TBP 20% diluent/H N O3/H2 O liquid-liquid extraction system: equilibrium data normalization of nitric acid, ruthenium and zirconium

International Nuclear Information System (INIS)

Oliveira, C.A.L.G. de; Araujo, B.F. de.

1991-11-01

The extraction behavior of nitric acid, nitrosyl ruthenium nitrate and zirconium hydroxide nitrate in the system tri-n-butyl phosphate (TBP) 20% -diluent was studied. The main purpose was to obtain enough data to elaborate process flowsheets for the treatment of irradiated uranium fuels. During the runs, the equilibrium diagrams of nitric acid, ruthenium and zirconium were settled. From the achieved data, the influence of nitric acid, ruthenium, zirconium and nitrate ions concentration in the aqueous phase was checked. Furthermore, the density and the surface tension of the aqueous and organic phases were determined, gathering the interfacial tension after the contact between the phases. (author)

Characteristics and mechanism of explosive reactions of Purex solvents with Nitric Acid at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Miyata, Teijiro [Radiation Application Development Association, Tokai, Ibaraki (Japan); Takada, Junichi; Koike, Tadao; Tsukamoto, Michio; Watanabe, Koji [Department of Fuel Cycle Safety Research, Nuclear Safety Research Center, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan); Ida, Masaaki [JGC PLANTECH CO., LTD (Japan); Nakagiri, Naotaka [JGC Corp., Tokyo (Japan); Nishio, Gunji [Research Organization for Information Science and Technology, Tokai, Ibaraki (Japan)

2000-03-01

This investigation was undertaken to make clear the energetic properties and mechanism of explosive decomposition of Purex solvent systems (TBP/n-Dodecane/HNO{sub 3}) by Nitric Acid at elevated temperatures using a calorimetric technique (DSC, ARC) and a chromatographic technique (GC, GC/MS). The measurement of exothermic events of solvent-HNO{sub 3} reactions using DSC with a stainless steel sealed cell showed distinct two peaks with maxima at around 170 and 320degC, respectively. The peak at around 170degC was mainly attributed to the reactions of dealkylation products (n-butyl nitrate) of TBP and the solvent with nitric acid, and the peak at around 320degC was attributed to the exothermic decomposition of nitrated dodecanes formed in the foregoing exothermic reaction of dodecane with nitric acid. By using the data obtained in ARC experiments, activation energies of 123.2 and 152.5 kJ/mol were determined for the exothermic reaction of TBP with nitric acid and for the exothermic pyrolysis of n-butyl nitrate, respectively. Some possible pathways were considered for the explosive decomposition of TBP by nitric acid at elevated temperatures. (author)

The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

International Nuclear Information System (INIS)

Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

2017-01-01

In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

Initiation Temperature for Runaway Tri-n-Butyl Phosphate/Nitric Acid Reaction

Energy Technology Data Exchange (ETDEWEB)

Rudisill, T.S.

2000-11-28

During a review of the H-Canyon authorization basis, Defense Nuclear Facility Safety Board (DNFSB) staff members questioned the margin of safety associated with a postulated tri-n-butyl phosphate (TBP)/nitric acid runaway reaction due to the inadvertent heating of a canyon tank containing greater than 3000 lbs (1362 kg) of TBP. The margin of safety was partially based on experiments and calculations performed by the Actinide Technology Section (ATS) to support deletion of indication of tank agitation as a Safety Class System. In the technical basis for deletion of this system, ATS personnel conservatively calculated the equilibrium temperature distribution of a canyon tank containing TBP and nitric acid layers which were inadvertently heated by a steam jet left on following a transfer. The maximum calculated temperature (128 degrees C) was compared to the minimum initiation temperature for a runaway reaction (greater than 130 degrees C) documented by experimental work in the mid 195 0s. In this work, the initiation temperature as a function of nitric acid concentration was measured for 0 and 20 wt percent dissolved solids. The DNFSB staff members were concerned that data for 0 wt percent dissolved solids were not conservative given the facts that data for 20 wt percent dissolved solids show initiation temperatures at or below 130 degrees C and H-Canyon solutions normally contained a small amount of dissolved solids.

Behavior of zirconium in nitric medium in the extraction with TBP 30% V/V in dodecane

International Nuclear Information System (INIS)

Azevedo, H.L.P. de.

1979-10-01

The extraction of 10 -2 M zirconium by TBP 30% V/V in dodecane from nitric acid solutions is studied as a function of the following parameters : nitric acid concentration, temperature and the presence of radiolytic degradation products of the organic phase. For this study natural zirconium is irradiated in order to obtain Zr-95, used as a tracer. The experimental results are discussed considering the displacement of the equilibrium in the systems studied as a function of different experimental variables. (Author) [pt

Thermal decomposition of organic solvent with nitric acid in nuclear fuel reprocessing plants

Energy Technology Data Exchange (ETDEWEB)

Koike, Tadao; Nishio, Gunji; Takada, Junichi; Tukamoto, Michio; Watanabe, Kouji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Miyata, Sadaichirou

1995-02-01

Since a thermal decomposition of organic solvent containing TBP (tributyl phosphate) with nitric acid and heavy metal nitrates is an exothermic reaction, it is possible to cause an explosive decomposition of TBP-complex materials formed by a nitration between the solvent and nitric acid, if the solvent involving TBP-complex is heated upto a thermal limit in an evaporator to concentrate a fuel liquid solution from the extraction process in the reprocessing plant. In JAERI, the demonstration test for explosive decomposition of TBP-complex by the nitration was performed to elucidate the safety margin of the evaporator in the event of hypothetical explosion under auspices of the Science and Technology Agency. The demonstration test was carried out by heating TBP/n-dodecane solvent mixed with nitric acid and uranium nitrate. In the test, the thermal decomposition behavior of the solvent was examined, and also a kinematic reaction constant and a heat formation of the TBP-complex decomposition were measured by the test. In the paper, a safety analysis of a model evaporator was conducted during accidental conditions under the explosive decomposition of the solvent. (author).

Rapid quantification of TBP and TBP degradation product ratios by FTIR-ATR

International Nuclear Information System (INIS)

Gillens, A.R.; Powell, B.A.; Clemson University, Clemson, SC

2013-01-01

Tri-n-butyl phosphate (TBP) is the key complexant within the plutonium and uranium reduction extraction process used to extract uranium and plutonium from used nuclear fuel. During reprocessing TBP degrades to dibutyl phosphate (DBP), butyl acid phosphate (MBP), butanol, and phosphoric acid over time. A method for rapidly monitoring TBP degradation is needed for the support of nuclear forensics. Therefore, a Fourier transform infrared spectrometry-attenuated total reflectance (FTIR-ATR) technique was developed to determine approximate peak intensity ratios of TBP and its degradation products. The technique was developed by combining variable concentrations of TBP, DBP, and MBP to simulate TBP degradation. This method is achieved by analyzing selected peak positions and peak intensity ratios of TBP and DBP at different stages of degradation. The developed technique was tested on TBP samples degraded with nitric acid. In mock degradation samples, the 1,235 cm -1 peak position shifts to 1,220 cm -1 as the concentration of TBP decreases and DBP increases. Peak intensity ratios of TBP positions at 1,279 and 1,020 cm -1 relative to DBP positions at 909 and 1,003 cm -1 demonstrate an increasing trend as the concentration of DBP increases. The same peak intensity ratios were used to analyze DBP relative to MBP whereas a decreasing trend is seen with increasing DBP concentrations. The technique developed from this study may be used as a tool to determine TBP degradation in nuclear reprocessing via a rapid FTIR-ATR measurement without gas chromatography analysis. (author)

Recovery Ce from Ce - TBP Used Oxalic Acid

International Nuclear Information System (INIS)

Purwani, MV; Subagiono, R.; Suyanti

2007-01-01

Recovery or stripping Ce from Ce - TBP product of monazite sand used oxalic acid. Ce - TBP as organic phase and oxalic acid as aqueous phase and as strong precipitant compound to precipitate metal element. The stripping product as Ce - oxalic precipitate. The influence parameter were percentage of oxalic acid, volume ratio of Ce-TBP with oxalic acid, time and rate of stripping. At stripping of 25 ml Ce - TBP used oxalic acid, the optimum condition were achieve at using 5% oxalic acid, volume ratio of Ce - TBP : 5% oxalic acid = 1 : 1, time of stripping 7.5 minute and rate of stripping 150 rpm. At the optimum condition was obtained the recovery efficiency was 100%. (author)

Thermodynamics and kinetics of thermal decomposition of dibutylalkyl and dipentylalkyl phosphonate-nitric acid systems

International Nuclear Information System (INIS)

Chandran, K.; Brahmananda, C.V.S.; Anthonysamy, S.; Srinivasan, T.G.; Ganesan, V.

2013-01-01

Tributyl phosphate (TBP) is used in the reprocessing industry for the separation of uranium and plutonium from the spent nuclear fuels by PUREX process. A variety of dialkylalky/phosphonates were synthesised and their extraction behaviour on actinides was studied in this laboratory. The superior extraction characteristics of phosphonates make them useful for several metal recovery applications in the nuclear fuel cycle. However, higher solubility of phosphonates in aqueous phase as compared to TBP, introduces higher chances of the formation of thermally active 'red oil' like substances during the evaporation of aqueous streams. Thermal stability of neat and nitric acid solvated homologues of four dibutylalkyl phosphonates namely, dibutylpropyl phosphonate (DBPrP), dibutylbutyl phosphonate (DBBP), dibutylpentyl phosphonate (DBPP), dibutylhexyl phosphonate (DBHeP), and two dipentylalkyl phosphonates viz. dipentylbutyl phosphonate (DPBP), dipentylhexyl phosphonate (DPHeP) were studied. Experiments were conducted using an adiabatic calorimeter in heat-wait-search mode. Various stoichiometry of nitric acid-solvated DBalP and DPalP were prepared by equilibrating the respective organic with 4-15.6 M nitric acid followed by separation. Neat DBalP and DPalP are stable up to the temperature of ∼ 555 K while their acid-solvates decomposed in the temperature range 380-403 K. The results also indicated that the presence of nitric acid accelerated the decomposition of phosphonates. Decomposition of these acid solvated phosphonates is found to be exothermic and follows first order kinetics. The onset temperature, adiabatic temperature rise, pressure rise, decomposition enthalpy and activation energy were found to strongly depend on the nitric acid content of the acid-solvates. The studies also indicate that dibutylalkyl and dipentylalkyl phosphonates are also prone to form 'red oil' like substances under extreme conditions and can lead to run-away reactions

Determination of the trace TBP in industrial feed liquid by gas chromatography

International Nuclear Information System (INIS)

Gao Yuehua; Jiang Junqing; Mu Ling; Yang Songtao

2012-01-01

The determination of the trace TBP in kerosene of the industrial feed liquid by gas chromatography is studied in the paper. It first takes the purification treatment for the kerosene containing trace TBP. The plutonium is removed by 0.2 mol/L ferrous sulfamate-1 mol/L nitric acid using the back-extraction. The uranium and the nitric acid in the organic phase are removed by the deionized water. The impurity which affect the measurement of the TBP and is harmful to the gas chromatograph are eliminated. Then the content of the TBP of the organic phase can be determined by gas chromatography. Results show that the measuring range of the content of the TBP is 0.02% ∼ 2%. The precision of the method is better than 5% and the recovery is between 95%∼106%. (authors)

Some features of formation and dissolution of a series of Pu(IV) and Zr alkyl and butyl alkyl phosphates in the system TBP -n-dodecane - nitric acid - water

International Nuclear Information System (INIS)

Markov, G.S.; Moshkov, M.M.; Kokina, S.A.

