Recovery of Uranium from Seawater by Immobilized Tannin

Abstract

Tannin compounds having multiple adjacent hydroxy groups have an extremely high affinity for uranium. To prevent the leaching of tannins into water and to improve the adsorbing characteristics of these compounds, we tried to immobilize tannins. The immobilized tannin has the most favorable features for uranium recovery; high selective adsorption ability to uranium, rapid adsorption rate, and applicability in both column and batch systems. The immobilized tannin can recover uranium from natural seawater with high efficiency. About 2530 μg uranium is adsorbed per gram of this adsorbent within 22 h. Depending on the concentration in seawater, an enrichment of up to 766,000-fold within the adsorbent is possible. Almost all uranium adsorbed is easily desorbed with a very dilute acid. Thus, the immobilized tannin can be used repeatedly in the adsorption-desorption process.     

Recovery of uranium by tannin immobilized on agarose

Tannin, which is a ubiquitous and inexpensive material, was immobilized on agarose gel to produce an excellent adsorbent for uranium recovery from seawater. Optimal conditions for the immobilization of tannin on agarose gel by both the epichlorohydrin and cyanuric chloride coupling procedures were examined in detail. The resulting immobilized tannin has a highly selective ability to adsorb uranium and applicability in both column and batch systems. This adsorbent can recover uranium from natural seawater with high efficiency. The maximum adsorption capacities were 1850 μg uranium g^?1 adsorbent for the tannin immobilized on agarose gel by the epichlorohydrin coupling procedure and 1062 μg g^?1 adsorbent for that produced by the cyanuric chloride coupling procedure.     

球形聚合单宁-纤维素树脂的制备及吸附性能

单宁与多聚甲醛交联合成单宁酚醛聚合物,再以环氧氯丙烷为交联剂,将单宁酚醛聚合物与纤维素通过反相悬浮交联制备球形聚合单宁-纤维素树脂。通过傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）对球形聚合单宁-纤维素树脂的结构进行了表征,并考察了球形聚合单宁-纤维素树脂对盐酸小檗碱的吸附性能。结果表明,球形聚合单宁-纤维素树脂具有多孔的结构,树脂网络中含有大量的酚羟基;球形聚合单宁-纤维素树脂对盐酸小檗碱具有较好的吸附性能,当盐酸小檗碱浓度为600 mg·L^-1、吸附温度为298 K时,最大饱和吸附量可达245.92mg·g^-1;球形聚合单宁-纤维素树脂对盐酸小檗碱的吸附过程符合Langmuir吸附等温模型和准二级吸附动力学方程,热力学研究数据表明球形单宁-纤维素树脂对盐酸小檗碱的吸附是一个自发放热的物理吸附过程。该树脂在分离提纯生物碱方面具有潜在的应用前景。     

A New Type of Amidoxime-Group-Containing Adsorbent for the Recovery of Uranium from Seawater

Abstract

A new type of adsorbent containing amidoxime groups for the recovery of uranium from seawater was synthesized by the radiation-induced graft polymerization of acrylonitrile onto polymeric fiber followed by amidoximation with hydroxylamine. When amidoxime groups were introduced superficially on the fiber, the amount of uranium adsorbed by the amidoxime groups was higher than that with the amidoxime groups introduced homogeneously in the fiber. The introduction of the poly(acrylic acid) chain and the increase in temperature and flow rate in the adsorption process were effective in increasing the amount of adsorbed uranium. Although alkali metals and alkaline earth metals were found in the adsorbent, the concentration factors for these metals were less than 1/10³ of that for uranium. The present adsorbent had a high stability to various treatments such as contact with alkali and seawater.     

