CN112547026A - Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater - Google Patents

Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater Download PDF

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CN112547026A
CN112547026A CN202011174988.5A CN202011174988A CN112547026A CN 112547026 A CN112547026 A CN 112547026A CN 202011174988 A CN202011174988 A CN 202011174988A CN 112547026 A CN112547026 A CN 112547026A
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uranium
adsorption
seawater
plmr
pao
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马春新
温顺喜
王宁
刘荣荣
王佳文
陈琳
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Hainan University
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Abstract

The invention discloses a uranium adsorption material, a preparation method thereof and application thereof in adsorption recovery of uranium in seawater. This uranium adsorption material utilizes macroporous resin's super high specific surface area and porosity intensive dispersion load amidoxime, enables amidoxime's active group fully to expose, improves adsorption rate and adsorption capacity to uranium in the sea water greatly, draws with its application and the uranium in the sea water, has to uranium high selectivity absorption, and adsorption rate is fast, and the capacity is big, circulated use, characteristics such as good to sea water tolerance, can used repeatedly, the enrichment of uranium in the especially adapted sea water is drawed.

Description

Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater
Technical Field
The invention relates to a uranium adsorption material, in particular to a uranium adsorption material formed by nonpolar macroporous resin loaded polyamidoxime, and also relates to application of the uranium adsorption material in adsorption recovery of uranium in seawater, belonging to the technical field of seawater uranium extraction.
Background
Nuclear power has gained rapid development in recent decades as an excellent new energy source to replace traditional fossil fuels. However, uranium ores on land provide nuclear energy consumption for no more than 100 years globally. In order to ensure the long-term rapid development of the nuclear power industry, the development of uranium resources in seawater which can be used by human for more than ten thousand years is urgently needed. However, despite this, Uranium (UO) in seawater2 2+) Ultra-low concentration of
Figure BDA0002748452090000011
And the complex marine environment severely limit the efficient extraction of uranium from seawater on a large scale. Uranium adsorption technology has been studied more extensively than other strategies such as chemical precipitation, electrochemical extraction, ion exchange and liquid extraction, and is the most promising method for extracting uranium from seawater for large-scale industrialization. Today, various uranium adsorbent materials are being explored, such as inorganic adsorbents, polymer-based adsorbents, various types of nanostructured materials (including MOF, PAF, COF, POP and more recently 2D nanostructured xylenes, more recently biomass adsorbents, etc.
In recent years, the recovery of uranium from seawater has attracted increasing attention due to the high adsorption capacity, excellent specificity and relatively low production costs of amidoxime-based materials. Various methods have been developed to improve uranium in seawater. The adsorption performance of amidoxime-based Adsorbents for Uranium may be increased by, for example, designing ultrafine nanofibers (Xie, s.; Liu, x.; Zhang, b.; Ma, h.; link, c.; Yu, m.; Li, l.; Li, j. electrophoretic nano fibers for urea Extraction from sea water.j. mater.chem.a.2015,3(6), 2552-inch 2558.) or a porous structure (Wang, d.; Song, j.; Lin, s.; Wen j.; Ma, c.; Yuan, y.; Lei, m.; Wang, x.; Wang, n.; Wu H.A Marine-injected Hybrid for high efficiency ion), which may result in increased adsorption performance of the amidoxime-based Adsorbents, such as to Uranium, which may result in greater exposure to the amidoxime group adsorption performance of the amine. For example, the amidoxime group on the surface of the inorganic two-dimensional nanomaterial with a large specific surface area (Qian, Y.; Yuan, Y.; Wang, H.; Liu, H.; Zhang, J.; Shi, S.; Guo, Z.; Wang, N.high efficiency organic Uranium Adsorption by saline alumina/Polydopamine Graphene Oxide nanocomposite. J.mater.Chem.A.2018,6(48), 24one 24685 676.), including Graphene Oxide and xylene flakes, can greatly improve the Adsorption capacity of Uranium. In addition, Uranium adsorption performance can be significantly improved by dispersing amidoxime functional polymers into hydrogels without traditional porous structures (Wang, X.; Liu Q.; Liu, J.; Chen, R.; Zhang, H.; Li, R.; Li, Z.; Wang, J.3D Self-Assembly polyethylene Modified Graphene Oxide Hydrogel for the Extraction of organic from Aqueous solution. appl.Surf. Sci.2017, 426, 1063-. The uranyl ions migrate to the interior. However, although the adsorption performance of uranium can be greatly improved by the above method, since the marine environment is complicated and severe, in order to recover uranium from seawater in large quantities, it is still necessary to further improve the adsorption capacity and rate of an amidoxime group.
