Masao Tamada

Enhanced trace phosphate removal from water by zirconium(IV) loaded fibrous adsorbent

This study was investigated for the trace phosphate removal at high feed flow rate by ligand exchange fibrous adsorbent. The zirconium(IV) loaded bifunctional fibers containing both phosphonate and sulfonate were used as a highly selective ligand exchange adsorbent for trace phosphate removal from water. The precursory fiber of the bifunctional fibers was co-grafted by polymerization of chloromethylstyrene and styrene onto polyethylene coated polypropylene fiber and then bifunctional fibers were prepared by Arbusov reaction followed by phosphorylation and sulfonation. Phosphate adsorption experimental work was carried out in column approach. Phosphate adsorption increased with decreasing the pH of feed solutions. An increase in the feeds flow rate brings a decrease in both breakthrough capacity and total adsorption. The effect of competing anions on phosphate adsorption systems was investigated. The experimental findings reveal that the phosphate adsorption was not affected in the presence of competing anions such as chloride and sulfate despite the enhancement of the breakthrough points and total adsorption. Due to high selectivity to phosphate species, low concentration level of phosphate (0.22 mg/L) was removed at high feed flow rate of 450 h(-1) in space velocity. The adsorbed phosphate on the Zr(IV) loaded fibrous column was quantitatively eluted with 0.1 M NaOH solution and then the column was regenerated by 0.5M H2SO4 for the next adsorption operation. During many adsorption-elution-regeneration cycles, no measurable Zr(IV) was found in the column effluents. Therefore, the Zr(IV) loaded bifunctional fibrous adsorbent is to be an effective means to treat wastewater to prevent eutrophication in the receiving water bodies for long time without any deterioration.

Aquaculture of Uranium in Seawater by a Fabric-Adsorbent Submerged System

Abstract The total amount of uranium dissolved in seawater at a uniform concentration of 3 mg U/m3 in the world’s oceans is 4.5 billion tons. An adsorption method using polymeric adsorbents capable of specifically recovering uranium from seawater is reported to be economically feasible. A uranium-specific nonwoven fabric was used as the adsorbent packed in an adsorption cage 16 m2 in cross-sectional area and 16 cm in height. We submerged three adsorption cages in the Pacific Ocean at a depth of 20 m at 7 km offshore of Japan. The three adsorption cages consisted of stacks of 52 000 sheets of the uranium-specific non-woven fabric with a total mass of 350 kg. The total amount of uranium recovered by the nonwoven fabric was >1 kg in terms of yellow cake during a total submersion time of 240 days in the ocean.

A weak-base fibrous anion exchanger effective for rapid phosphate removal from water.

This work investigated that weak-base anion exchange fibers named FVA-c and FVA-f were selectively and rapidly taken up phosphate from water. The chemical structure of both FVA-c and FVA-f was the same; i.e., poly(vinylamine) chains grafted onto polyethylene coated polypropylene fibers. Batch study using FVA-c clarified that this preferred phosphate to chloride, nitrate and sulfate in neutral pH region and an equilibrium capacity of FVA-c for phosphate was from 2.45 to 6.87 mmol/g. Column study using FVA-f made it clear that breakthrough capacities of FVA-f were not strongly affected by flow rates from 150 to 2000 h(-1) as well as phosphate feed concentration from 0.072 to 1.6mM. Under these conditions, breakthrough capacities were from 0.84 to 1.43 mmol/g indicating high kinetic performances. Trace concentration of phosphate was also removed from feeds containing 0.021 and 0.035 mM of phosphate at high feed flow rate of 2500 h(-1), breakthrough capacities were 0.676 and 0.741 mmol/g, respectively. The column study also clarified that chloride and sulfate did not strongly interfere with phosphate uptake even in their presence of equimolar and fivefold molar levels. Adsorbed phosphate on FVA-f was quantitatively eluted with 1M HCl acid and regenerated into hydrochloride form simultaneously for next phosphate adsorption operation. Therefore, FVA-f is able to use long time even under rigorous chemical treatment of multiple regeneration/reuse cycles without any noticeable deterioration.

Fine Fibrous Amidoxime Adsorbent Synthesized by Grafting and Uranium Adsorption–Elution Cyclic Test with Seawater

Abstract Fibrous amidoxime adsorbents were prepared by radiation‐induced co‐grafting of acrylonitrile (AN) and methacrylic acid (MAA) and subsequent amidoximation. Adsorption of uranium in seawater was evaluated by pumping seawater into the adsorbent column. The best monomer ratio of AN and MAA was 7:3 for continual usage of uranium adsorption. Though hydrochloric acid is an effective eluting agent for the metals adsorbed on the adsorbent, amidoxime groups were simultaneously damaged after five cycles of adsorption–desorption. This deterioration was reduced by an alkaline treatment of the adsorbents after each elution. Furthermore, various organic acids were examined as elution agents. It was found that the 80% of adsorption activity was still maintained after five cycles of adsorption–desorption when tartaric acid was used for eluting agent.

