Americium removal from nitric acid waste streams

Separations research at the Rocky Flats Plant /RFP/ has found ways to significantly improve americium removal from nitric acid/7M/ waste streams generated by plutonium purification operations. Partial neutralization of the acid waste followed by solid supported liquid membranes /SLM/ are useful in transferring and concentrating americium from nitrate solutions. Specifically, DHDECMP /dihexyl-N, N-diethylcarbamoylmethylphosphonate/ supported on Accurel polypropylene hollow fibers assembled in modular form transfers >95% of the americium from high nitrate /6.9M/, low acid /0.1M/ feeds into 0.25M oxalic acid stripping solution. Maximum permeabilities were observed to be 0.001 cm sec^–1, consistent with typical values for other systems. The feed:strip volume ratio shows an inverse relationship to the fraction of metal ion transferred. Cation exchangers may be used to concentrate americium from the strip solution. Furthermore, OØD/iB/CMPO /or CMPO/ /octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide/ has been tested in an extraction chromatography mode. Preliminary results show CMPO to be effective in removing americium if the feed is neutralized to 1.OM acidity and iron/III/ is complexed with 0.20M oxalic acid.     

Americium separations from nitric acid process effluent streams

Plutonium recovery operations offer several points at which americium removal may be attempted, and we are evaluating two classes of materials targeted at different steps in the process. Extraction chromatography resin materials loaded with three different alkylcarbamoyl phosphinates and phosphine oxides are assessed for Am removal efficiency and Am/Fe selectivity from 1–7M nitric acid solutions. Commercial and experimental anion exchange resins are evaluated for total alpha-activity removal from post-evaporator solutions whose composition, relative to the original nitric acid effluent, is reduced in acid and greatly increased in total salt content. With both classes of materials, americium and/or total-alpha reduction is sufficient to meet regulatory requirements even under sub-optimal conditions. Batch distribution coefficients and column performance data are presented.     

Plutonium(III) oxidation under α-irradiation in nitric acid solutions

Plutonium(III) oxidation under high energy α-irradiation in nitric acid solutions has been studied relative to concentrations of both nitric acid (0.12–2.9 mol/l) and plutonium (1.4–10 mmol/l) using spectrophotometric techniques. Curium-244 has been used as the basic alpha-irradiation source. It has been stated that in solutions with nitric acid concentrations lower than 0.5 mol/l plutonium(III) does not oxidize completely. In the course of the process the formation of a plutonium(IV) peroxide complex is observed. Increase in the nitric acid concentration results in that in both the rate and degree of plutonium(III) oxidation. When c_{HNO 3} is higher than 0.5 mol/l the peroxide complex does not form and the process assumes an autocatalytic character. It has also been shown that plutonium(III) oxidation kinetics is significantly affected by nitrous acid, one of the nitrate ion radiolysis products. To describe plutonium chemical transformations under irradiation in nitric acid solutions, a kinetic scheme is proposed. The calculations have been carried out on a BESM-6 computer; a satisfactory agreement between the calculated and experimental data has been obtained.     

Plutonium removal by ion exchange chromatography

A study of Pu recovery at trace level from U solutions by ion exchange technique is presented. Plutonium retention >99.5% onto strong anionic resin, AG-X8, from nitric acid solutions and a 92% recovery using 0.4M HNO₃ at 60°C as eluent, were obtained. Uranium interference in Pu sorption from mixed U/Pu nitrate solutions with low U/Pu ratio (25) was not verified. However, for high U/Pu ratio solutions (10000), uranium interference in Pu retention on the resin, decreases to 59%. Selecting the loading conditions and using AG-X4 resin, 99% Pu retention was achieved. The Pu product is still contaminated with U and another purification cycle is recomended. A scheme for U/Pu first cycle separation is proposed.     