Disclosure of Invention
Aiming at the defects of an amidoxime-based material for adsorbing uranium in the prior art, the invention aims to provide a uranium adsorbing material consisting of macroporous resin loaded with polyamidoxime, wherein the uranium adsorbing material is prepared by fully dispersing and loading amidoxime by utilizing ultrahigh specific surface area and porosity of macroporous resin, so that active groups of amidoxime can be fully exposed, and the adsorption rate and the adsorption capacity of uranium in seawater are greatly improved.
The second purpose of the invention is to provide a method for preparing uranium adsorbing material with simple steps and low cost.
The third purpose of the invention is to provide an application of a uranium adsorption material in the aspect of adsorbing uranium in seawater, wherein the uranium adsorption material has high selective adsorption on uranium in seawater, and has the advantages of high adsorption rate, large capacity, good tolerance on seawater, reusability, and is particularly suitable for enrichment and extraction of uranium in seawater.
In order to achieve the technical purpose, the invention provides a uranium adsorption material which is composed of nonpolar macroporous resin loaded with polyamidoxime.
The technical scheme of the invention utilizes the supermolecule effect (mainly hydrophobic aggregation) between the nonpolar macroporous resin and the polyamidoxime to ensure that the PAO can be firmly loaded on the surface of a pore channel of the nonpolar macroporous resin. Due to the ultrahigh specific surface area and porosity of the microporous resin, almost all amidoxime groups can be exposed and then efficiently participate in the uranium adsorption process. In addition, the micron-sized non-polar macroporous resin particles can be easily filled into the adsorption column and efficiently filter seawater, which can also greatly improve the adsorption rate and avoid the adhesion of various marine microorganisms.
As a preferable scheme, the polyamidoxime is uniformly dispersed on the surface of the macroporous resin and in the pore channels of the macroporous resin.
As a preferable scheme, the nonpolar macroporous resin is macroporous resin D101, macroporous resin HP-20, macroporous resin HPD-300, macroporous resin NKA or macroporous resin AB-8. The nonpolar macroporous resin and the polyamidoxime can firmly adsorb the polyamidoxime on the surface of the nonpolar macroporous resin and the inner surface of a pore through supermolecular action.
In a preferable embodiment, the mass ratio of the polyamidoxime to the nonpolar macroporous resin is 3-25: 100, and more preferably 15-20: 100. Most preferably 17.8: 100. The polyamidoxime and the nonpolar macroporous resin need to be controlled in a proper proportion range, if the polyamidoxime is in an excessively high proportion, the pore diameter of the nonpolar macroporous resin is blocked, the filtering function is reduced, and the uranium enrichment process in seawater is difficult to meet.
The invention also provides a preparation method of the uranium adsorption material, which comprises the step of dipping the nonpolar macroporous resin in the polyamidoxime alkaline aqueous solution to obtain the uranium adsorption material.
In a preferred embodiment, the concentration of the polyamidoxime in the basic aqueous polyamidoxime solution is 10-50 mg/mL, and the pH is 9-11.
Preferably, the dipping time is 8 to 16 hours.
The invention also provides an application of the uranium adsorption material, which is applied to adsorption recovery of uranium in seawater.
Preferably, the pH of the seawater is 4-9.
The Polyamidoxime (PAO) of the invention is synthesized according to the prior published literature by the following specific steps: first, in a heated round-bottom flask in a water bath at 45 ℃, NH was added to the round-bottom flask2OH HCl (10.88 g, 150mmol) was dissolved in DMF (100.0 mL). Then Na was slowly added2CO3(9.54g, 90mmol) and NaOH (2.40g, 60 mmol). After stirring with a magnetic stirrer for 2 hours, PAN (6.36g, 120mmol) was added and dissolved completely for at least 30 minutes, followed by reaction at 65 ℃ for 24 hours. Finally, DMF (50mL), NH2OH·HCl(4.2g，60mmol)，Na2CO3(3.82g, 36mmol) and NaOH (0.86g, 24mol) were added to a round bottom flask and the reaction was continued at 65 ℃ for 24 hours. The reaction mixture was centrifuged at 10000r/min for at least 10 minutes, and then the supernatant was dropped into 900mL of ultrapure water to precipitate a white powder. After filtration and collection, the precipitate was dried in vacuo at 55 ℃ for 24 hours to obtain the prepared PAO, which was soluble in 0.3mol/L NaOH (FIG. 5).
