids (PBTC, HEDP, NTMP, EDTMP, HDTMP, DTPMP), each organic phosphoric acidThe concentration of the aqueous solution was 1mg/L (in terms of P) and the volume of the solution was 100 mL, and 0.05 g of HCl-NH was added to each solution 2 -Uio-66 was added to each aqueous solution of organic phosphoric acid and shaken in a constant temperature shaker at 25 ℃.
2) The organic P concentration in the solution was measured after 0.45 μm filter membrane was used to take the solution at each time point of 0.5h, 1h, 1.5h, 2h, 4h, 6h, 9h, 12h and 24h with a syringe. According to the experimental result, the removal rate of six organophosphorus in the solution after 0.5h of reaction is more than 90 percent (calculated by P), and the organophosphorus is not desorbed later.
3) Performing solid-liquid separation on the MOFs material and the solution after adsorption of each organic phosphoric acid aqueous solution, washing and soaking the MOFs material and the solution for 30min by using 0.01mol/L NaOH solution, then washing the MOFs material and the solution to be neutral by using ultrapure water, and washing and soaking the MOFs material and the solution for 30min by using 0.01mol/L HCl solution for activation and regeneration; and (3) cleaning the regenerated MOFs material by using ultrapure water until no organic phosphorus appears in the solution, wherein the pH value of the solution is nearly neutral, and performing solid-liquid separation and then vacuum drying on the composite material at room temperature.
4) And (3) repeating the steps (1) and (2) on the regenerated MOFs material, wherein the removal rate of six organic phosphorus in the solution after the reaction is more than 80% (calculated as P).
Operating procedure according to example 1, NH 2 The adsorption effect of HCl-Uio-66 on six organic phosphoric acids at different times is summarized in FIG. 1 (see the right panel of FIG. 1). It can be seen that NH 2 The adsorption effect of HCl-Uio-66 on the six organic phosphoric acids was stabilized in about 0.5 h.
Examples 1 to 1
The procedure of example 1 was repeated except that NH was added 2 -HCl-Uio-66 was replaced with Uio-66 of equal mass, with the final experimental results: the adsorption effect of Uio-66 on six organophosphates at different times is summarized in FIG. 1 (see left panel of FIG. 1). It can be seen that the adsorption effect of Uio-66 on six organophosphoric acids was stable for about 1 h.
Examples 1 to 2
The procedure of example 1 was repeated except that the pH of the aqueous solution of organophosphoric acid (PBTC) was adjusted to 3, 5, 7, 9 or 11 and the amount of zirconium ion eluted in the solution 0.5h after the reaction was summarized in FIG. 2.
Example 2
The same method as that of example 1 is adopted to treat the organic phosphorus in the water body, and the difference is that: each organic phosphoric acid aqueous solution is added with potassium sodium tartrate with the final concentration of 10 mmol/L which is approximately equal to 0.289 g/L. The experimental results are as follows: the removal rate of six organic phosphorus in the solution after reaction is more than 80 percent.
Example 3
The same method as that of example 1 is adopted to treat organic phosphorus in the water body, and the difference lies in that: sodium sulfate was added to each of the aqueous solutions of organic phosphoric acid to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of six organic phosphorus in the solution after reaction is more than 80 percent.
Example 4
The same method as that of example 1 is adopted to treat organic phosphorus in the water body, and the difference lies in that: each aqueous solution of organic phosphoric acid was added to a final concentration of 10 mmol/L trisodium citrate. The experimental results are as follows: the removal rate of six organic phosphorus in the solution after reaction is more than 80 percent.
Example 5
The same method as that of example 1 is adopted to treat the organic phosphorus in the water body, and the difference is that: sodium bicarbonate was added to each aqueous solution of organic phosphoric acid to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of six organophosphorus in the solution after reaction is more than 80 percent.
Example 6
The same method as that of example 1 is adopted to treat the organic phosphorus in the water body, and the difference is that: sodium nitrate was added to each of the organic phosphoric acid aqueous solutions to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of six organophosphorus in the solution after reaction is more than 80 percent.
Example 7
The same method as that of example 1 is adopted to treat organic phosphorus in the water body, and the difference lies in that: each aqueous solution of organic phosphoric acid was added with sodium chloride to a final concentration of 100 mmol/L. The experimental results are as follows: the removal rate of six organophosphorus in the solution after reaction is more than 85 percent.