Uranium removal from nitric acid raffinate solution by solvent immobilized PVC cement

The present work deals with uranium removal from a nitric acid raffinate (waste) solution using prepared solvent (tri-butyl phosphate, TBP) immobilizing PVC cement (SIC) as a suitable adsorbent. The studied relevant factors affecting uranium adsorption onto SIC adsorbent involved; contact time, solution molarity, initial uranium concentration and temperature. The obtained adsorption isotherm of uranium onto the SIC adsorbent was fitted to Langmuir, Freundlich and Dubinin–Radushkviech (D–R) adsorption models. The results showed that the obtained equilibrium data fitted well the Langmuir isotherm. Additionally, it was found that the adsorption process obeys the pseudo second-order kinetic model. On the other hand, the calculated theoretical capacity of our prepared SIC adsorbent reached about 17 g U/kg SIC. Uranium adsorption from the studied raffinate solution was carried out applying the attained optimum conditions. The obtained data showed that 58.4 mg U/5 g SIC were adsorbed. However, using of 2 M HNO₃ solution as an eluent, 93 (54.3 mg U) from the adsorbed amount were eluted.     

Plutonium measurements in Hanford DOE site waste samples

This paper describes development work to prepare a method to measure absolute²³⁹Pu content and Pu-isotopics by ICP-MS in acidified Hanford DOE-site samples which are very high in⁹⁰Sr,⁹⁹Tc, and¹³⁷Cs radioactivity and which are frequently high in organic carbon content. Samples with very large⁹⁰Sr and¹³⁷Cs contents have historically been difficult to analyze for Pu content by each of three alpha-counting techniques in use at SRS, and analysis by ICP-MS in these samples is complicated by the high organics content. We report an ion exchange chemical preparation to obtain fraction of Pu that does not contain any fission product contribution and no interfering organics to allow measure of absolute²³⁹Pu and of²³⁹Pu through²⁴¹Pu isotopics by ICP-MS. The method uses a²⁴²Pu spike to measure Pu recovery and is demonstrated in this paper with three distinct commercially available resins and with over 300 samples. Measured absolute²³⁹Pu contents in sixty-three spiked/unspiked duplicates have agreed within 15% precision. Overall²⁴²Pu recoveries were near 90% with 25% precision. Comparisons of absolute²³⁹Pu contents measured directly on three samples agreed within the quoted 25% uncertainty.     

Removal of nitric acid from a simulated high level liquid waste by a safe chemical denitration

The heat and off-gas generation behavior was experimentally examined during a safe chemical denitration, pre- and mild-denitration, of simulated HLLW with a nitric acid concentration of 2 to 7.5 M. The maximum heat and off-gas generation were no more than 100 cal/s·1 and about 0.8 l/min, respectively. The solution temperature does not reach boiling temperature and no solution was squirted out from the denitration vessel. The pre-and mild-denitration technique could be considered as one of safe methods for removing nitric acid from the HLLW with various nitric acid concentrations. The pre- and mild-denitration also has an advantage to improve the filtration characteristics of precipitates produced by the denitration of simulated HLLW. The denitration of HLLW with 7.5M nitric acid concentration induced formation of “very easy-to-filter” solid. Moreover, a good filter cake washing is possible.     

Cellulosic-based hydrogel from biomass material for removal of metals from waste water

Abstract

Cellulose and carboxymethyl cellulose (CMC), prepared from rice straw, were used for hydrogel preparation, separately or in a mixture of both of them in a ratios of 1:1, 1:4, 1:9, 2:3 and 3:7 (by weight).They were polymerized with partially neutralized acrylic acid (AA) in the presence of potassium persulphate, as initiator, and vinylsulphone (VS), as cross-linker. Moreover, glutaraldehyde, N,N-methylene bis acrylamide (MBA) and Epichlorohydrin (ECH) were used as cross-linker for the mixture of 1:1 of Cellulose: CMC. The mechanism of the polymerization was studied and the resulted hydrogels were characterized for their appearances, yields percentage, and water absorbencies. The Fourier transform infrared spectroscopy (FT-IR) and XRD analysis were also investigated for the hydrogel samples. Since the textile industry produces large volumes of wastewaters which contain hazardous compounds such as dyes, heavy metals like Cu(II), and surfactants, so we aimed in this research to use the hydrogel samples for Cu²⁺ absorption that can be presented in the wastewater. The FT-IR spectrum, before and after absorption, indicated that the prepared hydrogels were able to absorb the Cu²⁺. The Cu²⁺ ions can be recovered and dried to be reused again as well as the hydrogel samples can be available again for reuse.     