1990-01-01

The formation and composition of salts produced on interaction of a series of alkyl- and butylalkylphosphoric acids having alkyl radical chain lengths from C 4 to C 1 0 with Pu(IV) and Zr in organic and aqueous phases of the system TBP - n-dodecane -nitric acid - water were studied. The composition of compounds was found to depend on the conditions of their formation, defined first of all by the HNO 3 concentration in aqueous and organic phases. (author) 12 refs.; 4 figs.; 1 tab

Safe handling of TBP and nitrates in the nuclear process industry

International Nuclear Information System (INIS)

Hyder, M.L.

1994-07-01

A laboratory and literature study was made of the reactions of tri-n-butyl phosphate (TBP) with nitric acid and nitrates. Its goal was to establish safe conditions for solvent extraction processes involving these chemicals. The damaging explosions at the Tomsk-7 PUREX plant in Russia graphically illustrated the potential hazard involved in such operations. The study has involved a review of prior and contemporary experiments, and new experiments to answer particular questions about these reactions. TBP extracts nitric acid and some metal nitrates from aqueous solutions. The resulting liquid contains both oxidant and reductant, and can react exothermically if heated sufficiently. Safe handling of these potentially reactive materials involves not only limiting the heat generated by the chemical reaction, but also providing adequate heat removal and venting. Specifically, the following recommendations are made to ensure safety: (1) tanks in which TBP-nitrate complexes are or may be present should be adequately vented to avoid pressurization. Data are supplied as a basis for adequacy; (2) chemically degraded TBP, or TBP that has sat a long time in the presence of acids or radiation, should be purified before use in solvent extraction; (3) evaporators in which TBP might be introduced should be operated at a controlled temperature, and their TBP content should be limited; (4) evaporator bottoms that may contain TBP should be cooled under conditions that ensure heat removal. Finally, process design should consider the potential for such reactions, and operators should be made aware of this potential, so that it is considered during training and process operation

Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Meze, F

2004-02-15

This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

TBP determination in nitric acid solutions from solvent extraction process

International Nuclear Information System (INIS)

Kuada, T.A.; Carvalho, E.I. de; Araujo, I. da C.; Cohen, V.H.

1988-07-01

Heavy organic phases have been observed on some occasions during TBP extraction process. These products, described as red oils, were considered as the main cause for process failures, specially in evaporators and concentrators. In view of safety aspects it is necessary to control organic concentration in product and waste solutions. The proposed method involves the organic removal by chloroform as a first step, followed by purification onto a silica gel column. The results are given from analysing TBP and its degradation product (DBP) by gas chromatography. (author) [pt

Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

International Nuclear Information System (INIS)

Spencer, B.B.

1995-08-01

DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660±0.092 at 25 C, and extraction enthalpy is -5. 46±0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 x 10 6 ±3.56 x 10 4 at 25 C; reaction enthalpy was -9.610±0.594 kcal/mol. Nitration complexation constant is 8.412±0.579, with an enthalpy of -10.72±1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured

Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

Energy Technology Data Exchange (ETDEWEB)

Spencer, B.B.

1995-08-01

DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

Influence of nitric acid on the kinetic of complexation of uranyl nitrate extracted by TBP

International Nuclear Information System (INIS)

Pushlenkov, M.F.; Zimenkov, V.V.

1982-02-01

The effect of nitric acid on the solvatation rate of uranyl nitrate with tributyl phosphate is studied. In the process of mass transfer, it is shown that nitric acid enables the extraction of uranyl nitrate, therefore its concentration in the organic phase exceeds that in equilibrium solution. Subsequently uranyl nitrate ''displaces'' nitric acid. The presence of the acid in aqueous and organic phases affects in a complicated manner the rate of solvatation of uranyl nitrate with tributyl phosphate [fr

Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

International Nuclear Information System (INIS)

Chitnis, R.R.; Dhami, P.S.; Gopalkrishnan, V.; Wattal, P.K.; Ramanujam, A.; Murali, M.S.; Mathur, J.N.; Bauri, A.K.; Chattopadhyay, S.

2000-10-01

A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

Separation Of Uranium From Fission Products Zr And Ru With 30% TBP (Tri Butyl Phosphate) Dodecane In Nitric Acid Medium As An Extract Material

International Nuclear Information System (INIS)

Herdady, R. Didiek; Masduki, Busron; Sigit

2000-01-01

Separation of uranium from fission products Zr and Ru in batch process with Tbp 30% - dodecane in nitric acid medium has been investigated. The extraction was carried out on various acidity of 1,006 M, 1.990 M, 2,980 M, 4,006 M, and 5,006 M, and uranium concentration in feed of 100.30 g/l; 149.96 g/l, 250.30 g/l and 300.7 g/l. The results showed that equilibrium of extraction was achieved at 25 minutes, enhancement factor of ruthenium increased and of zirconium decreased Utilization of grand concentration of uranium in feed caused decreasing of distribution coefficient, zirconium and ruthenium. The better contribution of experiments was obtained at the acidity of 2 M and uranium concentration in feed of 149.9 g/l with the decontamination factor of zirconium, FD zr-u was 1,65 and of ruthenium, FD ru-u was 1,52

Development of a chromatographic micro-system for radionuclides analysis in nitric acid media

International Nuclear Information System (INIS)

Losno, Marion

2017-01-01

Radionuclides analysis is a key point for nuclear waste management and nuclear material control. Several steps of sample modification have to be carried out before measurements in order to avoid any interferences and improve measurement precision. However those different steps are long, irradiating and difficult to achieve in gloveboxes. Moreover they produce liquid and solid waste. The goal of the study is to offer a new alternative to the use of solid phase extraction column for radionuclides separation in hard nitric acid medium. The system will decrease the amount of nuclear waste due to the analysis and automatize the different steps of the analysis. A plastic device made of COC containing a micro solid phase extraction column is first designed. Stationary phase is a poly(AMA-co-EDMA) monolith synthesized in situ. Its structure is adjustable and its functionalization versatile with a high resistance to nitric acid medium. Exchange capacity is 150 mg/g of monolith for TBP and TBP/CMPO column and up to 280 mg/g of monolith in case of DAAP. Exchange coefficients are determined for U(VI), Th(IV), Eu(III) and Nd(III) for 3 different extractants (and Pu(IV) in case of TBP column). Monolith synthesis is transferred in centrifugal device and hydrodynamic behavior studied. U,Th/Eu separation was finally carried out in both classic and centrifugal micro-system on TBP column. (author) [fr

Mass transfer studies in miniature Rotating Disc Contactor (RDC) with 30% TBP/nitric acid biphasic system

International Nuclear Information System (INIS)

Balasubramonian, S.; Sivakumar, D.; Kumar, Shekhar; Kamachi Mudali, U.

2014-01-01

The rotating disc contactor is the widely used liquid-liquid extraction equipment for its high throughput and efficiency. In this work mass transfer performance of the miniature RDC column for the 30% TBP/nitric acid biphasic system was studied in terms of the operating variables such as rotor speed and flow rate of the aqueous and organic phase. The RDC column used in the experiments was shown. The column shell is made up of thick glass having diameter of 10.5 cm and height 100 cm. The rotor diameter is 5.3 cm and stator opening diameter is 6.3 cm. Totally 25 number of rotor discs were welded in the rotating shaft. This shaft was aligned in such a way that each rotor was placed in the centre of the compartment formed in between the two stator rings. The experiments were carried out to study the effect of rotor speed and superficial velocity of the dispersed and continuous phase on mass transfer efficiency. The organic solvent was made as the continuous phase and O/A ratio was set as 4 in both the continuous to dispersed phase(c-d) and dispersed to continuous phase (d-c) mass transfer experiments. The Number of Transfer Units (NTU) was estimated based on the solvent phase. The graphical representation of NTU was shown. The NTU value was observed as 4 and 3 respectively for extraction and stripping at the combined through put of 60 L/h and the rotor speed of 1000 rpm. This corresponds to the Height of Transfer Unit (HTU) value of 15 cm and 20 cm respectively for d-c and c-d mass transfer. The estimated overall mass transfer coefficient was increasing with rotor speed and superficial velocity of the liquid phases. The overall mass transfer coefficient also increases with increase in hold up

The determination of molar volumes of uranous nitrate and nitric acid in systems of U(NO3)4-HNO3-H2O and U(NO3)4-HNO3-30% TBP kerosene

International Nuclear Information System (INIS)

Tao Chengying

1986-01-01

The data of molar volumes of uranous nitrate and nitric acid are necessary for the calculation of the changes in phase volume during the extraction in U(NO 3 ) 4 -HNO 3 /30%TBP-kerosene system. However, the data of the partial molar volume of U(NO 3 ) 4 are not available in literature. In the present work, the molar volumes of U(NO 3 ) 4 and HNO 3 are calculated by linear fitting of the experimental data. The result of the molar volume of HNO 3 is consistent with those in literature

Resolution of TBP-H/sub 2/MBP-HDBP-H/sub 3/PO/sub 4/. Application to UO/sub 2/(NO/sub 3/)/sub 2/-TBP, Th(NO/sub 3/)/sub 4/-TBP, and ZrO(NO/sub 3/)/sub 2/-TBP systems. [Separation of dibutyl phosphoric acid, monobutylphosphoric acid and orthophosphoric acid from tri-butylphosphate

Energy Technology Data Exchange (ETDEWEB)

Pires, M A.F.; Abrao, A

1981-04-01

Several schemes for the separation of dibutylphosphoric acid (HDBP), monobutylphosphoric acid (H/sub 2/MBP) and orthophosphoric acid (H/sub 3/PO/sub 4/) as hydrolytic and radiolytic degradation products from tri-n-butylphosphate (TBP) were studied. For the resolution of a HDBP, H/sub 2/MPB and H/sub 3/PO/sub 4/ mixture in TBP-diluent, or in TBP-diluent-heavy metal nitrate (U-VI, Th-IV or Zr-IV), techniques such as ion exchange chromatography, ion chromatography and separation onto a chromatographic alumina column were investigated. For the identification, determination and analytical resolution following up for the several systems studied, techniques such as refraction index measurement, electrical conductivity measurement, molecular spectrophotometry and gas chromatography were applied. Special emphasis was given to the separation using alumina column where the HDBP acid was retained and eluted selectively for its separation from TBP-varsol-uranyl nitrate mixtures. This analytical procedure was applied to the samples coming from the Uranium Purification Pilot Plant in operation at the Centro de Engenharia Quimica (IPEN).

