Recovery of molybdenum by solvent extraction from simulated high level liquid waste

Journal of Radioanalytical and Nuclear Chemistry - In this study, simple and a rapid solvent extraction method is investigated to recover Mo(VI) from simulated HLLW. The (NH4)6Mo7O24·4H2O...     

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.     

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.     

Formation and filtration characteristics of solids generated in a high level liquid waste treatment process

The solids formation behavior in a simulated high level liquid waste (HLLW) was experimentally examined, when the simulated HLLW was treated in the ordinary way of actual HLLW treatment process. Solids formation conditions and mechanism were closely discussed. The solids formation during a concentration step can be explained by considering the formation of zirconium phosphate, phosphomolybdic acid and precipitation of strontium and barium nitrates and their solubilities. For the solids formation during the denitration step, at least four courses were observed; formation of an undissolved material by a chemical reaction with each other of solute elements (zirconium, molybdenum, tellurium) precipitation by reduction (platinum group metals) formation of hydroxide or carbonate compounds (chromium, neodymium, iron nickel, strontium, barium) and a physical adsorption to stable solid such as zirconium molybdate (nickel, strontium, barium).     

Selective separation behavior of silica gel for zirconium in simulated high level radioactive liquid waste

Zirconium in simulated high level radioactive liquid waste (HLLW) was selectively adsorbed and separated by self-made high adsorption activity silica gel. The selective adsorption mechanism was analyzed according to the structure character of self-made silica gel and performance of zirconium in acid simulated HLLW. The results show that the adsorption selectivity of self-made silica gel for zirconium is strong, because zirconium has higher positive charge and zirconium ion hydrolyzes easily. Distribution coefficient of self-made silica gels for zirconium is 53.5 ml/g. There are 6.5 (OH)/nm² on the surface on self-made silica gels which provide more adsorption activity places, thus self-made silica gels have higher adsorption capacity for zirconium (31.4 mg/g). The elution rate of the adsorption of zirconium on self-made silica gel by 0.2 mol/l H₂C₂O₄ is more than 99%. The solubility of the self-made silica gel in nitric acid is low, the chemical stability of self-made silica gel is very strong.     

Effect of phosphate ion on filtration characteristics of solids generated in simulated high level liquid waste

The effect of phosphate ion on the filtration characteristics of solids generated in a high level liquid waste was experimentally examined. Addition of phosphate ion into the simulated HLLW induced the formation of phosphate such as zirconium phosphate and phosphomolybdic acid. The filtration rate of zirconium phosphate abruptly dropped in the midst of filtration because of a gel-cake formation on the filter surface. The denitration of the simulated HLLW contained zirconium phosphate improved the filterability of this gelatinous solid. The filtration rates of denitrated HLLW decreased with increase of the phosphate ion concentration, since the solids formed by denitration had irregular particle size and configuration in the simulated HLLW with phosphate ion. To increase the filtration rate of denitrated HLLW, a solid suspension filtration tester was designed. The solid-suspension accelerated the filtration rate only in the simulated HLLW with more than 1500 ppm phosphate ion concentration. Under this condition, the simple agitation can easily suspend the constituent solids of filter cake in the solution and a much higher filtration rate can be obtained because the filter cake is continuously swept from the filter surface by rotation of propellers.     

Solid formation behavior during the conditioning of simulated high level liquid waste for transuranic elements extraction

The acidity change and solid formation in a simulated high level liquid waste (HLLW) containing precipitate were experimentally examined, when the acidity was reduced from 2M to 0.5M by denitration or simple dilution. The acidity of the simulated HLLW containing precipitate could be adjusted from 2M to around 0.5M by means of denitration or dilution, as well as the case of simulated HLLW without precipitate. The precipitation fractions of Zr, Mo and Te during denitration decreased with increasing amount of the precipitate already contained in the simulated HLLW. The amount of solid formed in the dilute simulated HLLW also decreased with increasing amount of precipitate in the simulated HLLW. Two process flow sheets for preparing HLLW for transuranic elements extraction were developed. One was a denitration process and the other a dilution process.     

New extractant for selective recovery of palladium from high level radioactive waste

Use of di- or tri-thioether instead monothioether permits to increase both efficiency and selectivity of the extraction of palladium. This selectivity allows the separation of palladium contained in nuclear fuel reprocessing solution in a single step.     

Denitration of simulated radioactive liquid waste

Journal of Radioanalytical and Nuclear Chemistry - Radioactive liquid wastes containing large amounts of nitric acid (approx. 4–7 M) generated in the nuclear fuel cycle are very...     