Recovery of cadmium from waste of scallop processing with amidoxime adsorbent synthesized by graft-polymerization

Abstract Fabric adsorbent having amidoxime function was synthesized by radiation-induced graft-polymerization. This adsorbent was applied to the removal of Cd from the scallop waste. The scallop waste was homogenized as a pre-treatment. The obtained top layer was used for the Cd absorption experiment at various pH conditions. At pH 6, the adsorbent showed the highest performance in Cd adsorption. The concentration factor was thousand for Cd. Preliminary column experiment was also carried out. The amidoxime adsorbent recovered 96.1% of Cd in the waste solution.

Adsorption Efficiency of a New Adsorbent Towards Uranium and Vanadium Ions at Low Concentrations

Abstract A new type of fibrous adsorbent with excess amidoxime groups was synthesized by radiation-induced graft polymerization. Glycidyl methacrylate (GMA) was first radiation‐grafted on polyethylene‐coated polypropylene nonwoven fabrics and chemically modified with 3,3′-iminodipropionitrile [NH (–CH2–CH2–CN)2] (IDPN), which was further reacted with hydroxylamine to obtain graft chains containing two amidoxime groups per graft repeating units. The adsorption properties of this new adsorbent for uranium (U), vanadium (V), lead (Pb), copper (Cu), and cobalt (Co) ions at low concentrations (3.3–1000 ppb) were investigated by a batch process. The adsorbent showed enhanced adsorption capacity for uranium and vanadium ions. In adsorption studies from a mixture of metal ions in aqueous solutions, the adsorbent showed selectivity for metal ions in the following order: V > U ≫ Cu ≥ Pb ≫ Co. The selectivity of the adsorbent was assessed by determining the distribution coefficient D, of the metal ions studied. The U and V ions were shown to be up to six times more selectively adsorbed onto the new adsorbent than the other metal ions.

Preparation of polyvinylcarbazole thin film with vapor deposition polymerization

N-vinylcarbazole (NVCz) was evaporated toward a substrate of a glass slide coated with silver 100 nm thick with the existence of a redheated filament. The processes of vapor deposition polymerization (VDP) and annealing were observed with in-situ infrared reflection absorption spectroscopy. The filament temperature of 2300 K and the substrate temperature of 266 K were effective to retard the re-evaporation of deposited NVCz. After NVCz was deposited on the above conditions and then annealed at 285 K, the resulting VDP film had a number average molecular weight of 1.1 × 104 and a polymer yield of 88%.

High-speed recovery of antimony using chelating porous hollow-fiber membrane

A porous hollow-fiber membrane containing an iminodiethanol (IDE) group as the chelate-forming group was applied to the recovery of antimony in the permeation mode. An antimony solution was forced to permeate through the pores of the chelating porous hollow-fiber membrane, driven by a transmembrane pressure. The membrane with a thickness of 0.7 mm and a porosity of 70% had an iminodiethanol group of 1.6 mol/kg of the membrane and a water flux of 0.95 m/h at 0.1 MPa and 298 K. The breakthrough curves of antimony overlapped irrespective of the permeation rate of the antimony solution ranging from 2 to 20 ml/min, i.e. the residence time across the membrane thickness ranging from 3.4 to 0.34 s, because of negligible diffusional mass-transfer resistance of the ionic species of antimony to the iminodiethanol group. At antimony concentrations below 10 mg/l (pH 4.0), a linear adsorption isotherm was obtained. The adsorbed antimony was quantitatively eluted by permeation of 2 M hydrochloric acid through the pores of the membrane.

Convection-aided collection of metal ions using chelating porous flat-sheet membranes

Chelating porous membranes were prepared by radiation-induced graft polymerization of an epoxy-group-containing monomer onto a polyethylene flat sheet and subsequent conversion of the epoxy group to an iminodiacetate group as a chelate-forming group. The chelating group density on the resultant porous flat-sheet membrane of 1.0 mol/kg was comparable to that of commercially available chelating beads. The pure water permeability of the membrane was 40% that of the trunk porous membrane, which was used for microfiltration. During the permeation of a copper chloride solution through the membrane, diffusional mass-transfer resistance of copper ion was negligible, since the ion was transported by convective flow through the pore. The tensile strength and elongation at break of the membranes were measured as a function of dose of electron-beam irradiation, the degree of grafting, and the chelating group density to determine an applicable range for practical use.

Production of l(+)-lactic acid by immobilized cells of Rhizopus oryzae with polymer supports prepared by γ ray induced polymerization

Rhizopus oryzae cells producing l(+)-lactic acid were immobilized with polymer supports prepared from polyethyleneglycol (no. 400) dimethacrylate as a monomer by γ ray induced polymerization. The production of lactic acid by immobilized cells was influenced by both water content and the support structure. A feasible polymer support had a water content greater than about 80% and a porous structure. The positive effect of immobilization on lactic acid production was found when the immobilization yield was greater than 65%. The specific rate of lactic acid production from immobilized cells reached a value 1.8 times higher than that of free cells.