The preparation method of the polyamidoxime-supported macroporous resin (PLMR) specifically comprises the following steps: 100 mL of macroporous resin D101, HP-20, HPD-300, NKA or AB-8 was immersed in 3mL of a PAO basic aqueous solution (10-50 mg/mL, pH. apprxeq.10) and shaken for 12 h. The PLMR composite particles (white) were washed with alkaline water (pH 8) and kept in ultrapure water at 0-5 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the technical proposal of the invention is to use the macroporous adsorption tree with larger specific surface area and porosityAnd the PAO is loaded on the surface of the macroporous resin and the inner surface of the pore of the macroporous resin by utilizing the supermolecular force, almost all amidoxime groups of the PAO can be exposed due to the ultrahigh specific surface area and porosity of the macroporous resin, and then the PAO efficiently participates in the uranium adsorption process, so that the PLMR formed by the nonpolar macroporous resin loaded with the polyamidoxime has ultrahigh-efficiency uranium adsorption performance. The PLMR is adsorbed in high-concentration seawater (32ppm) added with uranium for 72 hours, and the adsorption quantity (U) of the PAO to the seawater is increasedPAO) Up to 995 +/-39 mg/g, and the uranium element adsorption quantity (U) of the composite material (PLMR) with PAO loaded on macroporous resinPLMR) Reaching 150 +/-5.9 mg/g. After 10 times of adsorption and elution cycles, the adsorption efficiency can reach 517 +/-21.3 mg/g in the standard solution concentration of uranium-added pure water of 16 ppm.
In addition, the adsorption of uranium is realized by filtering natural seawater through a filling column mode by using a uranium adsorption material rarely in the prior art, and the PLMR takes macroporous resin in the prior art as a carrier, macroporous resin particles can be easily filled into the adsorption column and efficiently filters the seawater, so that the adsorption rate can be greatly improved, the adhesion of various marine microorganisms is avoided, the adsorption column can be directly used for recycling seawater uranium, and after 120 hours, the uranium absorption capacity of the polyamidoxime can be greatly improved to 1039 +/-46 mg/g when the uranium-added seawater standard solution concentration is 32 ppm. In a large-scale offshore experiment, the PLMR shows ultra-efficient uranium adsorption performance, and 90.6 +/-2.1 percent of uranium in 1000mL of seawater can be removed after filtering for 48 hours by 200mg of PLMR. More importantly, after 200g of seawater is filtered by the PLMR, the uranium adsorption capacity of the PAO can reach 14.16 +/-1.39 mg/g within 10 days, and the average daily adsorption efficiency of the PAO is 1.416mg/g which is far higher than that of the existing PAO-based adsorbent.
The uranium adsorption material has high selectivity for adsorbing uranium in seawater, and the adsorption quantity of the uranium adsorption material to other metal elements is far lower than that of uranium.
The preparation method of the uranium adsorption material is simple, low in cost and beneficial to large-scale popularization and application.
The uranium adsorption material provided by the invention has good device performance and chemical stability, and still has good adsorption performance in a repeated use process.
Drawings
Fig. 1, a is a schematic diagram of a PLMR preparation process, which is to soak an original macroporous resin in a PAO solution to prepare a PAO-loaded resin, so as to simply and rapidly prepare an engineering uranium adsorbent; b is N2DTG curves for PAO, PLMR and U-PLMR under atmosphere; c is the pore size distribution of the original resin, 17.8/100 and 22.6/100 composite resin. d is the FT-IR spectrum of PAO, Resin and PLMR; e is SEM image showing virgin, 17.8/100 and 22.6/100 composite resins; f is PLMT adsorption isotherm and pore size distribution (insert) data under a nitrogen atmosphere; g is the XPS spectra for PLMR (mPAO/mResin ═ 17.8/100), U-uptake and PLMR and uranyl ions.