Plutonium extraction from mixed aqueous media. Plutonium—Uranium separation

A systematic study is presented on Pu IV extraction with tri-n-butyl phosphate and trilaurylamine from binary mixtures of H₂SO₄ with HCl and HBr. The addition of sulfuric acid to the mentioned mineral acid solutions, was found to affect appreciably D_Pu, which recommended some useful purification procedures. The effect of water-miscible alcohols on the extraction of plutonium from HCl and HNO₃ solutions was also investigated.     

Starch-modified filters used for the removal of dyes from waste water

The present article proposes the use of starch-enriched flour as low-cost adsorbent of dyes. The adsorbents have been prepared by reticulation of starch-enriched flour using epichlorohydrin as crosslinking agent. These starch-modified filters exhibit interesting properties in terms of sorption rate. Studies concerning the sorption capacity are presented. The influence of the amine groups and the chemical structure of dyes are also studied. The regeneration procedure of the filters is showed and discussed. In order to explain the results, an adsorption mechanism mainly based on physical adsorption and interactions such as hydrogen bonds and ion-exchange due to the nature of the polymer network is proposed.     

NO2 removal on adsorbents prepared from coffee industry waste materials

A technology for obtaining carbonaceous adsorbents by physical and chemical activation of waste materials from coffee industry is described. The effect of pyrolysis temperature and type of activation procedure on the textural parameters, acid–base character of the surface and sorption properties of activated carbons has been tested. The resulting carbons were characterized by low-temperature nitrogen sorption, determination of pH and the number of surface oxygen groups. The sorption properties of the activated carbons obtained were characterized by evaluation of nitrogen dioxide adsorption in dry and wet conditions. The final products were adsorbents of specific surface area ranging from 5 to 2,076 m²/g and pore volume from 0.03 to 1.25 cm³/g, showing very diverse acidic–basic character of the surface. The results obtained in our study have proved that a suitable choice of the pyrolysis and activation procedure for coffee industry wastes permits production of adsorbents with high sorption capacity of nitrogen dioxide, reaching to 44.5 and 84.1 mg NO₂/g in dry and wet conditions, respectively.     

Solid formation in simulated high level liquid waste of relatively low nitric acid concentration

Solid formation in a simulated high level liquid waste (HLLW) was experimentally examined at 2M and 0.5M nitric acid concentrations. The precipitation studies were conducted by refluxing the simulated HLLW around 100°C. Zr, Mo, Te and Ru were major precipitation elements in both 2M and 0.5M HNO₃ solutions. The amount of precipitate in 2M HNO₃ solution decreased with decreasing Zr concentration and no precipitation was found in the solution without Zr. Only about 10% of Zr, Mo and Te were precipitated, if the Mo/Zr ratio in the 0.5M HNO₃ solution was kept below 0.5. Complete removal of Zr and Mo was the most effective way to prevent solid formation in the solution with 2M and 0.5M HNO₃ concentrations.     

Mineral sorbents for the removal of oil products from waste water

Properties of filtering-sorption materials based on basalt fibers and bentonite clays intended for the removal of oil products from water were studied. Optimal parameters of a feed providing the maximal purification efficiency with the minimal power consumption were determined.     

Sorption kinetics for the removal of aldehydes from aqueous streams with extractant impregnated resins

The sorption kinetics for the removal aldehydes from aqueous solutions with Amberlite XAD-16 and MPP particles impregnated with Primene JM-T was investigated. A model, accounting for the simultaneous mass transfer and chemical reaction, is developed to describe the process. It is based on the analogy to the diffusion and reaction in a stagnant liquid sphere, but corrected for the porosity and particle properties influencing the diffusion. The developed model describes the kinetic behavior of the process in the low concentration region rather well. However, in the high concentration region, larger discrepancies are observed. Initially, the influence of the flow rate was investigated to eliminate the effect of the external mass transfer. The influence of the particle morphology was investigated for both physical and reactive sorption. Physical sorption experiments were used to determine the factor τ that takes the particle properties influencing the diffusion into account. It was shown that the diffusion is faster in XAD-16 than in MPP impregnated systems. Reaction rate constant k _x was determined by fitting the model to the experimental data. Sorption of benzaldehyde appears to be significantly slower (k _x ∼10⁻⁴ l/mol s) than the sorption of pentanal (k _x ∼10⁻³ l/mol s) due to the slower chemical reaction. The influence of the particle size was investigated for the sorption of pentanal with XAD-16. It was observed that the particle size does influence the diffusion term, but does not have an effect on the reaction rate. On the other hand, the extractant loading influences the reaction rate slightly in the low concentration region, whereas the initial concentration of the solute has more pronounced effect.     

