CN115703059B - Preparation method of heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent - Google Patents
Preparation method of heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent Download PDFInfo
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 56
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 56
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013183 functionalized metal-organic framework Substances 0.000 title claims abstract description 14
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims abstract description 18
- -1 salt ammonium phosphomolybdate Chemical class 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical class [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 239000012621 metal-organic framework Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000013240 MOF-76 Substances 0.000 description 15
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 12
- 239000012267 brine Substances 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229940102127 rubidium chloride Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FAWNVSNJFDIJRM-UHFFFAOYSA-N [Rb].[Cs] Chemical compound [Rb].[Cs] FAWNVSNJFDIJRM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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 discloses a preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent, which comprises the step of loading inorganic material heteropolyacid salt ammonium phosphomolybdate (AMP) and ammonium phosphotungstate (AWP) with high adsorption capacity to rubidium and cesium ions into MOFs with large surface area and adjustable aperture by an in-situ synthesis method to obtain a composite material with a space three-dimensional skeleton and wrapped heteropolyacid salt. Can greatly reduce the loss of ammonium phosphomolybdate and ammonium phosphotungstate, improve the adsorption performance of rubidium and cesium, and has high adsorption rate and large adsorption capacity.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent.
Background
Among the rare metal elements, rubidium and cesium are commonly called as 'long-eye metal', mainly because the rubidium and cesium have the characteristics of good ductility, electric conductivity and thermal conductivity, strong chemical activity, excellent photoelectric effect performance and the like. It is used as important strategic resource and is widely applied in the fields of aerospace, energy, medicine, chemistry, optical communication system, electronic equipment and the like. Therefore, with the rapid development of the high-tech industry at home and abroad, rubidium, cesium and compounds thereof show great commercial value and broad development prospect, and the demand is rapidly increased.
The reserves of rubidium and cesium resources are rich in the world, but the absolute concentration of rubidium and cesium is low and the distribution is dilute, and because the rubidium and cesium have strong chemical activity, few independent rubidium and cesium mineral resources exist in nature and are mainly associated with other alkali metal minerals. Rubidium and cesium exist in the form of ions in water resources in addition to the accompanying components in the solid mineral resources. Rubidium-and cesium-containing ores gradually deplete and the price rises, and the most critical is that the crude extraction mode (high-temperature calcination and strong acid and alkali leaching) of the ores causes serious environmental pollution. In contrast, salt lakes also contain rich rubidium and cesium resources, so that research on how to extract and separate rubidium and cesium from salt lakes is significant.
Rubidium and cesium resources in China are mainly distributed in pesium and lepidolite in Xinjiang, sichuan, jiangxi, jiangsu, henan, hunan and other places, and in salt lakes of Qinghai and Tibet. In recent years, along with the continuous development of salt lake resources and the requirement of improving the comprehensive utilization rate, the separation and extraction of scattered elements are receiving more and more attention and importance. The concentration of rubidium and cesium in Qinghai Bohr sweat salt lake brine is not high, and the average concentration is 10.8mg L respectively -1 、0.034mg L -1 The content is low, and the lithium, sodium and potassium which are similar to a large amount of chemical properties coexist, so that the industrial development and utilization are difficult. At present, the exploitation and utilization process of rubidium and cesium resources in salt lake brine is not mature, and research on how to separate and extract rubidium and cesium from salt lake brine in a green and efficient manner has important theoretical significance and great economic value.