Fig. 2, a shows that the nonpolar macroporous resin obtains PLMRs with different mass ratios in polyamidoxime-based alkaline solutions with different concentrations, and the PAO uranium extraction efficiency of the PLMR in the standard solution concentration of uranium-added seawater of 32ppm and the uranium absorption performance of the whole material are shown; b and c are SEM images and EDS energy spectra of PLMR and U-PLMR; d and e are kinetic data of uranium adsorption in PLMR (17.8/100) in (8ppm, 16ppm, 32ppm) plus U seawater and uranium adsorption capacity of the pseudo second order model; f is the pH dependence of PLMR adsorption in (16ppm) uranium added seawater; g is the adsorption selectivity (100 times of the natural seawater in U, V, Co, Ni, Fe and Cu) of PLMR on uranyl ions tested by the PLMR in simulated seawater adsorption for 48h, namely Na, Mg, Ca and K; h is the adsorption capacity (purple column) and the elution recovery rate (red column) of uranium for 10 adsorption-desorption cycles, (eluent Na)2CO3 1.0M，H2O2 0.1M)。
FIG. 3, a is a built resin seawater filtering experimental facility; b is the removal rate of PLMR (200mg) to a standard solution of 100ppb of uranium-added pure water; c is the uranium element removal rate of PLMR (200mg) in natural seawater; d is that PLMR is circularly used in natural seawater for 10 times of adsorption and desorption.
Fig. 4, a is a large-scale experiment for recovering uranium from natural seawater, b is an adsorption column at the beginning of an adsorption column filtration natural seawater experiment and after the experiment is finished, and c is uranium and vanadium adsorption of PLMR (mPAO/mrein ═ 17.8/100) in natural seawater in 10 days by a seawater filtration and adsorption system.
FIG. 5, a is the chemical equation for the synthesis of neutral PAO; b is the conversion of water insoluble PAO to water soluble PAO containing negative charge.
FIG. 6, sectional SEM image and EDS energy spectrum of U-PLMR material adsorbed in a (32ppm) solution of uranium added seawater for 5 days.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The raw materials adopted in the following specific examples are all common commercial raw materials on the market:
polyacrylonitrile (PAN, 98.5%), hydroxylamine hydrochloride (NH)2OH HCl, 98.0%), N, N-dimethylformamide (DMF, 99.8%), sen (III) (95.0%), H2O2(30.0%), hydrochloric acid (HCl), sodium hydroxide (NaOH, 97.5%) from Macklin (12.0 mol/L). Sodium chloride (NaCl, 99.5%), sodium carbonate (Na)2CO397.5%), ammonium vanadate (NH)4VO3·xH2O, 99.5%), Nickel chloride hexahydrate (NiCl)2·6H2O, 99.0%), iron chloride hexahydrate (FeCl)3·6H2O, 99.5%), copper sulfate pentahydrate (CuSO)45H2O, 99.5%) and ethanol (C)2H5OH, 99.9%) was purchased from west longe technologies ltd (shantou, china). Five macroporous adsorbent resins (HP-20, D101, HPD-300, NKA and AB-8) were purchased from and incorporated into New Material science and technology Inc. (Zheng, China). Uranium nitrate hexahydrate [ UO2(NO3)2·6H2O， 99％]. Cobalt chloride hexahydrate (CoCl)2·6H2O, 99%) was from chu sheng wafer chemical limited (wuhan, china). All chemicals were used as received. All natural seawater is collected from the seaside of Wanning City in Hainan province of China, and can be used after being filtered by fine sand.
Synthesis of Polyamidoxime (PAO):
according to the published literature, poly (amidoximes) (PAOs) were synthesized. First, in a heated round-bottom flask in a 45 ℃ water bath, NH was added to the round-bottom flask2OH·HCl(10.88g，150mmol) was dissolved in DMF (100.0 mL). Then Na was slowly added2CO3(9.54g, 90mmol) and NaOH (2.40g, 60 mmol). After stirring with a magnetic stirrer for 2 hours, PAN (6.36g, 120mmol) was added and dissolved completely for at least 30 minutes, followed by reaction at 65 ℃ for 24 hours. Finally, DMF (50mL), NH2OH·HCl (4.2g，60mmol)，Na2CO3(3.82g, 36mmol) and NaOH (0.86g, 24mol) were added sequentially to a round bottom flask and the reaction was continued at 65 ℃ for 24 hours. The reaction mixture was centrifuged at 10000r/min for at least 10 minutes, and then the supernatant was dropped into 900mL of ultrapure water to precipitate a white powder. After filtration and collection, the precipitate was dried in vacuo at 55 ℃ for 24 hours to obtain the PAO prepared, which was soluble in 0.3mol/L NaOH.