Development of Sorbers for the Recovery of Uranium from Seawater. 1. Assessment of Key Parameters and Screening Studies of Sorber Materials

Abstract

At an average uranium content of 3.3 ppb the oceans can be considered as a very low-grade but practically unlimited source of uranium. Some essential chemical aspects of a large-scale sorptive recovery of uranium from seawater are discussed with special emphasis on required sorber properties such as high physical and chemical stability in seawater, fast and selective uptake of uranium, as well as a sufficient loading capacity. Systematic screening tests, including about 200 sorber materials on the basis of organic ion-exchange resins, identified cross-linked poly(acrylamidoximes) as the most promising candidate sorbers. Their uranium uptake closely approaches the uranium content of actually explored uranium ores.     

New and simple synthetic strategy for two-dimensional ultra-microporous aromatic framework for selective uranium capture in liquid

Uranium is a key element to improve nuclear energy demands, and thereby the extraction of uranium from seawater is a strategic way to address uranium sustainability. Herein, a novel two-dimensional porous aromatic framework (AO-PAF), which possesses an ultra-microporous architecture with an ordered structure, excellent stability and selectivity of uranium extraction from a liquid phase. AO-PAF shows excellent uranium adsorption capacities of 637 (mg/g) and 3.22 (mg/g) in simulated and natural seawater attributable to the selective uranium coordinating groups on highly accessible pores on the walls of open channels. In addition, benefiting from the super-hydrophilicity due to the presence of amidoxime groups attributes high selectivity and ultrafast kinetics with an uptake rate of 0.43 ± 0.03 (mg/g·day) and allowing half-saturation within 1.35 ± 0.09 days. This strategy demonstrates the potential of PAF not only recovery of uranium and can be extended for other applications by sensible planning of target ligands.     

Recovery of Uranium from Seawater

Abstract

Seawater contains various elements in solution. Deuterium, lithium, and uranium are the important ingredients for energy application at present and in the future. This paper deals with the recovery of uranium from seawater, with emphasis on the development of an adsorbent with high selectivity and rate of adsorption for uranium.

Polyacrylamidoxime chelating resins were synthesized from various co-polymers of acrylonitrile and cross-linking agents. The resulting resins with the chelating amidoxime group showed selective adsorption for uranium in seawater. The amount of uranium adsorbed from seawater at room temperature reached 3.2 mg/g resin after 180 days.

Polyacrylamidoxime fiber, which was prepared from polyacrylo-nitrile fiber and hydroxylamine, showed a high rate of adsorption for uranium. The polyacrylamidoxime fiber conditioned with 1 M HCl and 1 M NaOH adsorbed 4 mg U/g fiber from seawater in ten days.     

Performances of larch (larix gmelini) tannin modified urea–formaldehyde (TUF) resin and plywood bonded by TUF resin

Tannin from larch (Larix gmelini) bark extracts, as a natural renewable resource, was used to prepare tannin–urea–formaldehyde (TUF) resin. The chemical structures of larch tannin and TUF resin were characterized by matrix‐assisted laser desorption/ionization‐time of flight mass spectrometry and ¹³C nuclear magnetic resonance. The thermal behaviors of TUF resin were evaluated by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA). The performances of TUF resin were investigated by measuring the bond strength and formaldehyde emission of its bonded plywood. It was clearly shown that larch tannin is mainly composed of prodelphinidin repeating units. Phenolic groups were introduced into TUF resin mainly linked by methylene bond. Larch tannin has an adverse effect on the resin curing. However, it promoted the rigidity and flexibility of the glued system and upgraded the properties of plywood. Therefore, larch tannin could be applied in the modification of urea–formaldehyde resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41064.     

Effect of Ultrasonic Irradiation on the Recovery of Uranium from Seawater with Adsorbents

Abstract

Ultrasonic irradiation is reported to promote chelate formation between metal ions and polymeric ligands in solution (1). It is expected that the recovery of uranium from seawater with adsorbents is affected by ultrasonic irradiation because this process is also based on chelation between the ligands of the adsorbent and uranyl ion in seawater. In the present note, adsorption of uranium from seawater was carried out under ultrasonic irradiation with an amidoxime-group-containing polymeric adsorbent.     