Example 8
The same method as that of example 1 is adopted to treat organic phosphorus in the water body, and the difference lies in that: humic acid with a final concentration of 10 mg/L was added to each organic phosphoric acid aqueous solution. The experimental results are as follows: the removal rate of six organic phosphorus in the solution after reaction is more than 85 percent.
Example 9
The same method as in example 1 was used to treat organic phosphoric acid in water, with the following differences: mixing the six organic phosphorus in the step 1) according to equal concentration, and controlling the initial concentration of the mixed organic phosphorus to be 1mg/L (calculated as P). The experimental results are as follows: the removal rate of each organic phosphorus in the solution after reaction is more than 90 percent.
Example 10
The same method as that of example 1 is adopted to treat the organic phosphorus in the water body, and the difference is that: the organic phosphoric acid solution was replaced with dibutyl phosphate (DnBP) solution at a constant mass concentration, and the pH was adjusted to pH =5. The experimental results are as follows: the removal rate of the organic phosphorus in the solution after the reaction is more than 80 percent.
Example 11
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: to the organic phosphorus-containing solution was added sodium sulfate to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of organic phosphorus in the solution after reaction is more than 80 percent.
Example 12
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: adding trisodium citrate with the final concentration of 10 mmol/L into the solution containing the organophosphorus. The experimental results are as follows: the removal rate of organic phosphorus in the solution after reaction is more than 80 percent.
Example 13
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: sodium bicarbonate was added to the organophosphorus-containing solution to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of the organic phosphorus in the solution after the reaction is more than 80 percent.
Example 14
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: sodium nitrate was added to the solution containing organic phosphorus to a final concentration of 10 mmol/L. The experimental results are as follows: the removal rate of organic phosphorus in the solution after reaction is more than 80 percent.
Example 15
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: adding sodium chloride with the final concentration of 100 mmol/L into the solution containing the organic phosphorus. The experimental results are as follows: the removal rate of organic phosphorus in the solution after reaction is more than 85 percent.
Example 16
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: humic acid with the final concentration of 10 mg/L is added into the solution containing organic phosphorus. The experimental results are as follows: the removal rate of the organic phosphorus in the solution after the reaction is more than 80 percent.
Example 17
The same method as that of example 10 is adopted to treat the organic phosphorus in the water body, and the difference is that: sodium sulfate of 10 mmol/L, trisodium citrate of 10 mmol/L, sodium bicarbonate of 10 mmol/L, sodium nitrate of 10 mmol/L, sodium chloride of 100 mmol/L and humic acid of 10 mg/L are added into the solution containing organic phosphorus. The experimental results are as follows: the removal rate of organic phosphorus in the solution after reaction is more than 70 percent.
Example 18
A treatment method for removing common organic phosphorus in water by using amino-functionalized MOFs materials comprises the following specific steps:
1) Adjusting the pH of aqueous solutions of six organic phosphoric acids (PBTC, HEDP, NTMP, EDTMP, HDTMP, DTPMP) to 5.0 + -0.1, wherein the concentration of each organic phosphoric acid aqueous solution is 1mg/L (calculated by P);
2) Mixing MOFs materials and quartz sand according to a mass ratio of 6:1 (wherein, the quartz sand is 2 g), uniformly loading the mixture into a glass adsorption column (phi 32 multiplied by 360 mm) with a jacket, and simultaneously respectively placing microporous membranes with the diameter of 2 mu m at the top and the bottom of the column to prevent the loss of an adsorbent;
3) Each organic phosphoric acid aqueous solution is treated according to the following steps: pumping organic phosphorus-containing water into a glass adsorption column filled with fillers at the flow rate of 1BV/h by using a proper pipeline and a vacuum pump at the temperature of 25 +/-5 ℃, wherein the experimental result shows that the removal rate of organic phosphorus in outlet water treated by each organic phosphoric acid aqueous solution is more than 99 percent, and the treatment amount reaching a leakage point of all organic phosphorus treatment groups is about more than 530 BV;
4) And stopping operation when a leakage point is reached (the concentration of effluent P is more than 0.01 mg/L), disassembling the adsorption column filled with the MOFs material and the quartz sand adsorption material, washing and soaking the adsorption column with 0.01mol/L NaOH solution for 30min, then washing the adsorption column with ultrapure water to be neutral, washing the adsorption column with 0.01mol/L HCl solution for 30min for activation and regeneration, finally washing the adsorption column with ultrapure water to be neutral, drying the adsorption column at the low temperature of 50 ℃, wherein the regeneration rate of the MOFs material is more than 95% (namely, when the regenerated MOFs material is treated by repeating the steps (1) - (2) - (3), the treatment amount of each organic phosphoric acid water solution reaches more than 500BV of the leakage point after being treated).