Preparation of amidoxime-supported macroporous resin (PLMR) the polyamidoxime-supported macroporous resin (PLMR) is prepared by adopting a supramolecular interaction method. 100mg of macroporous resin D101, HP-20, HPD-300, NKA or AB-8) was immersed in 3mL of Polyamidoxime (PAO) alkaline aqueous solution (10-50 mg/g, pH 10, shaking for 12h on a shaker to obtain PLMR of different PAO loadings at different concentrations). As shown in fig. 1a, PLMR composite particles (white) were washed with alkaline water (pH 8) and then maintained in ultrapure water at 0 to 5 ℃.
TABLE 1 PAO adsorption amounts (40 mg/g of basic aqueous solution, pH. apprxeq.10) and uranium extraction amounts in (32ppm) uranium added seawater solutions for different macroporous resins
Figure BDA0002748452090000071
FTIR spectral analysis was collected from Perkin-Elmer LR-64912C (FT-IR, LR 64912C, Perkin-Elmer, USA). Ultraviolet-visible (UV-Vis) absorption spectra were recorded on a spectrophotometer (UV1800PC, AuCy Instrument, china). Calibration of binding energy was performed by X-ray photoelectron spectroscopy (XPS, Thermo ESCALAB 250XI, Thermo Electron Corporation, u.s.a) using the C1s peak at 284.82 eV. The 13C-NMR spectra were determined with Bruker Advance III 600M (Bruker AVANCE III 600M, Bruker, Germany). The specific surface area is measured by Brunauer-Emmett-TelDetermination of pressure P/P by the ler (BET) equation0And (3) a range. The pore size distribution curve was determined by using the equation isotherm Barrett-Joyne-Halenda (BJH) method. Energy Dispersive Spectroscopy (EDS) images consisted of Hitachi S-4800 field emission scanning electron microscopy (Japanese SEM). The pH value was measured by means of a pH meter (Metler-Tollido F2, Germany). Inductively coupled plasma mass spectrometry (ICP-MS, Agilent 7500ce, usa) was used to measure the adsorption capacity of uranyl ions and other metal ions in solution.
Calculation of uranium adsorption amount
The uranium absorption capacity of PLMR supramolecular composites can be calculated according to equation (1):
UPLMR＝WU/WPLMR (1)
wherein U isPLMR(mg/g) is the uranium absorption capacity of PLMR, WUAnd WPLMRThe uranium adsorption mass of the composite resin and the mass of the PLMR composite resin, respectively.
The adsorption capacity of PAO for uranium can be calculated by the following equation (2):
UPAO＝WU/WPAO (2)
wherein U isPAOIs the uranium adsorption capacity, W, of PAOUAnd WPAORespectively uranium adsorption mass and PAO.