Spectrophotometric Determination of Microamounts of Uranium previous Extraction with TBP-MIC

International Nuclear Information System (INIS)

Vera Palomino, J.; Palomares Delgado, F.; Petrement, J.; Fernandez Cellini, R.

1962-01-01

Selective extraction of uranium in nitric acid medium with a mixture of Tbp-MIC (1:10) has been achieved. Aluminium nitrate was used as salting agent. Complexing agents were added in order to avoid extraction of impurities. Extraction conditions have been studied so that extraction is almost practically complete in a single run. (Author) 19 refs

Study on the effect of free acidity and entrained TBP in UNPS on the quality of ADU powder

International Nuclear Information System (INIS)

Prudhvi Raju, P.V.S.N.; Mandal, D.

2015-01-01

Graphical abstract: From the experimental study it was found that mean particle size of precipitated Ammonium Di-Uranate (ADU) depends on the free acidity content and entrained TBP in Uranyl Nitrate Pure Solution (UNPS). It was found that as the free acidity as well as the entrained TBP content in UNPS increases, mean particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed as shown in below figures. - Highlights: • The mean particle size of precipitated ADU depends on the free acidity in UNPS. • The mean particle size of precipitated ADU also depends on the entrained TBP in UNPS. • As free acidity in UNPS increases, mean particle size of precipitated ADU decreases. • As entrained TBP in UNPS increases, particle size of precipitated ADU decreases. • Based on the experimental results two correlations were developed to find d p of ADU. - Abstract: The mean particle size and size distribution of Ammonium Di-Uranate (ADU) particles, precipitated during the precipitation reaction of Uranyl Nitrate Pure Solution (UNPS) with ammonia play an important role on the sintered density of UO 2 pellets. The quality of precipitated ADU depends on number of process parameters viz., pH of UNPS, concentration of uranium in UNPS, flow rate of ammonium hydroxide, temperature etc. However, the effects of the presence of free acid and entrained Tri-Butyl-Phosphate (TBP) in UNPS on the quality of ADU powder were not studied till date. Experiments were conducted to study the effect of free acidity and the presence of entrained TBP on the quality of precipitated ADU particles. It was found that as the concentration of free acid as well as the concentration of entrained TBP in UNPS increases, the particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed to determine the mean particle size of ADU; one is based on the free acid content of UNPS and the other is based on the

Study on the effect of free acidity and entrained TBP in UNPS on the quality of ADU powder

Energy Technology Data Exchange (ETDEWEB)

Prudhvi Raju, P.V.S.N. [Nuclear Fuel Complex, Hyderabad 500 062 (India); Mandal, D., E-mail: dmandal@barc.gov.in [Chemical Engineering Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

2015-09-15

Graphical abstract: From the experimental study it was found that mean particle size of precipitated Ammonium Di-Uranate (ADU) depends on the free acidity content and entrained TBP in Uranyl Nitrate Pure Solution (UNPS). It was found that as the free acidity as well as the entrained TBP content in UNPS increases, mean particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed as shown in below figures. - Highlights: • The mean particle size of precipitated ADU depends on the free acidity in UNPS. • The mean particle size of precipitated ADU also depends on the entrained TBP in UNPS. • As free acidity in UNPS increases, mean particle size of precipitated ADU decreases. • As entrained TBP in UNPS increases, particle size of precipitated ADU decreases. • Based on the experimental results two correlations were developed to find d{sub p} of ADU. - Abstract: The mean particle size and size distribution of Ammonium Di-Uranate (ADU) particles, precipitated during the precipitation reaction of Uranyl Nitrate Pure Solution (UNPS) with ammonia play an important role on the sintered density of UO{sub 2} pellets. The quality of precipitated ADU depends on number of process parameters viz., pH of UNPS, concentration of uranium in UNPS, flow rate of ammonium hydroxide, temperature etc. However, the effects of the presence of free acid and entrained Tri-Butyl-Phosphate (TBP) in UNPS on the quality of ADU powder were not studied till date. Experiments were conducted to study the effect of free acidity and the presence of entrained TBP on the quality of precipitated ADU particles. It was found that as the concentration of free acid as well as the concentration of entrained TBP in UNPS increases, the particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed to determine the mean particle size of ADU; one is based on the free acid content of UNPS and the other is based on

Effect of diluents on the extraction of actinides and nitric acid by bidentate organophosphorus compounds

International Nuclear Information System (INIS)

Rozen, A.M.

1986-01-01

The effect of dilutents on extraction by bidentate organophosphorus compounds (diphosphine dioxides, carbamoyl phosphonates, and phosphine oxides) was studied. Figures show the effect of dilutents on the extraction of americium by TOPO and by carbamoylmethylene phosphonate, and the effect of dilutents on the extraction of nitric acid and americium by carbamoylphosphine oxide. Also shown is the effect of dilutents on the extraction of americium by diphenyldioctyl methylenediphosphine dioxide, and the effect of dilutents on the extraction of americium by tetraphenylmethylenediphosphine dioxide. It was concluded that when TBP is added the distribution coefficient of Am increases but the effect of TBP may not be represented by the usual power relationship between the distribution coefficient and the TBP concentration, which would be expected if TBP was found to be very strong but for dilution by DCE it was relatively weak. The observed facts can be explained if it is assumed that TBP reacts with the bridging protons in the complex, which are free for dilution by benzene and are partially occupied when dichlorethane is used

Safety demonstration tests on thermal decomposition of nitrated solvent with nitric acid in nuclear fuel reprocessing plants. Contract research

International Nuclear Information System (INIS)

Tsukamoto, Michio; Takada, Junichi; Koike, Tadao; Watanabe, Koji; Uchiyama, Gunzou; Nishio, Gunji; Murata, Mikio

2001-03-01

The demonstration tests were conducted to investigate the safety of the ventilation system and integrity of the HEPA filters under the design basis accident (DBA) of the evaporator in the reprocessing plants. The tests were carried out by heating organic solvent (TBP/n- dodecane) mixed with nitric acid in a sealed vessel. It was possible to cause an explosive decomposition of TBP-complex formed by nitration of the solvent with nitric acid. The following was obtained by the analysis of the experimental results of the tests. From derivation by the experimental method, data on the maximum mass release rate and the maximum energy release rate in the explosion, as the solvent of 1 [kg] spouted out by the thermal decomposition, were obtained. They were 0.59 [kg/s] and 3240.3 [kJ/kg·s] respectively. The influence given on the cell ventilation system by this explosion was small and it was demonstrated that the safety of the HEPA filters could be secured. (author)

A study on enhancement of Np extraction by TBP through the electrochemical adjustment of Np valance by using a glassy carbon fiber column electrode system

International Nuclear Information System (INIS)

Kim, K. W.; Song, K. C.; Lee, I. H.; Choi, I. K.; Yoo, J. H.

1999-01-01

The Np valance state in nitric acid and the effect of nitrous acid on the Np valance composition were studied through ways of absorbance by spectrophotometer, extraction by TBP, and electrochemistry. Enhancement of Np extraction to 30 vol.% TBP was carried out through adjustment of Np valance state by using a glassy carbon fiber column electrode system. The Np solution used in this work consisted of only Np(V) and Np(VI) without Np(IV). The composition of Np(V) in the range of 0.5M ∼ 5.5 M nitric acid was 32% ∼ 19%. The electrolytic oxidation of Np(V) coexisting with Np(VI) in the solution enhanced Np extraction by 30 vol.% TBP about five times more than the one without the electrolytic oxidation. The facts were confirmed that the nitrous acid of less than about 10 -5 M acted as a catalyst to accelerate the chemical oxidation reaction of Np(V) to Np(VI) and the nitrous acid of more than 10 -3 M reduced Np(VI) to Np(V) reversely

Determination of TBP in nitric solutions of process

International Nuclear Information System (INIS)

Kuada, T.A.; Carvalho, E.I. de; Araujo, I. da C. de; Cohen, V.H.

1988-01-01

Heavy organic phases have been observed on some occasions during TBP extraction process. These products, described as red oils, were considered as the main cause for process failures, specially in evaporators and concentrators. In view of safety aspects it is necessary to control organic concentration in product and waste solutions. The proposed method involves the organic removal by chloroform as a first step, followed by purification onto a silica gel column. The results are given from analysing TBP and its degradation product (DBP) by gas chromatography. (author) [pt

Extractive distillation of nitric acid using the two-pot concept

International Nuclear Information System (INIS)

Counce, R.M.; Groenier, W.S.; Holland, W.D.; Jubin, R.T.; North, E.D.; Thompson, L.E. Jr.; Hebble, T.L.

1982-12-01

Experiments have confirmed the validity of a novel design for a nitric acid concentration system for use in shielded nuclear fuel reprocessing plants. Current plans for producing the scrub solution for the IODOX process require the concentration and recycle of low strength ( 3 ) 2 as the solvent and features two pots: an extractive distillation pot in which a concentrated acid product is obtained by contacting the acid feed with the solvent and a solvent recovery pot in which the solvent is dehydrated and recovered for recycle. In these experiments, a concentrated product of 89 wt % nitric acid was produced from azeotropic feed. The available vapor-liquid equilibria data for the Mg(NO 3 ) 2 -HNO 3 -H 2 O system has been empirically correlated, and a design methodology has been developed for the two-pot extractive distillation process

Investigation of antimony extraction from nitric acid solutions by tributyl phosphate

International Nuclear Information System (INIS)

Lakaev, V.S.; Smelov, V.S.

