CN110560018A - synthesis of P2O4 composite UiO-66 material and method for adsorbing and separating indium in liquid crystal panel by using same - Google Patents
synthesis of P2O4 composite UiO-66 material and method for adsorbing and separating indium in liquid crystal panel by using same Download PDFInfo
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- CN110560018A CN110560018A CN201910851278.2A CN201910851278A CN110560018A CN 110560018 A CN110560018 A CN 110560018A CN 201910851278 A CN201910851278 A CN 201910851278A CN 110560018 A CN110560018 A CN 110560018A
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 29
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 4
- 238000003795 desorption Methods 0.000 claims abstract 3
- 238000001179 sorption measurement Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910007746 Zr—O Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for synthesizing an extractant P2O4 composite metal organic framework material UiO-66 material and adsorbing and separating indium in a liquid crystal panel. The invention belongs to the technical field of indium recycling, and particularly relates to a method for recycling indium from a waste liquid crystal display screen panel. The method comprises the following steps: (1) after synthesis and preparation of UiO-66, adding an extractant P2O4 diluted by ethanol, oscillating and reacting for 24 hours in a shaking table, and drying at the temperature of 80-100 ℃ to prepare a P2O4/UiO-66 composite material; (2) preparing 0-1000ppm of InCl3 aqueous solution, adding 0.1-4 g/L of P2O4/UiO-66 composite material, adsorbing and separating indium at 25-45 ℃ of a shaking table at 200-300rpm under the condition that the pH value is 0-3, wherein the recovery rate of In3+ is more than 95%, and the desorption of In3+ can be realized by using 3mol/L hydrochloric acid, and the desorption efficiency can reach 88.8%. The composite material can be repeatedly used, and the recovery rate of the P2O4/UiO-66 composite material to In3+ is basically kept unchanged after 5 cycle tests; (3) the composite material is used for treating the solution of the waste liquid crystal panel soaked by dilute hydrochloric acid, has high selectivity on In3+, and has a recovery rate of over 95%.
Description
Technical Field
The invention belongs to the technical field of indium recycling, and particularly relates to a method for recycling indium from a waste liquid crystal display screen panel.
Background
With the development of science, people have widely used Liquid Crystal Displays (LCDs) as display screens of televisions and mobile phones, and the service life of one lcd panel is generally 3-5 years. With the upgrade of electronic products, a large amount of waste liquid crystal panels will be generated. The current research on recycling of liquid crystal displays is mainly focused on japan, germany and taiwan in our country. The processing target is mainly focused on the recovery of the noble metal indium. The liquid crystal panel contains an ITO film, and the main components of the ITO film are In3+ and In3+ which are directly discharged into the environment and possibly have carcinogenic effect on human bodies and damage the liver, heart, kidney and the like of the human bodies. And the recovered In3+ not only reduces the pollution caused by directly discharging the metal into the garbage, but also can generate good economic benefit. The conventional methods for recovering indium from liquid crystal panels mainly include cation exchange resin methods, acid leaching extraction methods, substitution or electrolysis. The related patents mainly exist.
In the patent of the method for extracting and separating indium and tin from indium-containing leaching slag (Redanhua and the like, application number CN 201510149137.8), P204 is adopted to simultaneously extract indium and tin, fluoride is adopted to perform complexation and reverse extraction of tin, and then hydrochloric acid is used to reversely extract indium, so that a large amount of raffinate generated by the method is difficult to treat, and the environmental protection is influenced.
In the patent of a method for recovering indium from indium-containing neutralized sediments obtained by directly leaching zinc concentrate (Tang Aiyong et al, application No. 200910311599.X), sponge indium is prepared by adopting a plurality of steps of primary sulfuric acid leaching, zinc powder enrichment, secondary sulfuric acid leaching, iron powder essence, P2O4 extraction, hydrochloric acid back extraction, chip replacement and the like.