The U adsorption kinetics of the resin can be described by the pseudo second order kinetic model equation (3):
Figure BDA0002748452090000081
wherein q istAnd q iseThe adsorption capacity (mg. g) of uranium during contact and equilibrium, respectively-1) Is the uranium adsorption capacity (mg. g) at a specific time-1). Adsorption rate constant k2[g·(mg-1·min)](ii) a t is contact time [ min ]]。
Characterization of PAO-loaded macroporous resin (PLMR):
polyamidoxime (PAO) synthesized from polyacrylonitrile was characterized by Fourier transform infrared spectroscopy (FT-IR).After the reaction was complete, PAN at 2246cm, as shown by d in FIG. 1-1The characteristic adsorption peak of the nitrile group (-C is equal to N) disappears completely. Instead, -C ═ N and-N-C-were each at 1654cm-1And 933cm-1Two distinct peaks appear, indicating that-C ≡ N has been converted to amidoxime and that the PAN to PAO conversion has been completed. In addition, the FT-IR spectrum of the prepared PLMR also showed the same characteristic peaks for Amidoxime (AO) -C ═ N and-N-O- (d in fig. 1), indicating that PAOs had been well dispersed into the composite resin. The adsorption properties of the hydrogel to uranium can be confirmed by x-ray photoelectron spectroscopy (XPS) (fig. 1 g). XPS spectra (UO) of uranyl ions2 2+) The original PLMR has no dual characteristic peak uranium-spiked UO2 2+The solution after adsorption, the specific double peaks (399.87eV,399.14eV) of the XPS spectrum of PLMR is evident in the adsorbed uranium (VI) (UO) representing the composite resin2 2+)。
In fig. 1 b shows thermogravimetric (DTG) curves of the original PAN, PAO and PLMR, which show the weight loss of the resin as a function of temperature. Different forms of materials have different characteristic peaks, with the peaks for PAN being significantly different from those for PAO, indirectly indicating that PAN undergoes a material transition. PAO loading on macroporous resins was demonstrated by comparing PAO and PLMR curves. In FIG. 1 f, at N2The porosity of the sample was verified by isothermal adsorption testing under atmosphere and the test results showed that the PLMR (mPAO/mResin ═ 17.8/100) Brunel-Emmett-Teller (BET) surface area was 578.3. + -. 61m2g-1. This is far higher than any form of amidoxime-based composite material reported at present. The calculated Barrett-Joyner-Halenda (BJH) pore volume of PLMR was 1.59cm3g-1With an average pore size of 13.10nm, the inset shows the pore size distribution of icurve. The very large specific surface area and various types of pore sizes promote diffusion of seawater and uranyl ions into the adsorbent. Meanwhile, the method for filtering seawater is adopted, so that the relative contact area between seawater and amidoxime groups is increased, and the adsorption efficiency of the resin is greatly improved. When immersed in PAO solutions of different concentrations, the mass of PAO loaded on the macroporous resin is not equal, and it will have a certain influence on the pore size distribution of the macroporous resin (figure)1, c). The loading of PAO increases and PAO may enter the pore volume and change the pore size distribution. The SEM photograph (e in fig. 1) shows that when mPAO/mrein is 17.8/100, the pores are not significantly changed, the pore structure of the nonpolar macroporous resin still exists, the adsorption is maintained at the molecular level, when mPAO/mrein is 22.6/100, the sample state has significant filament formation, pore blocking behavior and polymerization of PAO solution filaments are observed, and the uranium adsorption efficiency of PAO cannot be reflected in a short time. Uranium is rapidly extracted from seawater. As shown in the electron micrograph, there was no significant change after PAO adsorption by the virgin resin and before and after uranium adsorption by the composite resin. The pore diameters before and after adsorption are kept unchanged. The resin was immersed in the PAO solution. The surfaces of the pores and the channels adsorb a layer of PAO material. The resin has no adsorption capacity to uranium element, but has a large number of channels and a high specific surface area. The PAO is uniformly loaded in the pore canal and the surface of the macroporous resin through supermolecule acting force, and the efficiency and the capacity of absorbing uranium by the PAO are obviously improved under the action of the resin. The resin is widely applied to industrial production, has strong regeneration capacity and good mechanical property, and is repeatedly applied on a large scale for many times.