In recent years, methods for extracting rubidium and cesium in salt lake brine mainly comprise a precipitation method, an extraction method and an adsorption method. Although the recovery rate of rubidium and cesium resources extracted from aqueous solutions by using a precipitation method is relatively high, the precipitation method is often only suitable for the situation that the contents of rubidium and cesium ions in a solution system are high, and the use of the precipitation method is uneconomical due to the low contents of rubidium and cesium ions in brine. Therefore, the precipitation method has little research on extraction and separation of rubidium and cesium at low concentrations. Extraction is one of the important separation methods in the separation field, and foreign scientists research and use solvent extraction to extract alkali metals from the beginning of the 50 th century. So far, extraction technology has been developed for a long time, and extraction systems and extraction processes are mature and perfect. The extraction method has high separation efficiency, large production capacity, simple operation and easy continuous and amplifying operation, and is widely applied to the fields of chemical industry, metallurgy, food and the like. However, most of the common extracting agents used in the extraction method are organic agents, which are harmful to the environment and cause a certain pollution to the environment due to improper control. The adsorption method is more suitable for separating and enriching low-concentration rubidium and cesium resources from complex Chinese brine by combining the characteristics of high content and low concentration of salt lake brine. The method has the advantages of strong selectivity, convenient operation, simple process, high recovery rate and easy realization of industrialization, and is considered as the most potential production method for separating and extracting rubidium and cesium from salt lake brine. Therefore, the method is also widely applied and researched to separation of rubidium and cesium in salt lake brine.
The key of the adsorption method is the preparation of the adsorbent, and two main types of common adsorbents for separating and enriching rubidium and cesium in salt lake brine are: organic resins and inorganic materials. The organic ion exchanger is mainly chelating resin, which has large exchange capacity, is easily interfered by high-valence metal ions and has larger exchange potential, and is only suitable for column loading for on-line separation and enrichment such as flow injection, chromatography and the like. The inorganic adsorbent has good stability, heat resistance, radiation resistance, selectivity and excellent mechanical properties, and is widely applied to industrial adsorption separation processes.
Heteropoly acid salt is a common inorganic adsorption material for extracting and separating rubidium and cesium ions in solution, wherein most researches are carried out on ammonium phosphomolybdate and ammonium phosphotungstate, and the adsorption material has the advantages of large adsorption capacity and high partition ratio in an acidic medium. However, the ion exchanger is in a powder crystalline structure, has poor hydraulic property, is not easy to recover after being adsorbed, is easy to generate a sol-gel phenomenon, and has the defects of reduced adsorption rate and desorption rate caused by agglomeration and excessively high loss rate of the adsorbent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent. Can greatly reduce the loss of ammonium phosphomolybdate and ammonium phosphotungstate, improve the adsorption performance of rubidium and cesium, and has high adsorption rate and large adsorption capacity.
The invention is realized by the following technical scheme:
a preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent comprises the following steps:
dispersing metal ions, organic ligands and heteropolyacid salt in an organic solvent to obtain a first mixture, and carrying out hydrothermal reaction on the first mixture to obtain a second mixture, wherein the reaction temperature is 85-120 ℃ and the reaction time is 24-36 h; performing solid-liquid separation on the second mixture, and washing and drying the solid to obtain the heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent;
the mass ratio of the metal ions, the organic ligand and the heteropolyacid salt in the first mixture is 1 (0.8-1.5): 0.15-0.67); the metal ions are samarium ions and neodymium ions;
the organic ligand is one or more of isophthalic acid, trimesic acid, phthalic acid and terephthalic acid;
the heteropolyacid salt is ammonium phosphomolybdate and/or ammonium phosphotungstate;
the organic solvent is a mixture of N, N-Dimethylformamide (DMF), ethanol and water;
in the technical scheme, the precursor of the metal ion is samarium nitrate hexahydrate and/or neodymium nitrate hexahydrate;
in the technical scheme, the organic ligand is isophthalic acid and trimesic acid, and the molar ratio of the phthalic acid to the trimesic acid is (0-3): 1;
in the technical scheme, the mass ratio of the hexahydrated samarium nitrate, the isophthalic acid, the trimesic acid and the heteropolyacid salt in the first mixture is 1 (0.5-0.7), 0.3-0.5 and 0.15-0.67;
the heteropolyacid salt is ammonium phosphomolybdate and/or ammonium phosphotungstate.
In the technical scheme, the hydrothermal reaction is completed in a stainless steel lined polytetrafluoroethylene reaction kettle.
In the technical scheme, the organic solvent is a mixture of N, N-dimethylformamide, ethanol and water in a volume ratio of 1:1:0.8.