The technologies of the patents adopt the chelating agent P2O4 for extraction, a large amount of organic solvent is needed for assisting the extraction, and the subsequent back extraction process has the problems of easy loss of the organic solvent, difficult solid-liquid separation and the like.
In the patent of preparation method of impregnating resin for adsorbing scattered metal indium (III) (Liu military deep et al, application number CN 201811102086.3), styrene-divinyl macroporous adsorption resin is used as a carrier, and a mixed extraction agent of N1923 and phytic acid is used as an adsorption site to adsorb the scattered metal indium (III) in an acid solution system.
In recent years, Metal-organic frameworks (MOFs) have been developed, which are porous and can be made with different pore sizes and functionalized; thus, MOFs have been widely used in various fields, such as gas heterogeneous catalytic separation, sensors, drug separation, biomedical imaging, etc.; the composite material synthesized by loading the extractant on MOFs can not only solve the defect of difficult solid-liquid separation of the extractant, but also recover In3+ under acidic conditions, and has simple operation and good recycling performance.
Disclosure of Invention
[1] The technical problem to be solved by the invention is to provide a preparation method of a P2O4 composite metal organic framework material UiO-66 material with low cost, simple manufacture, excellent performance and acid resistance, and an In3+ of an LCD In an adsorption separation liquid crystal panel; has the advantages of high efficiency, energy saving, convenient operation, etc.
[2] In order to solve the technical problem, the synthesized material comprises the following steps:
The method comprises the following steps: ZrCl4(6.4mmol), terephthalic acid (6.4mmol) and DMF (180mL) are mixed and dissolved, then added into a polytetrafluoroethylene reaction kettle, reacted for 12 hours at 80 ℃, then the temperature is raised to 100 ℃ and then reacted for 24 hours, after natural cooling, ethanol is used for washing and centrifuging for 3 times, and then the mixture is dried in a vacuum drying oven for 80 ℃ for one night. And then ground. Adding the synthesized UiO-66 into P2O4 diluted by ethanol, vibrating the material in a shaker for 24 hours at the speed of 200 rpm and the temperature of 25 ℃, pouring a sample into a beaker, and drying the sample in an oven;
Step two: dissolving the ITO film of the liquid crystal panel: 10 g of the liquid crystal panel was taken, dissolved in 100ml of dilute hydrochloric acid, and used for adsorption studies.
[3] The P2O4/UiO-66 composite material synthesized by the steps has acid resistance and stable structure under the strong acid condition.
[4] Compared with the prior art, the invention has the beneficial effects that: the invention has simple preparation and acid resistance, and can be applied to acidic solution to absorb In3 +; 2 compared with the traditional method for recovering In3+, the method of the invention comprises the following steps: the method is simple to operate and recover, does not generate new chemical pollution, has good anti-interference performance, and can also recover In3+ under an acidic condition.
Drawings
FIG. 1XRD patterns of pure UiO-66, P2O4/UiO-66 composite material prepared by the present invention example 1, P2O4/UiO-66 composite material soaked in acidic condition, and P2O4/UiO-66 composite material eluted 3 times with ethanol.
FIG. 2 FT-IR plot of pure UiO-66, P2O4/UiO-66 composite of preparation 1 of the present invention, and P2O4/UiO-66 composite eluted 3 times with ethanol.
FIG. 3 is a photographic image of a P2O4/UiO-66 composite material prepared by the method of example 1.
FIGS. 4 and 5 SEM images of pure UiO-66, P2O4/UiO-66 composite material prepared by the inventive example 1.
FIG. 6 is a graph showing the adsorption kinetics of In3+ for P2O4/UiO-66 composite material prepared In example 1 of the present invention.
FIG. 7 is a graph showing the cycle performance of P2O4/UiO-66 composite material prepared In example 1 of the present invention against In3 +.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments, which are merely illustrative of the present invention and are not limited to the present invention.