Optimal amidoximation conditions of acrylonitrile grafted onto polypropylene by photoirradiation-induced graft polymerization

To prepare amidoxime (AO) adsorbents for uranium recovery from seawater, the optimum conditions for graft polymerization and amidoximation of acrylonitrile (AN) group and alkaline treatment of the AO group have been investigated in terms of the uranium adsorption capacity. AN has been grafted onto polypropylene (PP) fabric by photoirradiation-induced graft polymerization with benzophenone as the photoinitiator. A concentration of AN ≤1.0M, a photoirradiation time of 2 h, and a reaction temperature of 60°C proved to be optimal for the grafting of AN onto PP. The grafted AN groups were effectively converted into AO groups upon reaction with ≥5.0% (w/v) hydroxylamine solution at pH 7.0−9.0 for ≥16 h at 60−80°C. Although widely used for this purpose, we have shown that methanol is not an essential solvent for the amidoximation reaction. Conditioning of the AO group with KOH solution (alkaline treatment) proved to be effective for enhancing the uranium adsorption capacity of amidoximated PP-g-AN-AO fabric, which increased logarithmically with the conditioning time. The AO group density in the PP-g-AN-AO fabric increased linearly with the degree of AN grafting, whereas the uranium adsorption capacity of PP-g-AN-AO fabric conditioned with KOH reached a maximum at a degree of AN grafting of approximately 60%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs

The recovery of uranium (U) from seawater has been investigated for over six decades in efforts to secure uranium sources for future energy production. The majority of the research activities have focused on inorganic materials, chelating polymers, and nanomaterials. Previous studies of uranium adsorption from aqueous solutions, mainly seawater, are reviewed here with a focus on various adsorbent materials, adsorption parameters, adsorption characterization, and marine studies. Continuous progress has been made over several decades, with adsorbent loadings approaching 3.2 mg U/g adsorbent in equilibrium with seawater. Further research is needed to improve first, the viability including improved capacity, selectivity, and kinetics, and second, the sorbent regeneration for multicycle use. An overview of the status of the uranium adsorption technology is provided and future research needs to make this technology commercially competitive are discussed.     

Recovery of uranium from seawater. XII. Preparation and characterization of lightly crosslinked highly porous chelating resins containing amidoxime groups

A number of lightly cross-linked poly(acrylonitrile-co-divinylbenzene) beads (RN-5) have been synthesized by suspension polymerization. The use of solvating diluents such as chloroform, dichloroethane, and tetrachloroethane resulted in copolymer beads having highly porous structures. The chelating resins containing amidoxime as a functional group (RNH-5) have been prepared by the reaction of copolymer beads with 3% hydroxylamine in methanol. A detailed analysis is made of the pore structure of lightly cross-linked copolymers of acrylonitrile–divinylbenzene and their amidoxime derivatives in the anhydrous state including pore-size distribution, specific surface area, and pore structure in the aqueous media by means of gel permeation chromatography (GPC). A set of experiments have been performed to ascertain the potential of the resins for the adsorption of uranium from seawater. Because of their modified pore structures, the chelating resins exhibited a marked adsorption rate for uranium in seawater as high as 23 μg of U/cm³ of resin/day without alkaline treatment.     

Radial diffusion method for determining tannin in plant extracts

Tannin in plant extracts can be determined by reacting the tannin with a protein and quantitating the precipitated complex. In the new assay described here, a tannin-containing solution is placed in a well in a protein-containing agar slab. As the tannin diffuses into the gel and complexes with protein, a visible ring of precipitation develops. The area of the ring is proportional to the amount of tannin in the extract. The detection limit of the method is 0.025 mg tannic acid or condensed tannin and the precision is 6% (relative standard deviation). Tests with extracts of a variety of plants show that the new method gives results comparable to other precipitation methods and that the new method is superior for samples of unusual composition, such as aspen buds. The method has several advantages over other methods for determining tannin: The new method is very simple and requires neither complex reagents nor instruments. Components of the plant extract such as non-tannin phenolics or water-insoluble compounds do not interfere with the method. The assay is not subject to interference from the organic and aqueous solutions which are commonly used to extract tannin from plants.     