In the technical scheme, the method for dispersing the metal ions, the organic ligand and the heteropolyacid salt in the organic solvent adopts an ultrasonic and/or stirring dispersion method.
In the technical scheme, the reaction time of the hydrothermal reaction is 48 hours.
In the above technical scheme, the washing agent used for washing the solids in the second mixture is N, N-dimethylformamide and absolute ethyl alcohol.
In the technical scheme, the drying process is constant-temperature drying at 60-80 ℃.
In the technical scheme, the method further comprises the step of crushing the dried solid to a particle size of 2-3 mm to obtain the heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent.
The invention has the advantages and beneficial effects that:
the invention adopts an in-situ synthesis method to load ammonium phosphomolybdate and ammonium phosphotungstate into MOFs based on the strong chemical bond action between heteropolyacid salt and rubidium and cesium so as to improve the adsorptivity to rubidium and cesium. Because MOF-76 (Sm) in MOFs crystal material has larger aperture, and the dynamic diameter of the MOF-76 (Sm) is much larger than that of ammonium phosphomolybdate and ammonium phosphotungstate (10.5A), the phosphomolybdic acid and the ammonium phosphotungstate can be wrapped in the skeleton structure of MOF-76 (Sm) through an in-situ synthesis method, so that a novel composite material of the MOFs wrapped heteropolyacid with a space three-dimensional skeleton is obtained, the contact sites of rubidium and cesium and the heteropolyacid are increased, and the heteropolyacid is prevented from escaping. Compared with the traditional MOFs material, the specific surface area of the composite material AMP@MOFs/AWP@MOFs can be effectively increased, and the loss of ammonium phosphomolybdate and ammonium phosphotungstate can be greatly reduced.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent in an embodiment of the invention.
Figure 2 is an XRD diffractogram of the MOFs adsorbent product prepared in the comparative example of the present invention.
Fig. 3 is an SEM scan of MOFs adsorbent products prepared in the comparative example of the present invention.
FIG. 4 is a graph showing comparison of adsorption amounts of rubidium and cesium by MOFs adsorbent products prepared in comparative examples of the present invention.
FIG. 5 is an XRD diffraction pattern of the AMP@MOFs adsorbent product prepared in example 1 of the present invention.
FIG. 6 is an SEM scan of an AMP@MOFs adsorbent product prepared in example 1 of the present invention.
FIG. 7 is a graph showing comparison of adsorption amounts of rubidium and cesium by AMP@MOFs adsorbent products prepared in example 2 of the present invention.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the person skilled in the art better understand the solution of the present invention, the following describes the solution of the present invention with reference to specific embodiments.
Comparative example
Firstly, 1.76mmol of samarium nitrate hexahydrate and 1.4mmol of trimesic acid ligand are adopted as ligand preparation agents, namely the molar ratio of isophthalic acid to trimesic acid is (0:1), (1:1), (2:1) and (3:1); dissolved in a mixed solution of 15mL of N, N-Dimethylformamide (DMF), 15mL of absolute ethanol and 12mL of deionized water, and dissolved by ultrasonic stirring. Then pouring the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the reaction kettle into an oven, setting the reaction temperature to be 70-110 ℃ and reacting for 24-48h. And after the reaction, naturally cooling and taking out the reactant. Washing with DMF and absolute ethanol for several times, centrifuging, and vacuum drying at 60-85deg.C. Finally, a white flocculent product is obtained, and the product is further ground and then is stored in a sealing way. Isophthalic acid is adopted as ligand regulator, and the principle is that isophthalic acid is used for replacing trimesic acid, two carboxylic acids are arranged in isophthalic acid, after trimesic acid is replaced, coordination sites of trimesic acid are not completed naturally, and crystal lattice vacancies formed by different addition amounts of isophthalic acid are different. The resulting product and molar ratio of isophthalic acid to trimesic acid are labeled MOF-76 (0:1), MOF-76 (1:1), MOF-76 (2:1), MOF-76 (3:1), respectively.