1988-01-01

The effect of iodide, hydrogen and pertechnetate ions on antimony extraction by tri-n-butyl phosphate (TBP) from aqueous nitric acid solutions under irradiated nuclear fuel processing is investigated at room temperature. The coefficients of antimony distribution are shown to increase at the presence of technetium ions 2-3 times and iodine ions - 100 and more times. Variation of hydrogen ion concentration does not affect antimony extraction. The schemes of the mechanism of antimony extraction at the pressence of iodide and pertechnetate ions are presented. Compositions of the formed compounds are given

Behaviours of trinitratonitrosyl complexes of ruthenium in dilute nitric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Sugimoto, S [Radia Industry Co. Ltd., Takasaki (Japan)

1979-07-01

This study aimed to elucidate the protolysis and condensation processes of the Ru complexes in relation to the concentration of nitric acid. The compositions of the dissociated and undissociated complexes were determined by the extraction with tributyl phosphate (TBP) and absorption spectroscopy in order to follow the rather rapid protolysis reaction of the complexes. The test solutions were prepared by dissolving the freshly obtained complexes into 0.50 - 0.001 M nitric acid solutions. The amounts of the undissociated complexes were determined at different elapses of time in the test solutions. The protolysis became significant when the concentration was below 0.15 M, and the dissociation rate suddenly increased at this concentration. At the concentrations above 0.2 M, the absorption peak of the complexes at 480 nm survived even after 144 hours. But below 0.15 M, the formation of dissociation products by protolysis was observed after the disappearance of the absorption peak. The amount of dissociation products rapidly increased after the preparation of the test solution as the concentration decreased below 0.15 M.

The optimisation study of tbp synthesis process by phosphoric acid

International Nuclear Information System (INIS)

Amedjkouh, A.; Attou, M.; Azzouz, A.; Zaoui, B.

1995-07-01

The present work deals with the optimisation study of TBP synthesis process by phosphoric acid. This way of synthesis is more advantageous than POCL3 or P2O5 as phosphatant agents. these latters are toxic and dangerous for the environnement. The optimisation study is based on a series of 16 experiences taking into account the range of variation of the following parameters : temperature, pressure, reagents mole ratio, promoter content. the yield calculation is based on the randomisation of an equation including all parameters. the resolution of this equation gave a 30% TBP molar ratio. this value is in agreement with that of experimental data

Development of mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-Diluent System

Energy Technology Data Exchange (ETDEWEB)

Ochkin, A.; Gladilov, D.; Nekhaevskiy, S.; Merkushkin, A. [D. Mendeleev University of Chemical Technology of Russia, 9 Miusskay Sqr., Moscow, 125047 (Russian Federation)

2016-07-01

The nuclear fuel reprocessing is based on the PUREX process. Usually 30% TBP in hydrocarbon diluents is applied, then the composition of the organic phase can be expressed as H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-Pu(NO{sub 3}){sub 4}-TBP-diluent. The mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-dodecane system has been elaborated. Mole fractions and volume ones and rational activity coefficients have been used in order to create the system of equations on the base of mass action law. The method for calculating activity coefficients was provided. The formation constants of uranyl nitrate di-solvate and mono-solvate and di-solvate of acid have been determined. Interaction between uranyl nitrate di-solvate and dodecane and between TBP and dodecane was taken into account. Activity coefficients of nitric acid and uranyl nitrate in mixed solutions were considered. Errors of adequacy have been determined for the systems containing 30% and 12% TBP concentrations.

Study on the effect of gamma radiolysis on the chromatographic composition profile of tri-isoAmyl-phosphate-n-dodecane-nitric acid system

International Nuclear Information System (INIS)

Chaudhary, S.D.; Lokhande, Manisha; Bindu, M.; Tripathi, S.C.; Gandhi, P.M.

2013-01-01

Tri-Iso-Amyl phosphate (TiAP), a higher homologue of tri-butyl phosphate (TBP) is the solvent proposed for the reprocessing of the spent nuclear fuel of Fast Breeder Reactors (FBR) origin. TiAP-n-dodecane has extraction behavior comparable to that of TBP-n-dodecane system, without third phase formation and an aqueous solubility ∼ 19mg/L, that is far too less in case as compared to that with TBP(∼400gm/L). We have initiated our study to examine the radiolytic degradation behavior of TiAP-n-dodecane in comparison to that of TBP and explore its full potential for reprocessing of spent nuclear fuels. A 30% mixture of TiAP with n-dodecane equilibrated with nitric acid of concentrations 2M has been subjected to steady state gamma radiolysis using 60 Co source. The samples were irradiated for increasing absorbed dose of 6,12 and 18M rad. Each of these samples were subjected to gas chromatographic analysis under optimised condition using thermal conductivity detector. Separately, these samples were also methylated using diazomethane for the determination of acidic phosphate species as their volatile methyl ester

Contribution to the modelization of liquid-liquid extraction systems. Application to metallic nitrate extraction by TBP in nitric medium

International Nuclear Information System (INIS)

Ly, J.

1984-10-01

The validity of theoretical expression for activity coefficients, in concentrated aqueous solution, proposed by Mikulin-Stokes-Robinson and Ryazanov-Vdovenko is confirmed by numerous tests. This allows a better control of the reactivity of chemicals in the extraction system: nitric aqueous solution-TBP organic solution used in nuclear hydrometallurgy. A reliable methodology is proposed for the study of metal extraction mechanism. Application to palladium (II) evidences extracted species in the organic phase. Influence of degradation product from extractant radiolysis on the behavior of this metallic element is effected. 187 refs [fr

Zirconium for nitric acid solutions

International Nuclear Information System (INIS)

Yau, T.L.

1984-01-01

The excellent corrosion resistance of zirconium in nitric acid has been known for over 30 years. Recently, there is an increasing interest in using zirconium for nitric acid services. Therefore, an extensive research effort has been carried out to achieve a better understanding of the corrosion properties of zirconium in nitric acid. Particular attention is paid to the effect of concentration, temperature, structure, solution impurities, and stress. Immersion, autoclave, U-bend, and constant strain-rate tests were used in this study. Results of this study indicate that the corrosion resistance of zirconium in nitric acid is little affected by changes in temperature and concentration, and the presence of common impurities such as seawater, sodium chloride, ferric chloride, iron, and stainless steel. Moreover, the presence of seawater, sodium chloride, ferric chloride, and stainless steel has little effect on the stress corrosion craking (SCC) susceptibility of zirconium in 70% nitric acid at room temperatures. However, zirconium could be attacked by fluoride-containing nitric acid and the vapors of chloride-containing nitric acid. Also, high sustained tensile stresses should be avoided when zirconium is used to handle 70% nitric acid at elevated temperatures or > 70% nitric acid

Nitric Acid Poisoning: Case Report

International Nuclear Information System (INIS)

Quintero Giraldo, Maria Paulina; Quiceno Calderon, William de Jesus; Melo Arango Catalina

2011-01-01

Nitric acid (HNO 3 ) is a corrosive fluid that, when in contact with reducing agents, generates nitrogen oxides that are responsible for inhalation poisoning. We present two cases of poisoning from nitric acid gas inhalation resulting from occupational exposure. Imaging findings were similar in both cases, consistent with adult respiratory distress syndrome (ARDS): bilaterally diffuse alveolar opacities on the chest X-ray and a cobblestone pattern on computed tomography (CT).one of the patients died while the other evolved satisfactorily after treatment with n-acetyl cysteine and mechanical ventilation. The diagnosis of nitric acid poisoning was made on the basis of the history of exposure and the way in which the radiological findings evolved.

Alternative to Nitric Acid Passivation Project Overview

Science.gov (United States)

Lewis, Pattie L.

2013-01-01

The standard practice for protection of stainless steel is a process called passivation. This procedure results in the formation of a metal oxide layer to prevent corrosion. Typical passivation procedures call for the use of nitric acid which exhibits excellent corrosion performance; however, there are a number of environmental, worker safety, and operational issues associated with its use. The longtime military specification for the passivation of stainless steel was cancelled in favor of newer specifications which allow for the use of citric acid in place of nitric acid. Citric acid offers a variety of benefits that include increased safety for personnel, reduced environmental impact, and reduced operational costs. There have been few studies, however, to determine whether citric acid is an acceptable alternative for NASA and DoD. This paper details activities to date including development of the joint test plan, on-going and planned testing, and preliminary results.

Thermal decomposition studies on tri-iso-amyl phosphate in n-dodecane-nitric acid system

International Nuclear Information System (INIS)

Chandran, K.; Sreenivasalu, B.; Suresh, A.; Sivaraman, N.; Anthonysamy, S.

2014-01-01

Tri-iso-amyl Phosphate (TiAP) is a promising alternative solvent to TBP, with near similar extraction behaviour and physical properties but lower aqueous phase solubility and does not form third phase during the extraction of Pu(IV). In addition to the solubilised extractant, inadvertent entrainment of the extractant into the aqueous stream is a concern during the evaporation operation as the extractant comes into contact with higher nitric acid concentrations and metal nitrates. Hence the thermal decomposition behaviour of TiAP-HNO 3 systems has been studied using an adiabatic calorimeter in closed air ambience, under heat-wait-search mode (H-W-S)

EFFECTS OF NITRIC ACID ON CRITICALITY SAFETY ANALYSIS

Energy Technology Data Exchange (ETDEWEB)

Williamson, B.

2011-08-18

As nitric acid molarity is increased, there are two competing phenomena affecting the reactivity of the system. First, there is interaction between each of the 10 wells in the basket-like insert. As the molarity of the nitric acid solution is increased (it moves from 100% water to 100% HNO{sub 3}), the hydrogen atom density decreases by about 80%. However, it remains a relatively efficient moderator. The moderating ratio of nitric acid is about 90% that of water. As the media between the wells is changed from 100% water to 100% nitric acid, the density of the media increases by 50%. A higher density typically leads to a better reflector. However, when the macroscopic scattering cross sections are considered, nitric acid is a much worse reflector than water. The effectiveness of nitric acid as a reflector is about 40% that of water. Since the media between the wells become a worse reflector and still remains an effective moderator, interaction between the wells increases. This phenomenon will cause reactivity to increase as nitric acid molarity increases. The seond phenomenon is due to the moderating ratio changing in the high concentration fissile-nitric acid solution in the 10 wells. Since the wells contain relatively small volumes of high concentration solutions, a small decrease in moderating power has a large effect on reactivity. This is due to the fact that neutrons are more likely to escape the high concentration fissile solution before causing another fission event. The result of this phenomenon is that as nitric acid molarity increases, reactivity decreases. Recent studies have shown that the second phenomenon is indeed the dominating force in determining reactivity changes in relation to nitric acid molarity changes. When considering the system as a whole, as nitric acid molarity increases, reactivity decreases.