Biosorption of nickel in complex aqueous waste streams by cyanobacteria

A study was undertaken to determined if a suitable biosorbent could be found for removal of nickel at low concentrations (< 20 parts per million [ppm]) from a chemically complex wastewater effluent generated by electroplating operations. Algae and cyanobacteria were chosen as candidate biosorbent materials because they are easy to grow and they have the ability to withstand processing into biosorbent materials. Several species were screened for nickel-biosorption capacity initially, and three species of cyanobacteria were selected for further study based on their performance in the scoping tests. When compared to live controls, autoclaving improved the binding capacities of all three species, but usually biosorption data from experiments with live cells were more consistent. None of the three species was able to bind nickel efficiently in actual effluent samples. Further experimentation indicated that sodium ions, which were present in high concentrations in the effluent, were interfering with the ability of the cells to bind nickel. Adsorption isotherm plots for biosorption of nickel by two species ofAnabaena in NiCl₂-deionized water solutions were prepared. Managed by Martin Marietta Energy Systems, Inc., for the US Department of Energy under contract No. DEAC05-84OR21400.     

Desorption of nitric acid from boehmite and gibbsite

Solid-state Fourier transform infrared spectroscopy (FTIR), evolved gas analysis-FTIR (EGA-FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) have been used to investigate the desorption of nitric acid from boehmite and from gibbsite. Samples containing between 3 and 36% of adsorbed nitric acid by mass were prepared by placing the mineral in a 70% nitric acid solution or by the adsorption of nitric acid vapors in humid air. FTIR established that water-solvated nitrate was the main species adsorbed on the surface of either mineral under these conditions. The water-solvated nitrate vaporized as nitric acid at approximately 400 K with an enthalpy of desorption of approximately 50 kJ/mol for both surfaces. A second nitric acid desorption occurred at approximately 450 K and had an enthalpy of desorption of 85 kJ/mol (95 kJ/mol) for boehmite (gibbsite). This was assigned as desorption of partially solvated aluminum hydroxylated nitrate. Monodentate and bridging nitrate were also observed on the boehmite. These species desorbed at approximately 725 K as NO2 and O2 with an enthalpy of reaction of approximately 55 kJ/mol of NO2 desorbed.     

Adsorptive removal of lead-210 using hydroxyapatite nanopowders prepared from phosphogypsum waste

Journal of Radioanalytical and Nuclear Chemistry - Recently, several organic and inorganic adsorbents are used for the separation and purification processes of metal ions and removal of...     

Valorization of two waste streams into activated carbon and studying its adsorption kinetics,equilibrium isotherms and thermodynamics for methylene blue removal

Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC) with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB) onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g) of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.     

Denitrification and removal of heavy metals from waste water by immobilized microorganisms

Pseudomonas fluorescens, immobilized on soft polyvinyl chloride granules containing up to 35% softeners as carbon source, was used for simultaneous removal of nitrate and heavy metals. In typical continuous column operation, a 100 mg/L nitrate input solution was reduced to a 20 mg/L output at a feeding rate of 1500 mL/h, with a capacity of 14 kg/day/m³, and with an efficiency of 79%. In the same column, Pb(NO₃)₂ concentration was reduced from 1.0 to 0.05−0.1 mg/L and ZnSO₄ concentration was reduced from 10 to 5 mg/L.Pseudomonas aeruginosa immobilized on an O₂ plasma-treated melt blown polypropylene web was used for removing 95% of a 1.7 nCi PuCl₄ activity from a nuclear plant waste water in a batch operation.