The obtained product is subjected to XRD and SEM characterization, and the XRD patterns of different crystal lattice vacancies of figure 2 show that 4 MOF materials show characteristic close-packed structures and good structural consistency and have the same topological structure, so that the MOF-76 can resist the influence of partial trimesic acid ligand partial loss on the structure. The same SEM results for the different crystal lattice vacancies from fig. 3 indicate that, consistent with the results demonstrated by XRD, again, the addition of the modulator is demonstrated to not alter the framework structure of the MOF material.
Then the obtained product is subjected to simple adsorption experiments on rubidium and cesium ions, and the adsorbent is respectively added in the solution containing 1mmol L of rubidium and cesium -1 Is adsorbed in the rubidium chloride and cesium chloride solution. Results FIG. 4, where n PTA ：n BTC Represents the molar ratio of isophthalic acid to trimesic acid; it was found that by using different amounts of isophthalic acid, the adsorption of rubidium and cesium is improved to some extent without changing the framework of the MOF material, especially at n PTA ：n BTC The peak is reached at 2:1, probably because isophthalic acid partially replaces trimesic acid, allowing the MOF material to have more adsorption sites for rubidium and cesium ions.
Example 1
Preparation method of heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent
Samarium nitrate hexahydrate 4.49mmol, trimesic acid ligand 2.86mmol, isophthalic acid 2.85mmol,5g ammonium phosphomolybdate. Dissolved in a mixed solution of 20mL of N, N-Dimethylformamide (DMF), 20mL of absolute ethanol and 250mL of deionized water, and ultrasonically stirred for dissolution. Then moving to a stainless steel sleeve polytetrafluoroethylene reaction kettle, putting the reaction fluorine into an oven, and setting the reaction temperature to be 95 DEG CThe reaction was carried out for 24 hours. And after the reaction, naturally cooling and taking out the reactant. Washing for multiple times by using DMF and absolute ethyl alcohol, centrifuging, drying at constant temperature of 65 ℃ to obtain the heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent (AMP@MOF-76 adsorbent). The adsorbent is respectively added with 1mmol L of rubidium and cesium -1 Is adsorbed in the rubidium chloride and cesium chloride solution. Static saturation capacities were 0.52mmol L, respectively -1 、0.423mmol L -1 When the same amount of adsorbent is used for adsorbing the actual brine, the saturated adsorption amounts respectively reach 0.42mmol L -1 、0.35mmol L -1 。
The adsorbent was subjected to XRD and SEM characterization, and the XRD results are shown in fig. 5: XRD diffraction patterns of AMP, MOF-76, AMP@MOF-76-Rb and AMP@MOF-76-Cs show that ammonium phosphomolybdate is used as a modifier, and XRD spectra of modified MOF-76 and modified MOF-76 after adsorbing rubidium and cesium show that ammonium phosphomolybdate is successfully loaded on MOF-76, has no obvious influence on the structure of the ammonium phosphomolybdate, has no change and is wrapped by heteropolyacid salt, and can exist stably. In addition, the adsorption process has no obvious influence on the structures of the two adsorbents, which shows that the adsorbents have certain structural stability. SEM results are shown in fig. 6, again to a consistent conclusion.
Example two
6.75mmol of samarium nitrate hexahydrate, 2.86mmol of trimesic acid ligand and 2.85mmol of isophthalic acid are subjected to experiments on preparing the adsorbent from ammonium phosphomolybdate with different contents; the molar ratio of trimesic acid to ammonium phosphomolybdate is (1:1, 1:2, 1:4), respectively. Dissolved in a mixed solution of 45mL of N, N-Dimethylformamide (DMF), 45mL of absolute ethanol and 36mL of deionized water, and dissolved by ultrasonic stirring. Then the mixture is put into a stainless steel sleeve polytetrafluoroethylene reaction kettle, the reaction fluorine is put into an oven, the reaction temperature is set to 90 ℃, and the reaction is carried out for 24 hours. And after the reaction, naturally cooling and taking out the reactant. Washing with DMF and absolute ethanol for several times, centrifuging, and drying at 70deg.C in an incubator. Finally, the AMP@MOF adsorbent is obtained.