Study on the plutonium extraction and reextraction in radiolytic degraded system 30 % TBP-n-dodecane/HNO3-H2O

International Nuclear Information System (INIS)

Hoffmann, P.M.; Wronska, T.

1980-01-01

The degree of the complexation of plutonium(4) by the products of radiolysis of the system 30 % TBP-n-dodecane/HNO 3 -H 2 O as a function of radiation dose and concentration of nitric acid has been studied. The special method of calculation based on extraction equilibria was used. The retention of plutonium in the organic phase after single reductive reextraction has been determined. (author)

Behavior of silicon in nitric media. Application to uranium silicides fuels reprocessing

International Nuclear Information System (INIS)

Cheroux, L.

2001-01-01

Uranium silicides are used in some research reactors. Reprocessing them is a solution for their cycle end. A list of reprocessing scenarios has been set the most realistic being a nitric dissolution close to the classic spent fuel reprocessing. This uranium silicide fuel contains a lot of silicon and few things are known about polymerization of silicic acid in concentrated nitric acid. The study of this polymerization allows to point out the main parameters: acidity, temperature, silicon concentration. The presence of aluminum seems to speed up heavily the polymerization. It has been impossible to find an analytical technique smart and fast enough to characterize the first steps of silicic acid polymerization. However the action of silicic species on emulsions stabilization formed by mixing them with an organic phase containing TBP has been studied, Silicon slows down the phase separation by means of oligomeric species forming complex with TBP. The existence of these intermediate species is short and heating can avoid any stabilization. When non irradiated uranium silicide fuel is attacked by a nitric solution, aluminum and uranium are quickly dissolved whereas silicon mainly stands in solid state. That builds a gangue of hydrated silica around the uranium silicide particulates without preventing uranium dissolution. A small part of silicon passes into the solution and polymerize towards the highly poly-condensed forms, just 2% of initial silicon is still in molecular form at the end of the dissolution. A thermal treatment of the fuel element, by forming inter-metallic phases U-Al-Si, allows the whole silicon to pass into the solution and next to precipitate. The behavior of silicon in spent fuels should be between these two situations. (author)

Treatment of low level radioactive liquid waste containing appreciable concentration of TBP degraded products.

Science.gov (United States)

Valsala, T P; Sonavane, M S; Kore, S G; Sonar, N L; De, Vaishali; Raghavendra, Y; Chattopadyaya, S; Dani, U; Kulkarni, Y; Changrani, R D

2011-11-30

The acidic and alkaline low level radioactive liquid waste (LLW) generated during the concentration of high level radioactive liquid waste (HLW) prior to vitrification and ion exchange treatment of intermediate level radioactive liquid waste (ILW), respectively are decontaminated by chemical co-precipitation before discharge to the environment. LLW stream generated from the ion exchange treatment of ILW contained high concentrations of carbonates, tributyl phosphate (TBP) degraded products and problematic radio nuclides like (106)Ru and (99)Tc. Presence of TBP degraded products was interfering with the co-precipitation process. In view of this a modified chemical treatment scheme was formulated for the treatment of this waste stream. By mixing the acidic LLW and alkaline LLW, the carbonates in the alkaline LLW were destroyed and the TBP degraded products got separated as a layer at the top of the vessel. By making use of the modified co-precipitation process the effluent stream (1-2 μCi/L) became dischargeable to the environment after appropriate dilution. Based on the lab scale studies about 250 m(3) of LLW was treated in the plant. The higher activity of the TBP degraded products separated was due to short lived (90)Y isotope. The cement waste product prepared using the TBP degraded product was having good chemical durability and compressive strength. Copyright © 2011 Elsevier B.V. All rights reserved.

Spectrophotometric Determination of Microamounts of Uranium previous Extraction with TBP-MIC; Determinacion Espectrofotometrica de Microcantidades de Uranio previa extraccin con Metilisobutilcetona-Fosfato de Tributilo

Energy Technology Data Exchange (ETDEWEB)

Vera Palomino, J; Palomares Delgado, F; Petrement, J; Fernandez Cellini, R

1962-07-01

Selective extraction of uranium in nitric acid medium with a mixture of Tbp-MIC (1:10) has been achieved. Aluminium nitrate was used as salting agent. Complexing agents were added in order to avoid extraction of impurities. Extraction conditions have been studied so that extraction is almost practically complete in a single run. (Author) 19 refs.

Formation and electrical characteristics of silicon dioxide layers by use of nitric acid oxidation method

International Nuclear Information System (INIS)

Imal, S.; Takahashi, M.; Matsuba, K.; Asuha; Ishikawa, Y.; Kobayashi, Hikaru

2005-01-01

SiO 2 /Si structure can be formed at low temperatures by use of nitric acid (HNO 3 ) oxidation of Si (NAOS) method. When Si wafers are immersed in ∼ 40 wt% HNO 3 solutions at 108 deg C, ∼ 1 nm SiO 2 layers are formed. The subsequent immersion in 68 wt% HNO 3 (i.e., azeotropic mixture of HNO 3 with water) at 121 deg C increases the SiO 2 thickness. The 3,5 nm-thick SiO 2 layers produced by this two-step NAOS method possess a considerably low leakage current density (e.g. 1 x 10 2 A/cmi 2 at the forward gate bias, V G , of 1.5 V), in spite of the low temperature oxidation, and further decreased (e.g., 8 x 10 4 A/cm 2 at V G = 1.5 V) by post-metallization annealing at 250 deg C in hydrogen atmosphere. In order to increase the SiO 2 thickness, a bias voltage is applied during the NAOS method. When 10 V is applied to Si with respect to a Pt counter electrode both immersed in 1 M HNO 3 solutions at 25 deg C, SiO 2 layers with 8 nm thickness can be formed for 1 h(Authors)

Actinide extraction from ICPP sodium bearing waste with 0.75 M DHDECMP/TBP in Isopar L reg-sign

International Nuclear Information System (INIS)

Herbst, R.S.; Brewer, K.N.; Garn, T.G.; Law, J.D.; Rodriguez, A.M.; Tillotson, R.T.

1996-01-01

Recent process development efforts at the Idaho Chemical Processing Plant include examination of solvent extraction technologies for actinide partitioning from sodium bearing waste (SBW) solutions. The use of 0.75 M dihexyl-N, N-diethylcarbamoylmethylphosphonate (DHDECMP or simply CMP) and 1.0 M tri-n-butyl phosphate (TBP) diluted in Isopar L reg-sign was explored for actinide removal from simulated SBW solutions. Experimental evaluations included batch contacts in radiotracer tests with simulated sodium bearing waste solution to measure the extraction and recovery efficiency of the organic solvent. The radioactive isotopes utilized for this study included Pu-238, Pu-239, Am-241, U-233, Np-239, Zr-95, Tc-99m, and Hg-203. Extraction contacts of the organic solvent with the traced SBW stimulant, strip (back-extraction) contacts of the loaded organic solvent with either a 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) in nitric acid solution or an oxalic acid in nitric acid solution, and solvent wash contacts with sodium carbonate were performed

Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

Energy Technology Data Exchange (ETDEWEB)

Pitchaiah, K.C.; Sujatha, K.; Rao, C.V.S. Brahmmananda; Subramaniam, S.; Sivaraman, N.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2015-06-01

In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

Reaction kinetics and reaction heat on thermal decomposition of solvent containing unstable reactive hydrocarbons with nitric acid at Tomsk-7 reprocessing plant

International Nuclear Information System (INIS)

Nishio, Gunji; Watanabe, Kouji; Koike, Tadao; Miyato, Teijiro.

1996-12-01

For analyzing a cause of the Tomsk-7 accident at Russian reprocessing plant, it is necessary to determine reaction-rate constant and reaction heat for a thermal decomposition of TBP/kerosine containing unstable reactive hydrocarbons with nitric acid. In JAERI, the rate constant and reaction heat were obtained from data measured with a differential thermal analyzer (DTA) for unstable hydrocarbons such as n-butanol, n-butyl nitrate, aromatic hydrocarbons, and cyclic compounds. The safety evaluation of Tomsk tank ruptured by the reaction was carried out by heat balance calculations between heat generation and heat loss in the tank using these rate constants and reaction heats. Consequently, it is clear that the cause of the tank rupture would be due to an exothermic reaction of aromatic hydrocarbons in kerosine made by petroleum with the concentrated nitric acid of 14.2N. (author)

Kinetics modelling of the concentrated nitric acid reduction on 304L stainless steel

International Nuclear Information System (INIS)

Benoit, Marie

2016-01-01

In France, the spent nuclear fuel reprocessing involves the use of nitric acid at various concentrations and temperatures. The corrosiveness of these nitric mixtures leads to the use of corrosion resistant materials such as austenitic stainless steels (SS), which naturally forms a protective oxide layer under those conditions. The goal of this work is to study the influence of the passive layer on the mechanism and kinetics of concentrated nitric acid reduction reaction (NRR). We firstly focused on a single step in the reduction reaction (Fe(III)/Fe(II) couple in acidic solution) on passivated zirconium with different oxide layer thicknesses. The electrochemical impedance spectroscopy can lead to estimate the semiconducting properties of the film: the space charge capacitance (from the Mott-Schottky equation) allowed to estimate the number of charge carriers in the oxide. We experimentally compare the NRR on gold (on which no passive layer is formed) and SS, respectively. The chemical composition (chromium enrichment) and thickness of the SS passive layer are characterized by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS), and the mechanism and kinetics of NRR are studied by chrono-amperometry and EIS. On gold electrode, two mechanisms occur successively as a function of cathodic overpotential. at lower over potentials (0.85≤E/SHE≤1.15 V) we propose that NRR follows the Vetter's mechanism, whereas at higher over potentials (0.65≤E/ESH≤ 0.85 V), Schmid's mechanism may occur. On SS, the presence of the passive layer slows down the NRR by a factor 10"4. Moreover, depending on the experimental conditions (4 M to 8 M, 40 C to 100 C) Schmid's mechanism may occur or not in the potential range investigated. Finally, based on the EIS results, we propose a quantitative modelling of the NRR mechanism on stainless steel electrodes. (author) [fr

Co-extraction and co-stripping of U(VI) and Pu(IV) using tri-iso-amyl phosphate and tri-n-butyl phosphate in n-dodecane from nitric acid media under high loading conditions

Energy Technology Data Exchange (ETDEWEB)

Sreenivasulu, Balija; Suresh, Ammath; Sivaraman, Nagarajan; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2016-08-01

The extraction of Pu(IV) using 1.1 M solution of tri-iso-amyl phosphate (TiAP)/n-dodecane (DD) from plutonium nitrate solutions in nitric acid media was examined as a function of equilibrium aqueous phase metal ion concentration and equilibrium aqueous phase acidity at 303 K. The nitric acid concentration in the organic phase was measured as a function of equilibrium organic phase plutonium concentration. The co-extraction of U(VI) and Pu(IV) was studied using 1.1 M TiAP/DD system as a function of their equilibrium aqueous phase metal ion concentration and compared with 1.1 M tri-n-butyl phosphate (TBP)/n-DD system under identical conditions. Co-extraction and co-stripping of U(VI) and Pu(IV) were studied using 1.1 M TiAP/DD and 1.1 M TBP/DD systems in cross current mode to evaluate the number of stages required for the extraction and stripping of heavy metal ions (uranium and plutonium). The extraction and stripping efficiencies were calculated for both the systems. The saturation limit of the organic phase was also established in these studies.

