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Synthesis and Evaluation of Reusable Desferrioxamine B Immobilized on Polymeric Spherical Microparticles for Uranium Recovery Yoshitaka Takagai, Miki Abe, Chisa Oonuma, Michio Butsugan, William Kerlin, Ken Czerwinski, and Ralf Sudowe Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b02727 • Publication Date (Web): 23 Aug 2019 Downloaded from pubs.acs.org on August 26, 2019

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Industrial & Engineering Chemistry Research

Synthesis and Evaluation of Reusable Desferrioxamine B Immobilized on Polymeric Spherical Microparticles for Uranium Recovery Yoshitaka Takagai*†, ††, Miki Abe†, Chisa Oonuma†††, Michio Butsugan†††, William Kerlin††††, Ken Czerwinski†††† and Ralf Sudowe†††††

† Cluster of Science and Technology, Fukushima University, 1 Kanayagawa,

Fukushima 960-1296, Japan, †† Institute of Environmental Radioactivity, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan, †††Hitachi Chemical Techno Service Co. Ltd., 4-13-1 Higashi-cho, Hitachi, Ibaraki 317-8555 Japan, ††††Department of Chemistry and Biochemistry, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy. Las Vegas, NV 89154 USA, and †††††Department of Environmental & Radiological Health Sciences, Colorado State University, 1681 Campus Delivery, Fort Collins, CO 80523-1681, USA

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To whom correspondence should be addressed: [email protected]

Keywords: uranium; desfferioxmine; microparticle; adsorption; removal; recovery.


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ABSTRACT. The development of techniques for the separation and removal of uranium from water waste and other sources is an active area of research because of the increasing demand for uranium for nuclear energy generation. However, the number of reusable adsorption materials with specific sizes and uniform shapes and can exhibit strong affinity for uranium is still scarce. In this work, we describe the modification of an acrylic micropolymer resin with desferrioxamine B and the evaluation of its adsorption property for uranium(VI). The obtained microparticles with specific sizes exhibit a uniform spherical shape, thus enabling the design of either batch or continuous flow column adsorption systems with good adsorption ability for U(VI) and can endure highpressure conditions (at least 100 kgf/cm2 (equal to 9.8 MPa)). The mechanism of adsorption is investigated using chemical kinetics and thermodynamics. Selectivity experiments reveal that the present system adsorbs U selectively in the presence of high competitive ion concentrations. Furthermore, the reusability of the resin after 10 adsorption–desorption cycles is demonstrated.


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1. INTRODUCTION

The development of techniques for the separation and recovery of uranium from water waste or secondary sources is an imperative task in areas of growing demand such as nuclear energy fuels, nuclear waste water management, nuclear equipment decommissioning, and recycling. Specifically, the demand for uranium for nuclear energy generation is expected to increase to 53,010–90,820 tons U/year by 2035, whereas the current global production is 62,825 tons U/year.1 Accidents such as those encountered in the Fukushima Daiichi Nuclear Power Plant require the removal of fuel debris that contains uranium generated by core meltdowns, and the fuel debris from reactors 1–3 at the mentioned plant has been estimated to amount to 880 tons.2 Moreover, uranium catalysis is envisaged as a potential technology for the generation of useful gases, including hydrogen, from natural products (e.g., water),3–5 thus further supporting the expected increase in the demand of uranium with the advancement of technology.


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Concerning the methodologies for the separation and removal of uranium, numerous studies have been conducted on polymeric materials based materials,

11–14

membranes,

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ion exchangers,

6–10

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including natural polymerinorganic compounds,

17–26

organic–inorganic hybrid materials, 27–33 and microorganisms. 34–37 By contrast, relatively few articles have reported the reusability and uniformity of the removal material for uranium.

6,27,29

In this regard, fiber-type adsorbents have proved reusable and useful in

the removal of uranium38–45; however, they are difficult to apply to industrial packed column equipment because they cannot withstand high pressures. For industrial and analytical applications, the development of resins such as liquid chromatographic (LC) packed resins with certain sizes and uniform shapes have attracted considerable interest. To date, a commercially available TEVA® resin46 of this type has been developed by Eichrom Technologies, LLC. Nevertheless, alternative functional resins are needed to effectively separate targets that require different elution conditions. To fabricate these resins, a strong affinity ligand for uranium that also allows its quick release from the resin is necessary.