Example 1:
ZrCl41.5 g, terephthalic acid 1.06 g and DMF (180mL) are mixed and stirred for 10 minutes, added into a polytetrafluoroethylene reaction kettle after being dissolved, reacted for 12 hours at 80 ℃, then the temperature is raised to 100 ℃ and then reacted for 24 hours, after natural cooling, the mixture is washed and centrifuged for 3 times by ethanol, and then the mixture is ground in a vacuum drying oven at 80 ℃ for one night to obtain pure UiO-66. The synthesized UiO-66 was added with ethanol diluted P2O4, the material was shaken in a shaker for 24 hours at 200 rpm at 25 ℃ and the sample was poured into a beaker and dried in an oven.
FIG. 1XRD patterns of pure UiO-66, P2O4/UiO-66 composite material prepared by the present invention example 1, composite P2O4/UiO-66 composite material soaked in acidic condition, P2O4/UiO-66 composite material eluted 3 times with ethanol; XRD shows that P2O4 compounded UiO-66 still maintains the structure of the UiO-66, the compounded material is soaked in 3mol/L HCl for 24 hours, the structure is still unchanged, and the compound is washed by ethanol and centrifuged for 3 times, and the structure is still unchanged.
FIG. 2 is a FT-IR plot of pure UiO-66, P2O4/UiO-66 composite material of preparation 1 of the present example, P2O4/UiO-66 composite material eluted 3 times with ethanol; the Zr-O vibration peak at 748cm-1 is the Zr-O vibration peak of UiO-66, and the strong vibration peak at 1398cm-1,1578 cm-1,1657cm-1 is due to the characteristic vibration of carboxyl groups. Other weak peaks between 700 and 1200cm < -1 > belong to vibration peaks of aromatic benzene rings. These demonstrate the successful synthesis of UiO-66, which is in contrast to XRD. The P2O4/UiO-66 composite material has Zr-O vibration peak at 748cm-1, the strong vibration peak at 1402cm-1,1581cm-1,1657cm-1 is caused by the characteristic vibration of carboxyl, which indicates that the composite still has a structure for maintaining the UiO-66, and the result is in accordance with XRD, and compared with the pure UiO-66, the vibration peak of the carboxyl is shifted from 1398cm-1 to 1402cm-1, and the vibration peak of the carboxyl is shifted from 1578cm-1 to 1581cm-1, which is probably the result of the carboxyl bond of the UiO-66 being compounded with P2O 4; in addition, the complex also has 1031 cm-1 characteristic peak P-O-C bond, 1207cm-1 characteristic peak P ═ O bond and 1699cm-1 characteristic peak P-OH bond; the characteristic peaks of 2860cm-1 and 2960cm-1 are C-H bonds, which indicates that P2O4-UiO-66 is successfully compounded.
to verify that the P2O4/UiO-66 composite is a complex, not a UiO-66+ P2O4 mixture, due to the dissolution of P2O4 in ethanol; the P2O4/UiO-66 composite material is centrifugally cleaned for 3 times by ethanol, and the UiO-66+ P2O4 composite cleaned for 3 times is found to keep the characteristic peak of the UiO-66 and the characteristic peak of the P2O4, which indicates that the P2O4/UiO-66 composite material is successfully synthesized. This also confirms the XRD pattern of figure 1.
FIG. 3 is a photograph of P2O4/UiO-66 composite material prepared in accordance with example 1 of the present invention, from which it can be seen that the resultant material is in the form of a gel.
FIG. 4 is a scanning electron microscope image of a pure UiO-66 sample, which is porous, rough and irregular block, FIG. 5 is a scanning electron microscope image of a P2O4/UiO-66 composite material, the surface becomes smooth after surface recombination, and the porous structure disappears, which is probably due to the covering of P2O4 on the surface of the UiO-66.