Taking the composite adsorbent to obtain the rubidium-cesium-containing composite adsorbent with the concentration of 0.05mmol L -1 And (3) carrying out static adsorption experiments on rubidium chloride and cesium chloride. After 24h of adsorption, adsorb knotThe result is shown in fig. 7. Wherein n is BTC ：n AMP Represents the molar ratio of trimesic acid to ammonium phosphomolybdate; the results of this example show that with increasing AMP molar ratio, the amount of adsorbed rubidium and cesium in rubidium chloride and cesium chloride gradually increases, but the amount of adsorbed rubidium and cesium in the rubidium chloride and cesium chloride gradually decreases, indicating that the adsorption amount of the composite adsorbent cannot be increased significantly due to excessive AMP loading on MOF-76.
In addition, the adsorbents prepared in this example were subjected to adsorption control tests with respect to the MOF-76 (2:1) adsorbent of comparative example, and rubidium and cesium were contained in amounts of 0.05mmol L, respectively -1 Static adsorption experiments were performed on rubidium chloride and cesium chloride, and the data are shown in table 1:
TABLE 1
The result shows that after MOF-76 (2:1) is modified by AMP loading, the obtained composite adsorbent AMP@MOF-76 has obvious increase on the adsorption quantity of rubidium and cesium.
Relational terms such as "first" and "second", and the like may be used solely to distinguish one element from another element having the same name, without necessarily requiring or implying any actual such relationship or order between such elements.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (9)
1. A preparation method of a heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent is characterized by comprising the following steps:
dispersing metal ions, organic ligands and heteropolyacid salt in an organic solvent to obtain a first mixture, and carrying out hydrothermal reaction on the first mixture to obtain a second mixture, wherein the reaction temperature is 85-120 ℃ and the reaction time is 24-36 h; performing solid-liquid separation on the second mixture, and washing and drying the solid to obtain the heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent;
the mass ratio of metal ions, organic ligands and heteropolyacid salt in the first mixture is 1 (0.8-1.5): 0.15-0.67); the metal ions are samarium ions and neodymium ions;
the organic ligand is isophthalic acid and trimesic acid, and the molar ratio of the isophthalic acid to the trimesic acid is (0-3) 1;
the heteropolyacid salt is ammonium phosphomolybdate and/or ammonium phosphotungstate;
the organic solvent is a mixture of N, N-Dimethylformamide (DMF), ethanol and water.
2. The method according to claim 1, wherein the precursor of the metal ion is samarium nitrate hexahydrate and/or neodymium nitrate hexahydrate.
3. The preparation method according to claim 2, wherein the mass ratio of the hexahydrated samarium nitrate, isophthalic acid, trimesic acid and heteropolyacid salt in the first mixture is 1 (0.5-0.7): 0.3-0.5): 0.15-0.67;
the heteropolyacid salt is ammonium phosphomolybdate and/or ammonium phosphotungstate.
4. The method of claim 1, wherein the hydrothermal reaction is performed in a stainless steel lined polytetrafluoroethylene reactor.
5. The preparation method according to claim 1, wherein the organic solvent is a mixture of N, N-dimethylformamide, ethanol and water in a volume ratio of 1:1:0.8.
6. The preparation method according to claim 1, wherein the metal ions, the organic ligands and the heteropolyacid salt are dispersed in the organic solvent by ultrasonic and/or stirring dispersion.
7. The preparation method according to claim 1, wherein the reaction time of the hydrothermal reaction is 24 hours, and the drying process is constant-temperature drying at 60-80 ℃.
8. The process of claim 1 wherein the washing of the solids in the second mixture is performed with N, N-dimethylformamide and absolute ethanol.
9. The preparation method of claim 1, further comprising crushing the dried solid to a particle size of 2-3 mm to obtain the heteropolyacid salt functionalized MOF-based rubidium and cesium adsorbent.
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