Example 19
The same method as that in example 18 is adopted to treat the organic phosphorus in the water body, and the difference is that: in the step 1), potassium sodium tartrate with the final concentration of 10 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about more than 450 BV.
Example 20
The same method as in example 18 is adopted to treat organic phosphorus in the water body, and the difference is that: in the step 1), sodium sulfate with the final concentration of 10 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about 430BV or more.
Example 21
The same method as in example 18 is adopted to treat organic phosphorus in the water body, and the difference is that: in the step 1), trisodium citrate with the final concentration of 10 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about more than 480 BV.
Example 22
The same method as in example 18 is adopted to treat organic phosphorus in the water body, and the difference is that: in the step 1), sodium bicarbonate with the final concentration of 10 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about 475BV or more.
Example 23
The same method as that in example 18 is adopted to treat the organic phosphorus in the water body, and the difference is that: in the step 1), sodium nitrate with the final concentration of 10 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about 490BV or more.
Example 24
The same method as that in example 18 is adopted to treat the organic phosphorus in the water body, and the difference is that: in the step 1), sodium chloride with the final concentration of 100 mmol/L is added into each organic phosphoric acid aqueous solution, and the experimental result shows that the treatment amount reaching the leakage point of all organic phosphorus treatment groups is about more than 500 BV.
Example 25
The same method as in example 18 is adopted to treat organic phosphorus in the water body, and the difference is that: in the step 1), humic acid with the final concentration of 10 mg/L is added into each organic phosphoric acid aqueous solution. The experimental results are as follows: the throughput to the leak point for all organophosphorous treated groups was about 490BV or more.
Example 26
The same method as that in example 18 is adopted to treat the organic phosphorus in the water body, and the difference is that: in the step 1), six organic phosphorus are mixed together according to equal concentration, and the initial concentration of the mixed organic phosphorus is controlled to be 1mg/L (calculated by P). The experimental results are as follows: the throughput to the leak point for all organophosphorous treated groups was about 520BV or more.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A preparation method of amino-functionalized MOFs materials is characterized in that the amino-functionalized MOFs materials are prepared by taking zirconium as a metal center, hydrochloric acid as a regulator and amino terephthalic acid as an organic ligand, and the preparation method comprises the following steps:
1) Mixing and dissolving zirconium salt and 2-amino terephthalic acid in an organic solvent according to a molar ratio of 1.5 to 1.5, adding hydrochloric acid as a regulator, performing ultrasonic treatment until the zirconium salt and the 2-amino terephthalic acid are completely dissolved, placing the mixture into a closed reaction kettle, and then transferring the reaction kettle into an oven to react for 20-30 hours at 100-150 ℃;
2) And after the reaction in the step 1) is finished, carrying out centrifugal filtration on the reaction liquid to obtain a solid product, and washing and drying the solid product to obtain the amino functionalized MOFs material.
2. The method according to claim 1, wherein in step 1), the concentrations of the zirconium salt and the 2-amino terephthalic acid in the organic solvent are 12-15mM, respectively, and the molar ratio of the zirconium salt to the 2-amino terephthalic acid is 1.
3. The method of claim 1, wherein in step 1), the zirconium salt is zirconium chloride and the organic solvent is DMF.
4. Amino-functionalized MOFs material prepared by the method according to any one of claims 1 to 3.
5. Use of the amino-functionalized MOFs material according to claim 4 for the deep removal of organic phosphorus from wastewater.
6. The use according to claim 5, characterized in that the method of application comprises the steps of:
s1: adjusting the pH value of the water body containing the organic phosphorus to 5.0 +/-0.1;
s2: filling the amino-functionalized MOFs material into an adsorption column, and then introducing the organic phosphorus-containing water body with the pH adjusted in the step S1 into the adsorption column;
s3: and (3) after the adsorption inactivation in the step (S2), disassembling the MOFs material in the adsorption column, soaking the MOFs material in alkali liquor, washing the MOFs material to be neutral by using ultrapure water, soaking the MOFs material in acid liquor for activation regeneration, washing the MOFs material to be neutral by using the ultrapure water, drying the MOFs material, namely completing the activation regeneration, and then repeatedly applying the MOFs material in the step (S2).