Reduction and removal of neptunium from synthetic high level liquid waste by TRPO process

Valency control of neptunium is an important issue in the partitioning of high level liquid waste (HLLW) from power-reactor spent fuel treatment. The redox behavior of neptunium in HLLW is quite different from that in nitric acid because of the effect of the large amount of ions in HLLW. In order to remove neptunium from HLLW, we studied the reduction of neptunium in synthetic HLLW (SHLLW) to maintain its valency at IV so that it can be extracted by TRPO extractant in the well developed Chinese TRPO process. Five different reductants were tested and the reduction behavior was investigated. The influence of some active elements in SHLLW was studied. The mechanism that the reductants react with neptunium through Fe element was supposed and proved by experiments. The reduction rate of Np(V) was highly enhanced by Fe element. Finally, a hybrid reductant was suggested and good reduction efficiency was obtained.     

Selective separation of cesium from simulated high level liquid waste solution using 1,3-dioctyloxy calix[4]arene-benzo-crown-6

The 25,27-di(octyloxy)calix[4]arenebenzocrown-6 (CBC) in 1,3-alternate conformation was synthesized indigenously starting from its intermediates in good yield and purity. The extraction studies of CBC were carried out by using two different phase modifiers namely isodecyl alcohol and ortho-nitrophenyl hexyl ether. Detailed investigations on the effect of various parameters like, concentration of phase modifiers, aqueous phase acidity, ligand concentration, nitrate ion concentration and effect of temperature on extraction of cesium have been carried out. The concentration of phase modifiers was optimized to be 30 % in n-dodecane to ensure optimum extraction of cesium. Stoichiometry of the extracted complex determined by slope analysis method reveals 1:1:1 molar ratio for CsNO₃:CBC:HNO₃. The extraction process was found to be exothermic as determined from the plot of log K _ex versus 1/T. The solvent system with a composition 0.01 M CBC/30 % phase modifier/n-dodecane was found to be effective for selective separation of cesium from simulated high level liquid waste solution.     

Gross alpha-activity estimation in simulated high level waste after actinides partitioning by solid state nuclear track detection

The estimation of low level alpha activity is difficult in waste samples containing large concentration of salts and beta–gamma activity. In the present study, the feasibility of gross alpha-activity measurement for simulated high level waste (SHLW) in solution medium by alpha-track registration technique has been attempted. The results showed that it is possible to use this technique for gross alpha-activity estimation of ~200 Bq/mL in solution medium with a precision and accuracy of ~30%. The importance of measuring 200 Bq/mL alpha activity in SHLW solutions is that this value corresponds to about 4,000 Bq/g activity in the solid medium which is the safe disposable limit. The advantage of this method over other methods is that it is not sensitive to beta–gamma emitters and salts and is very simple and inexpensive.     

Separation of carrier-free 90Y from high level waste by supported liquid membrane using KSM-17

A generator system has been developed for the preparation of carrier-free ⁹⁰Y from ⁹⁰Sr present in the high level waste (HLW) of the Purex process by employing a supported liquid membrane (SLM) using 2-ethylhexyl-2-ethylhexyl phosphonic acid (KSM-17 equivalent to PC 88A) supported on a polytetrafluoro ethylene (PTFE) membrane. When uranium depleted Purex HLW at appropriate acidity is passed sequentially through octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) sorbed on chromosorb-102 (abbreviated as CAC) and Zeolite AR1 (synthetic mordenite) columns, all the trivalent, tetravalent and hexavalent metal ions and monovalent ¹³⁷Cs ions are sorbed. After adjusting to pH 2 with NaOH the resulting effluent is used as feed in a single stage membrane cell partitioned with a PTFE membrane impregnated with KSM-17 and having a feed and receiver compartment with 5.0 ml capacity each. The receiver compartment was filled with a 0.5M HNO₃ or 0.5M HCl stripping solution. ⁹⁰Y alone is preferentially transported across the membrane leaving behind all the impurities viz. ⁹⁰Sr, ¹²⁵Sb, ¹⁰⁶Ru, ¹⁰⁶Rh, etc. in the feed compartment. This technique can yield ⁹⁰Y in mCi levels in a pure and carrier-free form for medical applications. The feed can be reused repeatedly after allowing for ⁹⁰Y buildup.     

Sodium diffusion in sodium borosilicate glass used for immobilization of high level liquid waste

Diffusion of sodium in Mn and Ti bearing sodium borosilicate glass used for the immobilization of the high level waste at the Waste Immobilization Plant, Tarapur has been studied by heterogeneous isotopic exchange using ²⁴Na as the radiotracer for sodium. The temperature dependence of the self-diffusion coefficient of sodium in the glass was found to follow Arrhenius equation below the glass transition temperature.     