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Microbial metabolite desferrioxamine B (DFO), which is a trihydroxamate-based siderophore synthesized by microorganisms, has a very strong chelating ability for many ions under several conditions. In particular, the formation of DFO complexes with high-valence radionuclides such as U,47–49 Pu,50, and Th50 has been studied. Moreover, the combination of DFO with solid-phase bases including cellulose paper,51 6,6-nylon fiber,52, and silica gel53 for analytical applications has been reported. However, the incorporation of DFO on particles with specific sizes and uniform spherical shapes at the surface of polymers still constitutes a challenge owing to chain polymerization and/or the deactivation of the metal chelating site of DFO. In this study, we describe the immobilization of DFO on a spherical microparticle (MP) resin with a specific size by performing a step-by-step process via a commercially available LC bare polymer resin. Furthermore, the applicability of this reusable resin for the recovery of uranium is demonstrated. 2. EXPERIMENTAL METHODS

2.1. Apparatus


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A PerkinElemer Spectrum TwoTM infrared spectrometer with an attenuated total reflection (ATR) attachment (PerkinElemer Inc., Waltham, MA) was used for Fourier transform infrared spectroscopy (FTIR) analyses. A DXR2 series micro-Raman microscope (Thermo Fisher Scientific, Waltham, MA, USA) with a 532 nm laser source was employed to identify polymeric MPs. A JMS-T100LP AccuTOF LC-plus 4G time-offlight mass spectrometer (JEOL Ltd., Tokyo, Japan) with a direct analysis in real time ionization system was employed to measure the mass spectrum of polymeric MPs. A Hitachi SU8220 (Hitachi High-Technologies Co., Tokyo, Japan) cold-field-emission scanning electron microscope (FE-SEM) was employed under 15 kV and ×2,000– 150,000. The FE-SEM was further equipped with an X-Max with an area size of 50 mm2 (Oxford Instruments plc, Oxon, UK) to serve as an energy-dispersive X-ray spectrometer. The Multisizer 4 device (Beckman Coulter, CA, USA) was used to perform laser diffraction particle size measurements. For the pH measurements, a HORIBA handy D-50 pH meter equipped with a long ToupH combination 9680-10D electrode was used. This electrode probe was employed to directly measure the solution pH in a conical-shaped centrifuge tube. A TGK NTS-4000BH thermocontrolled


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shaker (Tokyo Rikakikai Co, LTD [EYELA], Tokyo, Japan) was utilized to shake the solutions containing the polymeric MPs. To measure the concentration of metal ions in solution, a NexION300S inductively coupled plasma mass spectrometer (PerkinElmer) was used with ultrapure O2 and He gas (>99.9999%) as reaction gases in a dynamic reaction cell. All vials and bottles were disposable and were made of polypropylene or tetrafluoroetylene–perfluoroalkylvinylether copolymer. 2.2. Materials and reagents

The five types of polymeric MPs employed in this work, namely, EG50, EG80, EG50OH, EG80OH, and EG50COOH, are commercially available LC stationary phase resins and were obtained via special order from Hitachi Chemical Co., Ltd., Tokyo, Japan. These materials are cross-linked acrylic ester polymers that were commercially prepared by the copolymerization of ethylene glycol dimethacrylate (E) and glycidyl methacrylate (G). The numbers following EG represent the blending ratio between E and G (e.g., EG50 is a blend of 50:50 E:G). In the EG–(XX)–OH series, the MPs have –


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OH groups on most of the surface, and EG–(XX)–COOH contains –COOH moieties on the surface. Finally, the EG50 and EG80 MPs have epoxy groups on the surface. Desferioxamine (DFO) was obtained from Novartis International AG (Basel-Stadt, Switzerland) as its methanesulfonate salt Desferal®. Metal mixture solutions of 52 elements were prepared by mixing the Multi-Element Solution® #2, #3, #4, and #5 standard stock solutions of metal ion mixtures (stable isotopes; concentration 10 ppm; PerkinElmer). Uranyl(VI) acetate (natural isotope ratio) was obtained from Wako Chemical Co., Ltd. (Osaka, Japan), and a 100 mg/L (as U) aqueous solution (in 6% HNO3) was prepared by dissolving it in ultrapure HNO3 concentration (61%). From this solution, a U(IV) standard solution was prepared as follows: One milliliter of the above 1 mg/L U(VI) solution was dried in a 50 mL beaker on a hotplate with heating. Thereafter, 5 mL of a 6 mol/L HCl solution and 0.7 g Zn were added. Fifteen minutes later (note: complete dissolution of Zn in the acid solution is not essential), the solution volume was defined by adding 6 M HCl into a 25 mL volumetric flask. Following this procedure, a 400 μg/L U(VI) solution (as U) was prepared. The concentrations of the U(IV) and U(VI) solutions were verified using inductively coupled plasma mass spectrometry (ICP-MS).