7. The method according to claim 6, wherein the organic phosphorus in step S1 is one or both of an organic phosphoric acid and an organic phosphate, the organic phosphoric acid is at least one of 2-phosphoric acid-1, 2, 4-tricarboxylic acid butane, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, 1, 6-hexamethylenediamine tetramethylene phosphonic acid, and diethylenetriamine pentamethylene methylene phosphonic acid, and the organic phosphate comprises dibutyl phosphate.
8. The method of claim 6, wherein in step S3, the alkali solution is 5 to 20mmol/L sodium hydroxide solution, and the washing and soaking time is 20 to 40min; the acid solution is a hydrochloric acid solution of 5 to 20mmol/L, and the washing and soaking time is 20 to 40min.
9. The application of claim 6, wherein the concentration of the water containing organic phosphorus in terms of P is less than 5mg/L, preferably less than 1mg/mL, and the flow rate of the water containing organic phosphorus passing through the MOFs material bed layer with amino functionalized in the adsorption column is 0.5-2BV/h, preferably 1BV/h.
10. The use of claim 6, wherein the inactivation of adsorption is recorded when the concentration of P in the effluent is greater than 0.01 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211510769.9A CN115722213A (en) | 2022-11-29 | 2022-11-29 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211510769.9A CN115722213A (en) | 2022-11-29 | 2022-11-29 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115722213A true CN115722213A (en) | 2023-03-03 |
Family
ID=85299457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211510769.9A Pending CN115722213A (en) | 2022-11-29 | 2022-11-29 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115722213A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351401A (en) * | 2023-03-29 | 2023-06-30 | 桂林理工大学 | Preparation method and application of ethylenediamine tetramethylene phosphonic acid modified UIO-66 adsorbent |
| CN116850949A (en) * | 2023-05-26 | 2023-10-10 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084138A (en) * | 2013-01-21 | 2013-05-08 | 华中师范大学 | Application of zirconium dioxide microspheres prepared by using microchannel injection auxiliary method to adsorptive enrichment of organophosphorus pesticide |
| CN103285829A (en) * | 2013-05-21 | 2013-09-11 | 燕山大学 | Method for removing trace phosphorus in wastewater through applying zirconium-based phosphate hybridization functional adsorbing agent |
| CN109916864A (en) * | 2019-01-28 | 2019-06-21 | 浙江省农业科学院 | Stable fluorescence metal-organic framework compounds preparation and the method for detecting organophosphorus pesticide in water |
| CN110813244A (en) * | 2019-11-17 | 2020-02-21 | 中山大学 | Modified zirconium-based organic metal framework adsorbent for adsorbing lead ions and preparation method and application thereof |
| CN111592150A (en) * | 2020-06-24 | 2020-08-28 | 南京大学 | Method for treating copper plating wastewater of hydroxyethylidene diphosphonic acid |
| CN114849650A (en) * | 2022-05-09 | 2022-08-05 | 南京大学 | Preparation method and application of double-surface-characteristic magnetically-modified zirconium MOFs adsorbent |
| CN114917873A (en) * | 2022-04-20 | 2022-08-19 | 珠海兴业新材料科技有限公司 | Preparation method and application of europium-based metal organic framework adsorption material Eu-MOF |
-
2022
- 2022-11-29 CN CN202211510769.9A patent/CN115722213A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084138A (en) * | 2013-01-21 | 2013-05-08 | 华中师范大学 | Application of zirconium dioxide microspheres prepared by using microchannel injection auxiliary method to adsorptive enrichment of organophosphorus pesticide |
| CN103285829A (en) * | 2013-05-21 | 2013-09-11 | 燕山大学 | Method for removing trace phosphorus in wastewater through applying zirconium-based phosphate hybridization functional adsorbing agent |
| CN109916864A (en) * | 2019-01-28 | 2019-06-21 | 浙江省农业科学院 | Stable fluorescence metal-organic framework compounds preparation and the method for detecting organophosphorus pesticide in water |
| CN110813244A (en) * | 2019-11-17 | 2020-02-21 | 中山大学 | Modified zirconium-based organic metal framework adsorbent for adsorbing lead ions and preparation method and application thereof |
| CN111592150A (en) * | 2020-06-24 | 2020-08-28 | 南京大学 | Method for treating copper plating wastewater of hydroxyethylidene diphosphonic acid |