Adsorption performance of PLMR on uranium: as shown in a in FIG. 2, U is present at a PAO concentration of 10 to 50mg/mlPLMRAnd UPAOAdsorbing uranium element. The uranium extraction efficiency of the PAO loaded resin is compared by screening composite resins loaded with different masses of PAO, and the optimal ratio PLMR is selected to be mPAO/mResin which is 17.8/100. When the solubility of the PAO alkaline aqueous solution is 40mg/mL, 17.8mg of PAO can be adsorbed on the resin with the mass of 100 mg. In (32ppm) natural seawater with added uranium, UPAOAnd UPLMRThe adsorption capacity of the adsorbent can reach 995 +/-31 mg/g and the adsorption time of 150 +/-5.9 mg/g is 72 hours. In FIG. 2, the adsorption time of the composite resin is 120 hours, UPAOCan reach 1039 +/-46 mg/g, UPLMRCan reach 157 +/-7.1 mg/g, and the adsorption reaches the balance. The PAO is loaded on the macroporous resin, the uranium extraction efficiency is rapidly enhanced, and the method is favorable for improving the high-efficiency utilization of the PAO and the large-scale and low-cost production
PLMR was adsorbed in (32ppm) uranium added seawater for 5 days. By SEM pictures and energy spectrometer(EDS) map (b in fig. 2), it can be seen that specific signal points of a large amount of uranium are uniformly distributed on the surface of PLMR (red), and SEM and EDS curves of PLMR in fig. 6 show that specific signal points of uranium element gradually decrease from the surface to the inside, indicating that PAO has also entered macroporous resin, which supports the rapid uranium extraction performance of PAO and indirectly increases the specific surface area of PAO in contact with seawater, improving the adsorption performance of PAO on uranium. PLMR can uniformly adsorb uranium in natural seawater, and is a promising adsorbent for extracting uranium from uranium. The pH of the external environment will significantly affect the uranium extraction capacity of the amidoxime functionalized uranium adsorbent and of the PLMR (e in FIG. 2). PLMR (m)PAO/mResin17.8/100) provides rapid and high uranium capacity U in pure water solutions of (16ppm) added uranium at different pH 4-9, optimum pH 7PAO350 + -19.5 mg/g, 536 + -21.2 mg/g and 620 + -35.0 mg/g for 2 hours, 12 hours and 24 hours, respectively. Most importantly, PLMR continues to show good uranium adsorption capacity at pH 8 (close to that of natural seawater). At pH 8, over 2h, 12h and 24h, UPAOValues of 316 + -16.2 mg/g, 466 + -18.1 mg/g and 525 + -21.9 mg/g, respectively, were reached, which allowed PLMR to have the potential to extract uranium from seawater. In addition, at a pH of 5-6, PLMR can still generate higher UPAOThe value: 450 + -18.3 mg/g at pH 5 and 580 + -22.4 mg/g at pH 6 (24 h). These results indicate that PLMR can also be used to efficiently recover uranium from acidic uranium-containing wastewater and can be used on a large scale. The ion selectivity of the composite resin was tested in a simulated seawater environment (f in fig. 2). Seawater contains many competing elements [ vanadium (V), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), zinc (Zn), etc. ]]Please select natural seawater as the substrate to prepare the test solution, and increase the concentration of V, Co, Ni, Fe, Cu, U, etc. to 100 times of the initial concentration, while the concentration of other metal elements remains unchanged. After the PLMR was nitrated, the amount of each metal element adsorbed was detected by ICP-MS. Experiments show that in simulated seawater environment, although the adsorption capacity of vanadium is slightly higher than that of uranium, the composite resin has good selectivity on uranium, and the adsorption capacity of other metal elements is far lower than that of uranium. Through 10 adsorption-desorption cycles, measureRecoverable U of uranium adsorption of PLMR in 16ppm uranium-supplemented seawaterPAO(g in FIG. 2). The desorption solution was a mixed solution (500mL of 1.0M Na)2CO3And 0.1M H2Mixed solution of O2). The adsorption time is 72h, and the desorption time is 1 h. After 10 cycles, the adsorption capacity of uranium is 517 +/-21.3 mg/g, and the higher adsorption capacity is still maintained.
In fig. 3d is an experiment of trying 4.1ppb in natural seawater with low uranium concentration, and the adsorption efficiency of 10 times of recovery is more than 92.4%, which is enough to meet the requirement of multiple times of adsorption in seawater. The PLMR has higher recoverability in low-uranium-bearing seawater and higher applicability in large-scale exploration. To study the adsorption and filtration performance of PLMR, uranium-added pure water (100ppb) was used in the experiment when the uranium element was at a low level. The uranium element removal rate reaches 67.4 percent after 12h of filtering circulation (a in figure 3) and (b in figure 3) in the adsorption filtering device. The removal rate of water after 24 hours of adsorption reaches 91.1%. The pictures show the original PLMR and the color after 24 hours. The result shows that the PLMR can be used for seawater purification and trace element enrichment and adsorption. It is possible to make full use of uranium in seawater.