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The pH buffer solution was prepared as follows: A 0.20 mol/L aqueous stock solution of sodium tetraborate decahydrate (borax) was prepared, and this solution was further diluted with distilled water to prepare 200 mM working pH buffer solutions adjusted to pH 9.4. Alternatively, a mixture solution of 200 mM phosphoric acid/acetic acid/boric acid was used as a wide-range pH buffer solution for a pH range of 2.0 to 9.0. An aqueous 0.10 mol/L HNO3 solution was employed to prepare pH 1.0 solutions. All other reagents and organic solvents (analytical grade materials or atomic absorption spectroscopic grade) were purchased from Wako Chemical Co., Ltd. (Osaka, Japan) and were used without further purification. 2.3. Preparation of DFO microparticles

The DFO immobilized on polymeric MPs (DMPs) were prepared as follows (Figure 1 shows the schematic reaction): For DFO–EG80, the pH of 20 mL of a 40 mg/mL DFO solution (dissolved in a 1:1 mixture of dimethyl sulfoxide and ultrapure water) was adjusted to 9.0 by using a 1 M sodium hydroxide aqueous solution in a 50 mL roundbottom flask. Thereafter, 400 mg EG80 was added into the flask and mixed by stirring


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for four hours at 80 °C in a water bath. The resulting suspension was then filtered using an Advantec membrane filter (mixed cellulose ester, 1.0 μm pore, 25 mm diameter, Advantec Inc., Tokyo, Japan) with aspiration (Büchi® V-500 vacuum pump, Switzerland), and the obtained DMPs were washed subsequently with methanol, 0.1 M aqueous HNO3 solution, and ultrapure water. The resulting DMPs were left to dry under vacuum at 25 °C for several days (typically two days) and were used in the sensing experiments without further purification. The rest of the DMP resins were fabricated after this procedure.


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Figure 1. Schematic reaction between DFO and polymeric MPs for chemical immobilization.


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2.4. Determination of the uptake amount of metal ions in DMPs by batch adsorption test

A total of 5.0 mg DMPs (typically DFO–EG80) was added to a 10.0 mL solution containing 1 μg/L metal ions, which was adjusted preferably to pH 9.35 by using 20 mM borax. The mixture was stirred at 210 rpm for 10 minutes at 25 °C, and the solution was filtered using a 0.8 μm Millex-AA syringe filter (Sigma-Aldrich, St. Louis, MO, USA) to separate unadsorbed free metal ions and solid DMPs. The concentration of the metal ions remaining in the filtrate was determined by ICP-MS, and the amount of metal ions that had been sorbed onto the DMPs was calculated by overall mass balance. To evaluate the adsorption percentage, the initial concentration was measured by conducting the same process without adding the DMPs (metal adsorption step). The adsorption amount qe (mg/g) per atom was calculated according to the following:

𝑞𝑒 =

(𝐶0 ― 𝐶𝑒)𝑉 𝑚

,

(1)

where C0 and Ce represent the initial concentration and equivalent concentration after the reaction of metal ions (mg/L) in the solution, respectively; V represents the initial


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volume (L) of the solution containing metal ions; and m is the mass (g) of the added MPs (g). Furthermore, the adsorption percentage (Ads(%)) of metal ions

and the

distribution constant (Kd) can be expressed by the following equations: 𝐴𝑑𝑠(%) = 𝐾𝑑 =

(𝐶0 ― 𝐶𝑒) 𝐶0

(𝐶0 ― 𝐶𝑒) 𝐶𝑒

.

× 100,

(2)

(3)

2.5. The kinetics

The reaction of the complexation of DMPs with the U(VI) ion can be expressed as follows: U + DMP ⇄ U-DMP. Moreover, considering the condition of [U]

Synthesis and Evaluation of Reusable ... - ACS Publications

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