| CN114917873A (en) * | 2022-04-20 | 2022-08-19 | 珠海兴业新材料科技有限公司 | Preparation method and application of europium-based metal organic framework adsorption material Eu-MOF |
| CN114849650A (en) * | 2022-05-09 | 2022-08-05 | 南京大学 | Preparation method and application of double-surface-characteristic magnetically-modified zirconium MOFs adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| LIQIONG LUO ET AL.: ""Hierarchical-pore UiO-66-NH2 xerogel with turned mesopore size for highly efficient organic pollutants removal"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 628, pages 705 - 716, XP087193228, DOI: 10.1016/j.jcis.2022.08.010 * |
| YUE TAO ET AL.: ""Highly efficient removal of glyphosate from water by hierarchical-pore UiO-66: Selectivity and effects of natural water particles"", 《JOURNAL OF ENVIRONMENTAL MANAGEMENT》, vol. 316, pages 115301 * |
| 刘俊: "《可食性包装材料质量检验》", 30 April 2017, 中国质检出版社, pages: 150 - 153 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351401A (en) * | 2023-03-29 | 2023-06-30 | 桂林理工大学 | Preparation method and application of ethylenediamine tetramethylene phosphonic acid modified UIO-66 adsorbent |
| CN116850949A (en) * | 2023-05-26 | 2023-10-10 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
| CN116850949B (en) * | 2023-05-26 | 2024-05-07 | 安徽农业大学 | UiO-W composite wood film and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115722213A (en) | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater | |
| Li et al. | Adsorption and photocatalytic desorption toward Cr (VI) over defect-induced hierarchically porous UiO-66-(OH) 2: a sustainable approach | |
| US20110155669A1 (en) | Method for trace phosphate removal from water using composite resin | |
| CN107840544B (en) | Electroplating wastewater treatment method | |
| Maximous et al. | Removal of heavy metals from wastewater by adsorption and membrane processes: a comparative study | |
| CN115041152B (en) | Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate in water | |
| CN110560012A (en) | Method for removing phosphorus in water by using resin-loaded hydrated iron oxide | |
| CN110523395B (en) | MOF-loaded resin composite adsorbent and preparation method and application thereof | |
| CN111298769B (en) | Preparation method and application of lanthanum-modified sycamore biochar | |
| CN113929492B (en) | Preparation method of hydrotalcite-like composite material for phosphorus recovery, product and application thereof | |
| CN111422942A (en) | Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin | |
| Ali et al. | Development of novel MOF-mixed matrix three-dimensional membrane capsules for eradicating potentially toxic metals from water and real electroplating wastewater | |
| CN108996807A (en) | A method of with nitrogen phosphorus in modified steel scoria-zeolite absorption degradation sanitary sewage | |
| Wang et al. | The mechanisms of conventional pollutants adsorption by modified granular steel slag | |
| Han et al. | Preparation of novel Ce (IV)-based MOF/GO composite and its highly effective phosphate removal from aqueous solution | |
| CN111422941A (en) | Method for deeply purifying phosphate radicals in water body by using imino resin | |
| Zhang et al. | Improving the phosphate adsorption performance of layered manganese oxide by ammonia plasma surface modification | |
| CN115505166A (en) | Thiourea modified resin-based nano material, preparation method and method for deeply removing selenate in water by using same | |
| CN103721689A (en) | Magnetic meso-porous silicon, preparation method of magnetic meso-porous silicon, magnetic meso-porous silicon adsorbent, preparation method and application of magnetic meso-porous silicon adsorbent | |
| CN106669620B (en) | A kind of preparation of modified zirconia mud adsorbent and the method for removing phosphate radical in water removal | |
| KR102344489B1 (en) | System for phosphate adsorption-desorption in aqueous phase using powdered-phosphate absorbent, and method for the same | |
| CN112661968B (en) | Method for preparing MOF adsorption material | |
| JP2000342962A (en) | Heavy metal adsorbent and production thereof | |
| CN104445715B (en) | Treatment method for removing high-concentration nickel-containing electroplating wastewater | |
| CN117843970A (en) | Preparation method and application of cerium doped-metal organic framework material for removing organic phosphorus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |