Antimony(III/V) removal from industrial wastewaters: treatment of spent catalysts formally used in the SOHIO acrylonitrile process.

A treatment and volume reduction process for a spent uranium-antimony catalyst has been developed. Targeted removal, immobilization and disposal of the uranium component has been confirmed, thus eliminating the radiological hazard. However, significant concentrations of antimony ([Sb] ≥ 25-50 mg L-1) remain in effluent from the process, which require removal in compliance with Korean wastewater regulations. Antimony(III/V) removal via co-precipitation with iron has been considered with optimal pH, dose and kinetics being determined. The effect of selected anions - Cl-, SO4 2- and PO4 3- - have also been considered, the latter present due to a prior uranium removal step. Removal of Sb(III) from both Cl- and SO4 2- media and Sb(V) removal from Cl- media to below release limits were found to be effective within 5 minutes at an iron dose of 8 mM (molar ratio, [FeIII]/[Sb] = 20) and a target pH of 5.0. However, Sb(V) removal from SO4 2- was significantly hampered requiring significantly higher iron dosages for the same removal performance. Phosphate poses significant challenges for the removal of Sb(V) due to competition between PO4 3- and Sb(OH)6 - species for surface binding sites, attributed to similarities in chemistries and a shared preference for an inner vs outer binding mechanism.

Evaluation of the behavior of uranium peroxocarbonate complexes in Na-U(VI)-CO3-OH-H2O2 solutions by Raman spectroscopy.

In this work, the formation of uranium species and their stabilities in Na-U(VI)-CO(3)-OH-H(2)O(2) solutions at different pHs are studied by Raman spectroscopy. In this solution, the UO(2)(O(2))(CO(3))(2)(4-) species was formed together with three other uranium species of UO(2)(O(2))(2)(2-), UO(2)(CO(3))(3)(4-), and a speculated uranium species of the uranyl carbonate hydroxide complex, UO(2)(CO(3))(x)(OH)(y)(2-2x-y), which showed remarkable Raman peaks at approximately 769, 848, 811, and 727 cm(-1), respectively. The UO(2)(O(2))(CO(3))(2)(4-) species disappeared at pH conditions where bicarbonate dominated, and its Raman peak could be clearly observed in only a narrow pH range from approximately 9 to 12. When the pH of the solution increased further, the UO(2)(O(2))(CO(3))(2)(4-) species changed to UO(2)(CO(3))(3)(4-) and the UO(2)(CO(3))(x)(OH)(y)(2-2x-y) species. Moreover, the UO(2)(O(2))(CO(3))(2)(4-) species continuously decomposed into uranyl tricarbonate in the carbonate solution at an elevated temperature because of the instability of the peroxide ion, O(2)(2-), in alkaline conditions.

Induction of macrophage death by clinical strains of Mycobacterium kansasii.

Mycobacterium kansasii is a facultative intracellular pathogen causing pulmonary disease in immunocompetent patients. Little is known about the host defense against M. kansasii and its intracellular survival strategy inside macrophages. In the present study, we obtained six clinical isolates from patients with M. kansasii pulmonary disease and investigated the intracellular growth and cytotoxic effects of M. kansasii inside mouse bone marrow-derived macrophages (BMDM) as well as cytokine secretion from BMDM. Interestingly, two isolates, SM-1 and 2693-20, displayed faster growth rates and higher levels of TNF-alpha secretion from macrophages when compared to the other strains. In addition, SM-1 and 2693-20 also induced massive cell death in BMDM and THP-1 acute monocytic leukemia cells, while the slow growing strains induced significantly lower levels of cell death. This cytotoxicity was mainly caused by necrosis, not apoptosis and it was TNF-alpha-independent. Caspase inhibitors failed to block M. kansasii-induced macrophage death. In addition, necrosis caused by the fast growing strains was accompanied by the loss of mitochondrial membrane potential (DeltaPsi(m)). When dissipation of DeltaPsi(m) was inhibited by the classical mitochondrial permeability transition (MPT) inhibitor cyclosporine A (CsA), macrophage necrosis was reduced. These results suggest that clinical isolates of M. kansasii that grow faster in macrophages induce higher levels of necrosis in a DeltaPsi(m) loss-dependent manner.

Pilot-Scale Treatment of a Spent Uranium Catalyst Formally Used in the SOHIO Process: Pilot Plant Verification of the SENSEI Process.

Approximately 7000 drums of waste uranium catalyst are currently present in Korea and require an appropriate treatment and waste management strategy. Recently, one such process has been developed and has proven successful at both laboratory and bench scales. The success of the process has culminated in its verification at a pilot plant scale. The purpose of this paper is to describe the catalyst treatment process and present results obtained from the pilot plant study that may be applicable to other such wastes. The individual unit technologies have been tested and verified, enabling process scale-up to be successfully proven. The final volume reduction of up to 80% has been confirmed with the successful separation, encapsulation, and immobilization of residue wastes, representing a potential cost saving of US$70 million compared to the direct disposal. The inactive silica component of the waste catalyst was purified and confirmed to be free of uranium. All effluents generated during the process were treated and satisfy the appropriate Korean release criteria. The process employs the concept of Selective Extraction of Nonradioactive Species, Encapsulation, and Immobilization, and is therefore introduced as the SENSEI process.

Effective removal of uranium via phosphate addition for the treatment of uranium laden process effluents.

We have investigated the suitability of phosphate addition, in the form MH2PO4 (M = Na+, K+ or NH4+), for the selective removal of uranium from a complex waste effluent. The effluent in question is generated as part of a treatment strategy for a spent uranium catalyst, used in the production of acrylonitrile (Sohio process), which has been in temporary storage in Korea since 2004. Both pH (3.0-11.0) and phosphate dosages (0.25-10 mM) have been screened to identify the optimal conditions of 6.25 and 1 mM, respectively, for an initial uranium concentration of 0.16 mM. Precipitation kinetics have been investigated revealing the rapid removal of uranium from solution, with 30 min found to be optimal. The effluent was effectively decontaminated via Meta-ankoleite (K(UO2)(PO4)·3H2O) formation to uranium levels below the Korean release limit of 1 ppm for uranium-bearing liquid wastes, with KH2PO4 addition being chosen for the real process. Final decontamination factors of the order of ≥ 8000 were readily achieved. Aluminium, calcium and iron containing coagulants were screened for the clean-up of the remaining supernatant, post-uranium removal, ensuring the final effluent meets the relevant release criteria (pH, total suspended solids, total phosphate and turbidity) for general, non-radioactive, effluents. A process scheme is presented and discussed for adaptation to similar uranium containing effluents.

Development of a continuous electrolytic system with discharging only one pH-controlled stream and its characteristics.

In order to produce only a pH-controlled solution without discharging any unused solution, this work has developed a continuous electrolytic system with an ion exchange membrane-equipped electrolyzer and a tank, called as a pH-adjustment reservoir, placed just in front of the electrolyzer, where as a target solution was fed into the pH-adjustment reservoir, a portion of the solution in the pH-adjustment reservoir was circulated through the cathodic or anodic chamber of the electrolyzer depending on the type of the ion exchange membrane used, and another portion of the solution in the pH-adjustment reservoir was discharged from the electrolytic system through the opposite electrode chamber with its pH being controlled. The internal circulation of the pH-adjustment reservoir solution through the anodic chamber in the case of using a cation exchange membrane and that through the cathodic chamber in the case of using an anion exchange membrane could make the solution, discharged from the other counter chamber, effectively acidic and basic, respectively. The phenomena of the pH being controlled in the system could be explained by the electro-migration of the ion species in the solution through the ion exchange membrane under a cell potential difference between the anode and the cathode and its consequently-occurring non-charge equilibriums and the electrolytic water-split reactions in the anodic and cathodic chambers.

Electrochemical conversion characteristics of ammonia to nitrogen.

In order to evaluate the electrolytic decomposition characteristics of ammonia to nitrogen, this work has studied several experimental variables of electrolytic ammonia decomposition. The effects of the pH and the chloride ion in the solution, kinds of anodes such as IrO(2,) RuO(2), and Pt on the electrolytic decomposition of ammonia were compared, and the existence of a membrane equipped in the cell, the changes of the current density, the initial ammonia concentration, and so on were investigated for the decomposition. The performances of the electrode were totally in the order of RuO(2) approximately IrO(2) > Pt in both the acid and alkali conditions. The ammonia decomposition was the highest at a current density of 80 mA/cm(2), over which it decreased, because the adsorption of the ammonia at the electrode surface was hindered by the hydroxyl ions in the solution. The ammonia decomposition yield increased with the concentration of the chloride ion in the solution. However, the increment rate became much lesser over 10 g/l of the chloride ion. The RuO(2) electrode among the tested anodes generated the most OH radicals which could oxidize the ammonium ion at pH 7.

Novel application of nanozeolite for radioactive cesium removal from high-salt wastewater.

Finding a striking peculiarity of nanomaterials and evaluating its feasibility for practical use are interesting topics of research. We investigated the application of nanozeolite's outstanding reactivity for a rapid and effective method for radioactive cesium removal in the wastewater generated from nuclear power plant accident, as a new concept. Extremely fast removal of cesium, even without stirring, was achieved by the nanozeolite at efficiencies never observed with bulk materials. The nanozeolite reached an adsorption equilibrium state within 1 min. Cesium adsorption by nanozeolite was demonstrated at reaction rates of orders of magnitude higher than that of larger zeolite phases. This observation was strongly supported by the positive correlation between the rate constant ratio (k2,bulk/k2,nano) and the initial Cs concentrations with a correlation coefficient (R(2)) of 0.99. A potential drawback of a nanoadsorbent is the difficulty of particle settling and separation because of its high dispersivity in solution. However, our results also demonstrated that the nanozeolite could be easily precipitated from the high-salt solution with ferric flocculant. The flocculation index reached a steady state within 10 min. A series of our experimental results met the goal of rapid processing in the case of emergency by applying the well-suited nanozeolite adsorption and flocculation.

Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation.

Identification of electrical degradation products of 4-chlorophenol in water.

The electrical decomposition of 4-chlorophenol in water was examined with iridium dioxide doped on atitanium electrode. A number of electrical degradation products of 4-chlorophenol, such as hydroquinone and chlorohydroquinone via the addition of hydroxyl radicals, and dichlorophenol through addition of chlorine radical, were observed as major products. Moreover, hydroxylated chlorobiphenylethers, hydroxylated dibenzo-p-dioxin/furans and hydroxylated chlorobiphenyls formed by a dimerization process during the electrolysis process of 4-chlorophenol were also observed. On the other hand, benzoquinone, muconic acid and aldehyde derivatives that were further oxidative products of hydroquinone formed by photocatalysis process, were not observed. The electrical decomposition products of 4-chlorophenol were trimethylsilylated and then identified by gas chromatography-mass spectrometry. The degradation rate of 4-chlorophenol in water by iridium oxide electrode was measured against the electrical process duration. After iridium electrical process for 120 min, about 50% of 4-chlorophenol was converted into a number of products through oxidation processes. On the basis of the identified products, the degradation pathways of 4-chlorophenol under electrolysis process were proposed.

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Effects of the different conditions of uranyl and hydrogen peroxide solutions on the behavior of the uranium peroxide precipitation.

The dynamic precipitation characteristics of UO(4) in different solution conditions (pH, ionic strength, uranium and H(2)O(2) concentrations) were characterized by measuring changes in the absorbance of the precipitation solution and by monitoring the change of particle size in a circulating particle size analyzer. The precipitation solution conditions affected the precipitation characteristics such as the induction time, precipitation rate, overall precipitation time, and particle size in a complex manner. With increases in both pH and ionic strength, the induction time was prolonged, and the individual particle size decreased, but the individual particles tended to grow by aggregation to form larger precipitates. The uranium concentration and the ionic strength of the solution affected the induction time and precipitation rate to the greatest extent.

Continuous electrolytic decarbonation and recovery of a carbonate salt solution from a metal-contaminated carbonate solution.

This work studied the characteristic changes of a continuous electrolytic decarbonation and recovery of a carbonate salt solution from a metal-contaminated carbonate solution with changes of operational variables in an electrolytic system which consisted of a cell-stacked electrolyzer equipped with a cation exchange membrane and a gas absorber. The system could completely recover the carbonate salt solution from a uranyl carbonato complex solution in a continuous operation. The cathodic feed rate could control the carbonate concentration of the recovered solution and it affected the most transient pH drop phenomenon of a well type within the gas absorber before a steady state was reached, which caused the possibility of a CO(2) gas slip from the gas absorber. The pH drop problem could be overcome by temporarily increasing the OH(-) concentration of the cathodic solution flowing down within the gas absorber only during the time required for a steady state to be obtained in the case without the addition of outside NaOH. An overshooting peak of the carbonate concentration in the recovered solution before a steady state was observed, which was ascribed to the decarbonation of the initial solution filled within the stacked cells by a redundant current leftover from the complete decarbonation of the feeding carbonate solution.

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.