Example 2:
250ml of an 18.96ppm aqueous solution of InCl3 were prepared and introduced into a 500ml Erlenmeyer flask, 0.2 g of the P2O4/UiO-66 composite prepared in example 1 were added, the parameters of the shaker being: at 25 ℃, 200r/min, pH 3; 2ml of the suspension was quantitatively sampled at different time intervals and filtered through a 0.22 μm aqueous membrane for a reaction time of 24 hours, and FIG. 6 is a graph showing the adsorption kinetics of In3+ to P2O4/UiO-66 composite material prepared In example 1 of the present invention. The above samples were quantified by ICP-OES analysis and plotted as kinetic curves in FIG. 6; as can be seen from FIG. 6, the P2O4/UiO-66 composite material has excellent adsorption performance and short reaction time.
Example 3:
Preparing 20ppm of an InCl3 aqueous solution, wherein the adding amount of an adsorbent is 1 g.L-1, the parameters of a shaking table are 25 ℃, 200r/min and the pH value is 3; filtering with 0.22 μm water system membrane, quantifying the above samples with ICP-OES, and drawing the adsorption cycle line of FIG. 7; FIG. 7 is an adsorption cycle line of P2O4/UiO-66 composite material prepared In the embodiment 1 of the present invention for In3 +; after 5 times of circulation, the adsorption rate of 99 percent can still be maintained.
example 4:
The liquid crystal panel was dissolved in an HCl solution having a pH of 0.58, and the indium solution C0 before the reaction was 12.47ppm and the indium solution Ct after the reaction was 0.171, and the adsorption rate was 98.6%.
Claims (7)
1. A method for synthesizing a P2O4/UiO-66 composite material and using the composite material for adsorbing and separating indium in a liquid crystal panel is characterized in that the method comprises the step of synthesizing the P2O4/UiO-66 composite material, and specifically comprises the following steps: the UiO-66 is synthesized by a solvothermal method, namely ZrCl4(6.4mmol) and terephthalic acid (6.4mmol) are dissolved in 150 mL of N, N-dimethylformamide, then the N, N-dimethylformamide and the terephthalic acid are transferred to a 200mL polytetrafluoroethylene reaction kettle, the reaction is carried out for 12h at 80 ℃, then the temperature is adjusted to 120 ℃ for reaction for 24h, the reaction is naturally cooled, then a sample is taken out, fully washed by deionized water and ethanol, centrifuged for 3 times, and then the sample is placed in a vacuum drying oven at 80 ℃ for drying for one day; thus obtaining the UiO-66 material; then adding UiO-66 into P2O4 diluted by ethanol, oscillating for 24 hours in a shaker at 25 ℃, volatilizing the ethanol at 80 ℃, and drying at 80-100 ℃ to synthesize the P2O4/UiO-66 composite material.
2. A P2O4/UiO-66 composite material synthesis and method for absorbing and separating indium in liquid crystal panel, characterized in that the composite material P2O4-UiO-66 is a gel, after absorbing and separating indium, it is easy to separate, and it can realize separation and recovery without centrifugation or filtration.
3. a P2O4/UiO-66 composite material and a method for adsorbing and separating indium in a liquid crystal panel are characterized in that the material has high indium adsorption speed, can achieve more than 95% of recovery rate within 1 hour, and has fast desorption rate.
4. A method for synthesizing a P2O4/UiO-66 composite material and using the composite material for adsorbing and separating indium In a liquid crystal panel is characterized In that the concentration of the In3+ solution is 1-1000 mg/L.
5. A P2O4/UiO-66 composite material synthesis and a method for using the composite material to absorb and separate indium in a liquid crystal panel are characterized in that the adding amount of the composite material is 0.1g/L-4 g/L.
6. A P2O4/UiO-66 composite material and a method for absorbing and separating indium In a liquid crystal panel are characterized In that the material can be used In an actual liquid crystal panel to separate and absorb In3 +.
7. A P2O4/UiO-66 composite material synthesis and method for using it to absorb and separate indium in liquid crystal panel, characterized by that the composite material recycles the performance well, through recycling 5 times, still can keep the indium recovery rate above 95%.
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