Selective Elution of Uranium from Amidoxime Polymer. II

Abstract

A separative elution of uranium from an amidoxime polymer which had been immersed in seawater was examined on its relation with the flow rate of acidic eluent. The elution with 0.5 M HC1 at S.V. ≤ 1 h^?1 or with 1.0 M HCl at S.V. ≤ 3 h^?1, which was started from the elution by 16.5 L/L _p of 0.1 MHCl at S.V. ≤ 3 h^?1, provided an eluate containing more than 80% of uranium adsorbed and separating from other metal ions except Fe(III) and Cu(II). The efficiency of uranium elution was hardly affected by the scale of the system employed. Acid consumption, which occurred predominantly in the elution with 0.1 M HCl, was ～1.4 mol/L _p . The results suggest that this elution method is promising in the recovery of uranium from seawater.     

Resistance and Tolerance of Terminalia sericea Trees to Simulated Herbivore Damage Under Different Soil Nutrient and Moisture Conditions

Resource availability, degree of herbivore damage, genetic variability, and their interactions influence the allocation of investment by plants to resistance and tolerance traits. We evaluated the independent and interactive effects of soil nutrients and moisture, and simulated the effects of herbivore damage on condensed tannins (resistance) and growth/regrowth (tolerance) traits of Terminalia sericea, a deciduous tree in the Kalahari desert that constitutes a major component of livestock diet. We used a completely crossed randomized-block design experiment to examine the effects of nutrients, water availability, and herbivore damage on regrowth and resistance traits of T. sericea seedlings. Plant height, number of branches, internode length, leaf area, leaf mass for each seedling, combined weight of stems and twigs, and root mass were recorded. Condensed tannin concentrations were 22.5 and 21.5% higher under low nutrients and low soil moisture than under high nutrient and high water treatment levels. Tannin concentrations did not differ significantly between control and experimental seedlings 2 mo after simulated herbivore damage. Tannin concentrations correlated more strongly with growth traits under low- than under high-nutrient conditions. No trade-offs were detected among individual growth traits, nor between growth traits and condensed tannins. T. sericea appeared to invest more in both resistance and regrowth traits when grown under low-nutrient conditions. Investment in the resistance trait (condensed tannin) under high-nutrient conditions was minimal and, to a lesser degree, correlated with plant growth. These results suggest that T. sericea displays both resistance and tolerance strategies, and that the degree to which each is expressed is resource-dependent.     

Uptake and recovery of gold by immobilized persimmon tannin

Some attempts were made to recover gold from aqueous systems using immobilized persimmon tannin. This adsorbent adsorbed gold from solutions containing hydrogen tetrachloroaurate(III) with high efficiency, whereas there was minimal adsorption from solutions containing gold(I) sodium thiomalate and sodium dicyanoaurate(I). The adsorption of gold was rapid, and was affected by the pH of the solution, temperature, external gold concentration and amount of adsorbent. Adsorbed gold was easily desorbed with 1 mol dm^?3 thiourea solution, indicating that immobilized persimmon tannin can be repeatedly re-used for the recovery of gold using adsorption-desorption cycles.     

Modifying biodegradable plastics with additives based on condensed tannin esters

Condensed tannins derived from Pinus radiata bark have been esterified and added to biodegradable plastics as extrusion compounded functional plastic additives. The presence of longer alkyl chain hexanoate esters promoted tannin miscibility in the commercial polyesters Bionolle? and Biopol? whereas short chain acetate esters tended to remain as discrete domains, acting as fillers in the processed plastics. In the aliphatic polyester Bionolle the presence of tannin esters at typical plastic additive loadings did not alter plastic mechanical properties whereas at 5% content in Biopol the tannin‐additives reduced both flexural and tensile properties. Similarly tannin esters do not alter the melt or glass transition temperatures of the polyesters, but tannin hexanoate at 5% can influence the crystallization temperatures. Artificially aging plastics realized the functionality these plant extracts can impart to plastics in acting to reduce ultraviolet (UV)‐induced plastic degradation. Results indicate the tannin‐additives likely provide a stabilising role through inhibiting UV penetration into the plastic, with color analysis suggesting the tannin moiety itself was sacrificial and preferentially degrading. The imparted UV stability was linked to the dissolution of tannin esters in the plastic with longer chain esters providing greater protection against UV degradation. Tannin esters showed potential as functional additives for biodegradable polymers enhancing the UV stability of the plastic. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41626.     