Co-extraction and co-stripping of U(VI) and Pu(IV) using tri-iso-amyl phosphate and tri-n-butyl phosphate in n-dodecane from nitric acid media under high loading conditions

International Nuclear Information System (INIS)

Sreenivasulu, Balija; Suresh, Ammath; Sivaraman, Nagarajan; Rao, P.R. Vasudeva

2016-01-01

The extraction of Pu(IV) using 1.1 M solution of tri-iso-amyl phosphate (TiAP)/n-dodecane (DD) from plutonium nitrate solutions in nitric acid media was examined as a function of equilibrium aqueous phase metal ion concentration and equilibrium aqueous phase acidity at 303 K. The nitric acid concentration in the organic phase was measured as a function of equilibrium organic phase plutonium concentration. The co-extraction of U(VI) and Pu(IV) was studied using 1.1 M TiAP/DD system as a function of their equilibrium aqueous phase metal ion concentration and compared with 1.1 M tri-n-butyl phosphate (TBP)/n-DD system under identical conditions. Co-extraction and co-stripping of U(VI) and Pu(IV) were studied using 1.1 M TiAP/DD and 1.1 M TBP/DD systems in cross current mode to evaluate the number of stages required for the extraction and stripping of heavy metal ions (uranium and plutonium). The extraction and stripping efficiencies were calculated for both the systems. The saturation limit of the organic phase was also established in these studies.

Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

International Nuclear Information System (INIS)

Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gubina, M.Yu.

1988-01-01

Stability concetration constants K and solubility of neptunium and plutonium complexes with di- and monobuthylphosphoric acids (APC) and with orthophosphoric and di-2-ethylhexyl-phosphoric acids in 30% TBP solution-n-dodecane system are determined by spectrophotometric titration and radiometry methods. Posibility of forecasting radiation-chemical behaviour of actinids according to data on K and APC radiation-chemical yield values is demonstrated

Vapor-liquid equilibria for nitric acid-water and plutonium nitrate-nitric acid-water solutions

International Nuclear Information System (INIS)

Maimoni, A.

1980-01-01

The liquid-vapor equilibrium data for nitric acid and nitric acid-plutnonium nitrate-water solutions were examined to develop correlations covering the range of conditions encountered in nuclear fuel reprocessing. The scanty available data for plutonium nitrate solutions are of poor quality but allow an order of magnitude estimate to be made. A formal thermodynamic analysis was attempted initially but was not successful due to the poor quality of the data as well as the complex chemical equilibria involved in the nitric acid and in the plutonium nitrate solutions. Thus, while there was no difficulty in correlating activity coefficients for nitric acid solutions over relatively narrow temperature ranges, attempts to extend the correlations over the range 25 0 C to the boiling point were not successful. The available data were then analyzed using empirical correlations from which normal boiling points and relative volatilities can be obtained over the concentration ranges 0 to 700 g/l Pu, 0 to 13 M nitric acid. Activity coefficients are required, however, if estimates of individual component vapor pressures are needed. The required ternary activity coefficients can be approximated from the correlations

Study of TBP stability limits in pyrolysis, radiolysis and hydrolysis

International Nuclear Information System (INIS)

Azzouz, A.; Attou, M.

1985-10-01

The present investigations deal with the determination of the stability limits of different degradation phenomena during TBP process achievement, its purification, storage or in radioelements extraction. The results were obtained using a simple and quick analysis method based on TBP:HC104 complex formation. The TBP is considered stable (when its degradation rate is less than 0,5% Vol.) for temperature less than 100 0 C and time contact value of about 2 hours. It was depicted that TBP has an appreciable stability under the following conditions: NaOH 0,1 N/TBP=0,5 ml/ml and time contact <4 hours; POC13/TBP=0,02 ml/ml and time contact <1 hour; concentrated acid/TBP=0,025 ml/ml and time contact <1 h. Radiation cumulative effect seems to be the main precursor of TBP degradation. However, its stability remains appreciable under certain conditions. Practically, in all the cases, TBP decomposition is mainly tied to C-O bond breakdown

Resolution of the mixture TBP-H/sub 2/ MPB-HDB-PH/sub 3/PO/sub 4/. Application to the systems UO/sub 2/(NO/sub 3/)/sub 2/-TBP, Th(NO/sub 3/)/sub 4/-TBP and ZrO(NO/sub 3/)/sub 2/-TBP

Energy Technology Data Exchange (ETDEWEB)

Pires, M A.F.; Abrao, A [Instituto de Pesquisas Energeticas e Nucleares, Sao Paulo (Brazil). Centro de Engenharia Quimica

1980-01-01

Tributylphosphate (TBP) is presently the most used extractant for uranium, thorium and zirconium technologies, both for the purification of these elements from their concentrates and for the recovery of heavy metals in the reprocessing of irradiated fuels. Nevertheless, in the presence of phosphoric acid, some degradation products are formed, such as: di-n-butylphosphoric acid (HDBP), monobutylphosphoric ancd (H/sub 2/MBP) and ortophosphoric acid. The accumulation of these degradation products in the organic phase of the liquid-liquid extraction processes is highly undesirable. In order to avoid this problem, the separation of the mixture HDBP, H/sub 2/MBP and H/sub 3/PO/sub 4/ in TBP-dilutent or TBP-diluent-uranyl, thorium of zirconyl nitrate was then studied. Several separation techniques were investigated: adsorption using a cationic resin saturated with U(VI), chromatography in macroporous polymers, chromatography in alumina columns. Refractive index and condutimetric measurements were carried out to follow up the separation processes. The best results were obtained in an alumina column.

Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

International Nuclear Information System (INIS)

Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gibina, M.Yu.

1989-01-01

The concentration stability constants (K s ) and solubility of neptunium and plutonium complexes with di- and monobutylphosphoric acids (APA), as well as with orthophosphoric acid in the system composed of 30% TBP + n-dodecane, have been determined by spectrophotometric titration and radiometry. The feasibility of predicting the radiative chemical behavior of actinides based on their K s values and the radiative chemical yield of APA has been demonstrated

Separation of U and Pu be the method of liquid chromatography with free stationary phase in TBP - white spirit - nitric acid system

International Nuclear Information System (INIS)

Litvina, M.N.; Malikov, D.A.; Maryutina, T.A.; Kulyako, Yu.M.; Myasoedov, B.F.

2006-01-01

Possibility is studied of the use of liquid chromatography with free stationary phase for U and Pu separation from organic extract obtained by direct dissolution of MOX-fuel in supercritical CO 2 containing TBP·nHNO 3 complex. As stationary phase solutions of TBP in white-spirit of different concentrations are used. Effect of composition of stationary and mobile phases on separation efficiency is investigated. It is shown that use of liquid chromatography with free stationary phase permits to separate U and Pu in conditions of TBP concentration gradient in stationary phase and HNO 3 concentration gradient in mobile one [ru

Corrosion resistance of zirconium in nitric acid

International Nuclear Information System (INIS)

Kajimura, H.; Morikawa, H.; Nagano, H.

1987-01-01

Slow strain rate tests are effected on zirconium in boiling nitric acid to study the influence of nitric acid concentration, of oxidizing ions (Cr and Ce) and of electric potential. Corrosion resistance is excellent and stress corrosion cracking occurs only for severe conditions: 350 mV over electric potential for corrosion with nitric acid concentration of 40 % [fr

Densification of ∼5 nm-thick SiO_2 layers by nitric acid oxidation

International Nuclear Information System (INIS)

Choi, Jaeyoung; Joo, Soyeong; Park, Tae Joo; Kim, Woo-Byoung

2017-01-01

Highlights: • Leakage current density of the commercial PECVD grown ∼5 nm SiO_2 layer has been decreased about three orders of magnitude by densification. • The densification of SiO_2 layer is achieved by high oxidation ability of O·. • Densities of suboxide, fixed charge (N_f) and defect state (N_d) in SiO_2/Si interface are decreased by NAOS and PMA. • Tunneling barrier height (Φ_t) is increased because of the increase of atomic density in SiO_2 layer. - Abstract: Low-temperature nitric acid (HNO_3) oxidation of Si (NAOS) has been used to improve the interface and electrical properties of ∼5 nm-thick SiO_2/Si layers produced by plasma-enhanced chemical vapor deposition (PECVD). Investigations of the physical properties and electrical characteristics of these thin films revealed that although their thickness is not changed by NAOS, the leakage current density at a gate bias voltage of −1 V decreases by about two orders of magnitude from 1.868 × 10"−"5 A/cm"2. This leakage current density was further reduced by post-metallization annealing (PMA) at 250 °C for 10 min in a 5 vol.% hydrogen atmosphere, eventually reaching a level (5.2 × 10"−"8 A/cm"2) approximately three orders of magnitude less than the as-grown SiO_2 layer. This improvement is attributed to a decrease in the concentration of suboxide species (Si"1"+, Si"2"+ and Si"3"+) in the SiO_2/Si interface, as well as a decrease in the equilibrium density of defect sites (N_d) and fixed charge density (N_f). The barrier height (Φ_t) generated by a Poole-Frenkel mechanism also increased from 0.205 to 0.371 eV after NAOS and PMA. The decrease in leakage current density is therefore attributed to a densification of the SiO_2 layer in combination with the removal of OH species and increase in interfacial properties at the SiO_2/Si interface.