Extracting uranium element from natural seawater: the environment in natural seawater is very complicated and includes various bacteria and microorganisms, and thus it is difficult to determine the amount of uranium extracted from natural seawater. For this purpose, a small uranium sorption test was performed to evaluate the large amount of uranium recovered from natural seawater. The PLMR has good seawater filtering performance, 200mg of the PLMR is adsorbed into a circulating device (c in figure 3), the removal rate of uranium elements can reach 76.3% in 12 hours, the removal rate of natural seawater is 90.6% in 48 hours, the color of the PLMR before and after the picture and 48 hours change can be reduced to a lower level, the operation is simple, and the method has good prospects in large-scale water quality tests. Through large scale offshore experiments, PLMR was placed between two sponges in a column in a seawater circulation device with an adsorption column (a and b in fig. 4). Samples were taken every two days and 10 days (c in FIG. 4). All samples were nitrated and the uranium and vanadium content determined by ICP-MS. U for 4 daysPAOThe value was 8.83. + -. 0.99 mg. After using 200g of PLMRAfter filtering 200T seawater, UPAOCan reach 14.16 +/-1.39 mg/g within 10 days, and UPLMRThe adsorption capacity reaches 2.14 +/-0.21 mg/g, in a test, because the composite resin can obtain uranium in super-natural seawater, the absorption capacity is high, the material preparation cost is low, the macroporous resin material is widely used for industrial production, is firm and durable, has good reproducibility, and is expected to become an industrial production material, and the seawater is recycled to extract uranium. As a result, the adsorption amount of vanadium was gradually higher than that of uranium with the lapse of time, and the adsorption amount of PAO reached 15.83. + -. 1.38mg/g at 10 days. This remains a problem to summarize, the present invention loads PAO to the surface of macroporous resin by supramolecular forces by using macroporous adsorption resin with large specific surface area and porosity, and by selecting PLMR (m) of optimal loading ratioPAO/mResin17.8/100), adsorbing in high-concentration seawater (32ppm) added with uranium for 72 hours to reach the uranium extraction amount (U) of PAOPAO)995 +/-39 mg/g and the total uranium extraction amount (U) of PLMRPLMR) 150. + -. 5.9 mg/g. In 16ppm uranium-added seawater, the adsorption capacity of uranium can reach 517 +/-21.3 mg/g after 10 adsorption-desorption cycles of PLMR. In the past, the adsorption mode of filtering uranium in natural seawater in a loading adsorption column which can adopt a filler is rare, in the test, uranium element in the natural seawater is circulated for 48 hours under the condition of circulating 200mg of adsorbent, the removal rate reaches 90.6%, in a large-scale offshore test, 200g PLMR is used for recovering and filtering 200 tons of natural seawater in total, and U is used for 10 daysPAO14.16. + -. 1.39mg/g, UPLMRIt was 2.14. + -. 0.21 mg/g. The composite resin provides a novel, fast and efficient adsorbent for large-scale extraction of uranium with low cost, and extraction of uranium from seawater can be engineered. The macroporous adsorption resin is widely used for traditional Chinese medicine extraction and sewage treatment, has good device performance and chemical stability, and still has good adsorption performance in the process of repeated use.

Claims (8)

1. A uranium adsorbent material, characterized in that: the polyamide resin is formed by loading polyamidoxime on nonpolar macroporous resin.
2. A uranium adsorbent material according to claim 1, wherein: the polyamidoxime is uniformly dispersed on the surface of the nonpolar macroporous resin and in the pore channels of the nonpolar macroporous resin.
3. A uranium adsorbent material according to claim 1, wherein: the nonpolar macroporous resin is macroporous resin D101, macroporous resin HP-20, macroporous resin HPD-300, macroporous resin NKA or macroporous resin AB-8.
4. A uranium adsorbent material according to any one of claims 1 to 3, wherein: the mass ratio of the polyamidoxime to the nonpolar macroporous resin is 3-25: 100.
5. A method of preparing a uranium adsorbent material according to any one of claims 1 to 4, wherein: and (3) dipping the nonpolar macroporous resin in a polyamidoxime alkaline aqueous solution to obtain the polyamide resin.
6. A method of producing a uranium adsorbent material according to claim 5, wherein: the concentration of the polyamidoxime in the polyamidoxime alkaline aqueous solution is 10-50 mg/mL, and the pH is 9-11.
7. A method of producing a uranium adsorbent material according to claim 5, wherein: the dipping time is 8-16 hours.
8. Use of a uranium adsorbent material according to any one of claims 1 to 4, wherein: the method is applied to adsorption recovery of uranium in seawater.
CN202011174988.5A 2020-10-28 2020-10-28 Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater Pending CN112547026A (en)

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