Design and Cost Studies on the Extraction of Uranium from Seawater

Abstract

For a country like Japan, which has very limited energy resources, nuclear power generation is an attractive energy option. However, since known domestic resources of uranium are limited, it is desirable to develop less-conventional uranium sources. To investigate the technical and economic feasibility of extracting uranium from seawater, a research program has been carried out since 1975 by the Metal Mining Agency of Japan, under sponsor-ship of the Ministry of International Trade and Industry. The program includes studies in the following research areas: chemical process selection, adsorbent development, continuous adsorption and elution performance, eluate recovery by steam stripping or electrodialysis, and secondary concentration of uranium in the eluate. Several site selections around the Japanese coast have been examined along with a comparison of various seawater contacting structures. Conceptual designs and tentative cost estimations have been conducted on two types of commercial plants: pumping and fixed bed, and direct sea current utilization. This paper summarizes the conceptual design and cost estimation results.     

Synthesis,characterization, and thermal behaviors of tannin stearates prepared from quebracho and pine bark extracts

Reported is the preparation of various condensed tannin stearates and the associated chemical characterization and thermal properties of these products. Stearate esters of condensed tannins from both quebracho and pine bark extracts were prepared in generally high, isolated yields from reaction with stearic acid chloride. Tannin esterification was confirmed by both Fourier transform infrared and nuclear magnetic resonance (NMR), and the average degree of stearate substitution was calculated from ¹H‐NMR analysis. Product degree of substitution (DS) was observed to proportionately increase with higher stearic acid chloride ratio with maximum DS values of 4.0 and 5.1 achieved for quebracho and pine tannins, respectively. Thermal analysis revealed that tannin stearate products have increased thermal stability with a degradation onset at significantly higher temperature for those samples possessing relatively greater DS. Analysis using differential scanning calorimetry revealed isolated products to consist of multiple components which exhibit interesting melt behaviors, a likely result from their work up on isolation. However, multiple melt features of the individual components in products were lost on heating to give single, broad melt endotherms due to coalescence of sample components. Furthermore, tannin stearate samples with high DS show relatively greater endothermic melting at higher temperature than those samples with lower DS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A new source of natural adhesive: Acacia mangium bark extracts co-polymerized with phenol-formaldehyde (PF) for bonding Mempisang (Annonaceae spp.) veneers

Acacia mangium is a fast-growing dicotyledonous tree species and has become the dominating plantation in Malaysia. It was grown particularly as a raw material for veneer, pulp, and paper industries. The chemical properties test in this study showed that the A. mangium tree bark contains higher extractive content as compared to the wood portion (sapwood). Tannin extracts from A. mangium tree bark were found to be rich in phenolic compounds and had the potential to replace conventional phenol-formaldehyde (PF) adhesive used in the plywood manufacturing industry. Tannin adhesive (tannin-paraformaldehyde) prepared from A. mangium bark tannin by cross-linking with paraformaldehyde were used for bonding of Mempisang (Annonaceae spp.) plywood board. However, the resulting bonding strength using tannin adhesive was found to be only suitable for interior grade application. Further extension of its application for interior and exterior grade plywood could be achieved with addition of PF (co-polymerization with resol) during the production process. The optimized formulation of tannin adhesive consists of A. mangium solid extracts (90 parts), commercial PF (10 parts), and paraformaldehyde (3%). Results have shown that the plywood shear strength complies with the requirement for European norms EN 314-1 and EN 314-2:1993, which includes the dry test, cold water test, and the boiling test.