Reductive stripping of Np using a n-butyraldehyde from a loaded TBP phase containing Np

International Nuclear Information System (INIS)

Lee, Eil Hee; Lim, Jae Kwan; Chung, Dong Yong; Yang, Han Beom; Kim, Kwang Wook

2008-01-01

The reductive stripping of Np using a n-butyraldehyde (NBA) from loaded organic solution containing Np, which was oxidative-extracted in a system of a 30 % TBP/NDD-2M HNO 3 and O/A=2 containing 0.005 M K 2 Cr 2 O 7 as an oxidant of Np, was studied. The stripping yields of Np was increased with an increasing the NBA concentration, with a decreasing the nitric acid concentration of stripping solution and with a decreasing the reaction temperature. The apparent reductive stripping rate equation was shown by the following equation : -d [Np]-O-r-g/dt = 1,524 exp(-2,906/T) [NBA] 0.92 [Np] Org . At 1.04 M NBA and 2 M HNO 3 , the stripping yield of Np and U was 70.1 %, and 7.1 %, respectively, and the separation factor of U over Np (=D U /D Np ) was about 30.4. Therefore, it was found that U and Np co-extracted in a system of TBP-NHO 3 could be effectively mutual-separated by the NBA.

TWOPOT: a computer model of the two-pot extractive distillation concept for nitric acid

International Nuclear Information System (INIS)

Jubin, R.T.; Holland, W.D.; Counce, R.M.; Beckwith, D.R.

1985-05-01

A mathematical model, TWOPOT, of the ''two-pot'' extractive distillation concept for nitric acid concentration has been developed. Prediction from a computer simulation using this model shows excellent agreement with the experimental data. This model is recommended for use in the design of large-scale, similar-purpose equipment. 9 refs., 15 figs., 2 tabs

Analytical resolution of the mixture TBP-HDBP-H2MBP-H3PO4

International Nuclear Information System (INIS)

Pires, M.A.F.

1983-01-01

Several schemes for the separation of dibutylphosphoric acid (HDBP), main degradation product of tributylphosphate (TBP), in TBP/diluent, TBP/diluent-uranyl nitrate and TBP/diluent-thorium nitrate mixture were studied. For the resolution of HDBP-TBP/diluent-heavy metal nitrates (U-VI,Th-IV) systems, techniques such as: in exchange chromatography, ion chromatography using common ion exchangers and chromatographic separation with alumina column were investigated. For the identification, determination and analytical resolution following up the several systems studied, techniques such as refraction index measurement, electrical conductivity measurement, molecular absorption spectrophotometry, gas chromatography and ion chromatography, were applied. The separation of HDBP component was achieved using an alumina column where it was adsorbed from the TBP/diluent-uranyl nitrate and selectively eluted. Several modifications of this procedure for samples from the Uranium Purification Pilot Plant at Instituto de Pesquisas Energeticas e Nucleares (Sao Paulo, Brazil) were made. Special emphasis was given to the determination of HDBP using the ion chromatography technique. HDBP along with any monobutylphosphate acid (H 2 MBP) and phosphoric acid (H 3 PO 4 ) were stripped from the organic phase into dilute sodium hydroxide. HDBP is separated from H 2 MBP and H 3 PO 4 by ion chromatography and determined by its peak height. The determination of degradation products from TBP in TBP/diluent-uranyl nitrate and TBP/diluent-thorium nitrate systems was then performed. The detection limit for dibutylphosphate is 1.0μg HDBP/ml of analyte solution. (Author) [pt

Nitric acid adduct formation during crystallization of barium and strontium nitrates and their co-precipitation from nitric acid media

International Nuclear Information System (INIS)

Mishina, N.E.; Zilberman, B.Ya.; Lumpov, A.A.; Koltsova, T.I.; Puzikov, E.A.; Ryabkov, D.V.

2015-01-01

The molar solubilities of Ba, Sr and Pb nitrates in nitric acid as a function of total nitrate concentration is presented and described by the mass action law, indicating on formation of the adducts with nitric acid. Precipitates of Ba(NO 3 ) 2 and Sr(NO 3 ) 2 crystallized from nitric acid were studied by ISP OES and IR spectroscopy. The data obtained confirmed formation of metastable adducts with nitric acid. IR and X-ray diffraction studies of the mixed salt systems indicated conversion of the mixed salts into (Ba,Sr)(NO 3 ) 2 solid solution of discrete structure in range of total nitrate ion concentration ∼6 mol/L. (author)

Containment of Nitric Acid Solutions of Plutonium-238

International Nuclear Information System (INIS)

Reimus, M.A.H.; Silver, G.L.; Pansoy-Hjelvik, L.; Ramsey, K.

1999-01-01

The corrosion of various metals that could be used to contain nitric acid solutions of Pu-238 has been studied. Tantalum and tantalum/2.5% tungsten resisted the test solvent better than 304L stainless steel and several INCONEL alloys. The solvent used to imitate nitric acid solutions of Pu-238 contained 70% nitric acid, hydrofluoric acid, and ammonium hexanitratocerate

Role of nitrous acid during the dissolution of UO2 in nitric acid

International Nuclear Information System (INIS)

Deigan, N.; Pandey, N.K.; Kamachi Mudali, U.; Joshi, J.B.

2016-01-01

Understanding the dissolution behaviour of sintered UO 2 pellet in nitric acid is very important in designing an industrial scale dissolution system for the plutonium rich fast reactor MOX fuel. In the current article we have established the role of nitrous acid on the dissolution kinetics of UO 2 pellets in nitric acid. Under the chemical conditions that prevail in a typical Purex process, NO and NO 2 gases gets generated in the process streams. These gases produce nitrous acid in nitric acid medium. In addition, during the dissolution of UO 2 in nitric acid medium, nitrous acid is further produced in-situ at the pellet solution interface. As uranium dissolves oxidatively in nitric acid medium wherein it goes from U(IV) in solid to U(VI) in liquid, presence of nitrous acid (a good oxidizing agent) accelerates the reaction rate. Hence for determining the reaction mechanism of UO 2 dissolution in nitric acid medium, knowing the nitrous acid concentration profile during the course of dissolution is important. The current work involves the measurement of nitrous acid concentration during the course of dissolution of sintered UO 2 pellets in 8M starting nitric acid concentration as a function of mixing intensity from unstirred condition to 1500 RPM

Extraction of zirconium(IV) and separation of 95Zr-95Nb from acidic thiocyanate media by LIX 54 and its mixtures with TBP

International Nuclear Information System (INIS)

Mishra, P.K.; Chakravortty, V.; Dash, K.C.; Das, N.R.; Bhattacharyya, S.N.

1990-01-01

Appreciable extraction of 95 Zr- 95 Nb by LIX 54 from aqueous HCl alone is not observed in the concentration range from 0.1 to 2 M HCl. Presence of thiocyanate ions results in appreciable extraction of this pair from such acid medium. Synergism has been observed in the extraction of zirconium(IV) by mixtures of LIX 54 and TBP from thiocyanate media, whereas there has been no appreciable synergism in case of niobium(V) under identical conditions. Slope analyses indicate the species extracted by pure TBP to be disolvate whereas for extraction by the mixtures of LIX 54 and TBP it is found to be monosolvate with respect to TBP. The extraction of both the metal ions have been found to depend on the concentration of acid as well as that of thiocyanate ions. Extraction increases with increase in percentage of either of the extractants. Effective separation of these congeneric pairs has been achieved by suitable choice of above system. Extraction is independent of aq. zirconium concentration up to 0.01 M above which it decreases. (orig.)

Dynamics of TBP binding to the TATA box

Science.gov (United States)

Schluesche, Peter; Heiss, Gregor; Meisterernst, Michael; Lamb, Don C.

2008-02-01

Gene expression is highly controlled and regulated in living cells. One of the first steps in gene transcription is recognition of the promoter site by the TATA box Binding Protein (TBP). TBP recruits other transcriptions factors and eventually the RNA polymerase II to transcribe the DNA in mRNA. We developed a single pair Förster Resonance Energy Transfer (spFRET) assay to investigate the mechanism of gene regulation. Here, we apply this assay to investigate the initial binding process of TBP to the adenovirus major late (AdML) promoter site. From the spFRET measurements, we were able to identify two conformations of the TBP-DNA complex that correspond to TBP bound in the correct and the opposite orientation. Increased incubation times or the presence of the transcription factor TFIIA improved the alignment of TBP on the promoter site. Binding of TBP to the TATA box shows a rich dynamics with abrupt transitions between multiple FRET states. A frame-wise histogram analysis revealed the presence of at least six discrete states, showing that TBP binding is more complicated than previously thought. Hence, the spFRET assay is very sensitive to the conformation of the TBP-DNA complex and is very promising tool for investigating the pathway of TBP binding in detail.

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction

International Nuclear Information System (INIS)

Lemaire, M.

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V SHE and between 0,5 V SHE and 1 V SHE . The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V SHE , products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Nitric acid flowsheet with late wash PHA testing

International Nuclear Information System (INIS)

Zamecnik, J.R.

1993-01-01

This Task Technical Plan outlines the activities to be conducted in the Integrated DWPF Melter System (IDMS) in ongoing support of the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) utilizing the Nitric Acid Flowsheet in the Sludge Receipt and Adjustment Tank (SRAT) and Precipitate Hydrolysis Aqueous (PHA) produced by the Late Wash Flowsheet. The IDMS facility is to be operated over a series of runs (2 to 4) using the Nitric Acid Flowsheet. The PHA will be produced with the Late Wash Flowsheet in the Precipitate Hydrolysis Experimental Facility (PHEF). All operating conditions shall simulate the expected DWPF operating conditions as closely as possible. The task objectives are to perform at least two IDMS runs with as many operating conditions as possible at nominal DWPF conditions. The major purposes of these runs are twofold: verify that the combined Late Wash and Nitric Acid flowsheets produce glass of acceptable quality without additional changes to process equipment, and determine the reproducibility of data from run to run. These runs at nominal conditions will be compared to previous runs made with PHA produced from the Late Wash flowsheet and with the Nitric Acid flowsheet in the SRAT (Purex 4 and Purex 5)

New Data on Joint Extraction of Nitric Acid, Uranium(VI) and Tetravalent Elements by Diluted TBP and New Approach to Modeling of their Distribution

International Nuclear Information System (INIS)

Zilberman, B.Ya.; Fedorov, Yu.S.; Puzikov, E.A.; Blazheva, I.V.