Filtration characteristics of slurry formed by denitration of simulated high-level liquid waste

Precipitate formation behavior in high-level liquid waste (HLLW) and its filtration characteristics were examined experimentally, using a simulated HLLW. The amount of precipitate formed by denitration became minimum, only at about 5% of Mo, Zr, Te and Ru, if the simulated HLLW was pre-heated until the total heat input exceeded 7.9·10⁶ J/I HLLW before denitration or denitrated with the total heat input of more than 1.1·10⁷ J/I HLLW. Under these conditions, a needle-shaped precipitate with 0.51.0 m diameter and 35 m length was formed. This precipitate can be separated easily by vacuum filtration. While, fine particles of about 0.1 m diameter were precipitated during denitration, if the simulated HLLW was denitrated under the conditions the amount of newly formed precipitate was not minimum. It was difficult to separate the fine particles by vacuum filtration.     

Impregnation of covalent organic framework into porous silica support for the recovery of palladium ions from simulated high-level liquid waste

Journal of Radioanalytical and Nuclear Chemistry - In the present study, a porous silica-based covalent organic framework incorporated composite was prepared using a solvothermal reaction and the...     

An advanced partitioning process for key elements separation from high level liquid waste

To separate MA(Am,Cm) and some fission product elements(FPs) such as Tc,Pd,Cs and Sr from high level liquid waste(HLLW) systematically,we have been studying an advanced aqueous partitioning process,which uses selective adsorption as the separation method.For this process,we prepared several novel adsorbents which were immobilized in a porous silica/polymer composite support(SiO 2-P).Adsorption and separation behavior of various elements was studied experimentally in detail.Small scale separation tests using simulated HLLW solutions were carried out.Pd(II) was strongly adsorbed by the AR-01 anion exchanger and effectively eluted off by using thiourea.Successful separation of Pd(II) from simulated HLLW was achieved.Tc(VII) also exhibited strong adsorption on AR-01 and could be eluted off by using U(IV) as a reductive eluent.Am(III) presented significantly high adsorbability and selectivity onto R-BTP/SiO 2-P adsorbents over various FPs including Ln(III).The R-BTP adsorbents were fairly stable in 3 M HNO 3,but instable against-irradiation-3M HNO 3.An advanced partitioning process consisting of three separation columns for the target elements separation from HLLW was proposed and the obtained experiment results indicated that the proposed process is essentially feasible.     

Removal of radionuclides from low level radioactive liquid waste by precipitation

Six elements in several organs of mice fed with Zn deficient diet (Zn-def. mice) and those fed with control diet (control mice) were analyzed by INAA. Zinc concentrations in the organs of Zn-def. mice were not distinctly lower than those of control mice except for bone and pancreas. However, Ce content increased significantly in all organs of Zn-def. mice compared with control mice, indicating the partial substitution of Co with Zn in metal proteins or other materials for the Zn-def. mice.     

Uranium recovery and purification from simulated waste streams containing high uranium concentrations with dispersion liquid membranes

Journal of Radioanalytical and Nuclear Chemistry - The suitability of dispersion liquid membranes (DLMs) to recover and purify uranium from simulated waste streams containing nitric acid, high...     

Study on selective separation of cesium from high level liquid waste using a macroporous silica-based supramolecular recognition absorbent

A macroporous silica-based supramolecular recognition absorbent (Calix[4]?+?Dodecanol)/SiO₂?CP, was prepared by successive impregnation and fixing the 1,3-[(2,4-diethylheptylethoxy)oxy]-2,4-crown-6-Calix[4]arene (Calix[4]arene-R14) and its molecule modifier 1-Dodecanol onto SiO₂ silica-based polymer support. The characterization of (Calix[4]?+?Dodecanol)/SiO₂?CP was examined by thermal gravimetry and differential thermal analysis and electron probe microanalysis. Relatively large separation factors of Cs and other metal ions (?? _Cs/M ⁿ⁺ ) above 60 were obtained in the presence of 3?M HNO₃. The adsorption data of Cs(I) fitted well with Langmuir isotherm and the maximum adsorption capacity was estimated to be 0.19?mmol?g^?1. The Cs(I) in 3?M HNO₃ were also effectively adsorption on (Calix[4]?+?Dodecanol)/SiO₂?CP in the column operation, and the loaded Cs(I) was successfully eluted with an eluent of H₂O. The column packed with (Calix[4]?+?Dodecanol)/SiO₂?CP had excellent reusability after three cycles.