2008-01-01

HNO 3 and U(IV) extraction by diluted TBP (tributyl phosphate) appeared significantly higher than believed earlier, requiring correction of mathematical model for extraction of all the species. The proposed model of HNO 3 extraction includes its dissolving in the extracted water, as well as its abduction to UO 2 (NO 3 ) 2 (TBP) 2 . Extraction of U(VI) and tetravalent elements is considered as reaction of their hydrated or partially hydrolyzed forms, the latter could be extracted themselves or as neutral forms with water liberation. The equation of element chemical reaction for modeling is determined by the slope of the linear part of the S-shaped curve representing D/S 2 function as a plot of HNO 3 concentration, where D is a distribution coefficient of the micro-component and S is a TBP concentration free of HNO 3 . The description of tetravalent element extraction in U(VI) presence needs the assumption of cation-cation interaction of element hydrolyzed forms with U(VI) in aqueous phase. Zr distribution is affected by micellar effects. (authors)

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid

International Nuclear Information System (INIS)

Lemaire, M.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V S HE and 0.3 V S HE and O.5 V S HE and 1 V S HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V S HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Modelling the liquid-liquid extraction of nitric acid and lanthanide nitrates by tributylphosphate. Study of the influence of the aqueous phase composition on the selectivity of rare earth separation

International Nuclear Information System (INIS)

Mokili, Bandombele

1992-01-01

This research thesis reports the application of advances in the modelling of liquid-liquid extraction to a quantitative processing of the selectivity of separations. It is here applied to the extraction-based separation of lanthanide nitrates by using the tributylphosphate (TBP) in nitric environment as this system is interesting for industrial applications in hydro-metallurgy of rare earths as well as in the processing of irradiated nuclear fuels. Experimental data are acquired and then used in the Mikulin-Sergievskii-Dannus model. Complete modelling is thus obtained which allowed the complex problem of extraction of nitric acid and of lanthanide to be addressed, and the existence of a hybrid solvate to be supported. A mathematical expression of the separation factor of two lanthanides is proposed and used to highlight its influencing parameters, i.e. water activity in the aqueous phase, and the rate of the effective extraction constants of the two elements to be separated. Experimental observations are thus interpreted. The selection of optimal separation conditions is thus justified, and, in some cases, the system selectivity can be predicted [fr

Image analysis of epicuticular damage to foliage caused by dry deposition of the air pollutant nitric acid.

Science.gov (United States)

Padgett, Pamela E; Parry, Sally D; Bytnerowicz, Andrzej; Heath, Robert L

2009-01-01

Nitric acid vapor is produced by the same photochemical processes that produce ozone. In the laboratory, concentrated nitric acid is a strong acid and a powerful oxidant. In the environment, where the concentrations are much lower, it is an innocuous source of plant nitrogen. As an air pollutant, which mode of action does dry deposition of nitric acid follow? We investigated the effects of dry deposition of nitric acid on the foliage of four tree species native to the western United States. A novel controlled environment, fumigation system enabled a four-week exposure at concentrations consistent with ambient diurnal patterns. Scanning electron microscopy and automated image analysis revealed changes in the epicuticular wax layer during fumigation. Exposure to nitric acid resulted in a reproducible suite of damage symptoms that increased with increasing dose. Each tree species tested exhibited a unique set of damage features, including cracks, lesions, and conformation changes to epicuticular crystallite structures. Dry deposition of atmospheric nitric acid caused substantial perturbation to the epicuticular surface of all four tree species investigated, consistent with the chemical oxidation of epicuticular waxes. Automated image analysis eliminated many biases that can trouble microscopy studies. Trade names and commercial enterprises or products are mentioned solely for information. No endorsements by the U.S. Department of Agriculture are implied.

Solvent extraction of thorium from nitrate medium by TBP, Cyanex272 and their mixture

International Nuclear Information System (INIS)

Mostaan Shaeri; Ahmad Rahbar Kelishami; Meisam Torab-Mostaedi

2015-01-01

The extraction behavior of thorium(IV) has been investigated with tri-butyl phosphate (TBP) and bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272) in kerosene from nitrate medium. The effect of operating variables including time, aqueous phase acidity (pH), extractant concentration and temperature were investigated. This study also examined the synergistic enhancement of the extraction of thorium(IV) from nitrate medium by mixtures of TBP and Cyanex272 for the first time. The optimum synergistic enhancement factor of 3.86 was obtained at a Cyanex272/TBP molar ratio of 1:4. (author)

Solvent extraction separation and spectrographic determination of palladium, rhodium and ruthenium in uranium

International Nuclear Information System (INIS)

Capdevilla, C.; Alduan, F. A.

1980-01-01

The determination of Pd, Rh and Ru in uranium at low ppm level, using solvent extraction has been studied. BPHA, TNOA, TOPO and TBP have been tried as complexing agents; TBP In hexane and 5 M nitric acid medium provides a virtually quantitative extraction. The layer containing the impurities is collected Into graphite powder, and this powder is analysed spectro graphically using carrier destination method with % CuF 2 as a carrier. (Author) 11 refs

Studies on the solvent extraction behaviour of Pu(IV) from nitric acid, nitric-perchloric acid and hydrochloric acids, by di,2-ethylhexyl phosphoric acid (HDEHP)

International Nuclear Information System (INIS)

Phal, D.G.; Kannan, S.K.; Ramakrishna, V.V.

1994-01-01

Extraction of plutonium (IV) from aqueous nitric acid, nitric-perchloric acid and hydrochloric acids by di,2-ethylhexyl phosphoric acid, the dimeric form of which is represented as H 2 Y 2 , in different diluents (dodecane, toluene and chloroform) was investigated. The composition of the extracted Pu(IV) species were found to be Pu(NO 3 ) 2 (HY) 2 , Pu(NO 3 )(ClO 4 )(HY 2 ) 2 , PuClY(HY 2 ) 2 and PuCl 2 (HY 2 ) 2 from nitric, nitric-perchloric and hydrochloric acids respectively, the last one being pre-dominant at high aqueous acidities (i.e. 5M HCl). Synergic enhancement in the extraction of Pu(IV) from different aqueous media, by the addition of thenoyltrifluoroacetone (HTTA) to HDEHP was also investigated and was attributed to the formation and extraction of the species PuX(TTA)(HY 2 ) 2 , and Pu(TTA) 2 (HY 2 ) 2 where X=Cl - or NO 3 - . The addition of the neutral extractant TOPO to H 2 Y 2 also resulted in synergism. The possible equilibria in these systems were inferred and the corresponding equilibrium constants determined. (author). 24 refs., 10 figs., 10 tabs

Stainless steel welding method with excellent nitric acid corrosion resistance

International Nuclear Information System (INIS)

Matsushita, Yukinobu; Inazumi, Toru; Hyakubo, Tamako; Masamura, Katsumi.

1996-01-01

The present invention concerns a welding method for a stainless steel used in a circumstance being in contact with a highly oxidizing nitric acid solution such as nuclear fuel reprocessing facilities, upon welding 316 type austenite steel containing Mo while giving excellent nitric acid resistance. A method of TIG welding using a filler metal having a composition of C, Si, Mn, P, S, Ni, Cr, Mo and Cu somewhat different from a stainless steel mother material in which C, Si, Mn, P, S, Ni, Cr and Mo are specified comprises a step of TIG-welding the surface of the mother material and a step of TIG-welding the rear face of the mother material, in which the welding conditions for the rear face of the mother material are such that the distance between the surface of the outermost welding metal layer on the side of the surface of the mother material and the bottom of the groove is not less than 5mm, and an amount of welding heat is made constant. As a result, even if the method is used in a circumstance being in contact with a highly corrosive solution such as nitric acid, corrosion resistance is not degraded. (N.H.)

MOCVD growth of InP-related materials using TBA and TBP

International Nuclear Information System (INIS)

Czub, M.; Strupinski, W.

1995-01-01

High quality epitaxial layers of GaAs, InP, AlAs, InGaAs, InGaP, InGaAlP have been grown by low-pressure metalorganic chemical vapor deposition using TMIn, TMGa, TMAl and the less hazardous group V precursors, temperature ranges of 570-650 C and 520-650 C, respectively. The V/III ratio as low as 1.5 was used to grow epilayers of InP. The 77 K mobility of InGaAs lattice matched to InP (grown with TBA) was 72360 cm 2 /(Vs) for n = 1.5 x 10 1 5/cm 3 and the thickness of 2 μm. Comparable photoluminescence parameters of InGaAlP between layers grown with TBP and PH 3 were achieved, but for InGaAlP (TBP) photoluminescence intensity was significantly lower than for InGaAlP (PH 3 ). The promising results allow one to apply of TBA and TBP for developing of device structures. (author)

Nitrogen isotope exchange between nitric oxide and nitric acid

International Nuclear Information System (INIS)

Axente, D.; Abrudean, M.; Baldea, A.

1996-01-01

The rate of nitrogen isotope exchange between NO and HNO 3 has been measured as a function of nitric acid concentration of 1.5-4M x 1 -1 . The exchange rate law is shown to be R=k[HNO 3 ] 2 [N 2 O 3 ] and the measured activation energy is E=67.78 kJ x M -1 (16.2 kcal x M -1 ). It is concluded that N 2 O 3 participates in 15 N/ 14 N exchange between NO and HNO 3 at nitric acid concentrations higher than 1.5M x 1 -1 . (author). 7 refs., 3 figs., 4 tabs

The nitric acid decomposition of calcined danburite concentrate of Ak-Arkhar Deposit

International Nuclear Information System (INIS)

Kurbonov, A.S.; Mamatov, E.D.; Suleymani, M.; Borudzherdi, A.; Mirsaidov, U.M.

2011-01-01

Present article is devoted to nitric acid decomposition of calcined danburite concentrate of Ak-Arkhar Deposit of Tajikistan. The obtaining of boric acid from pre backed danburite concentrate by decomposition of nitric acid was studied. The chemical composition of danburite concentrate was determined. The laboratory study of danburite leaching by nitric acid was conducted. The influence of temperature, process duration, nitric acid concentration on nitric acid decomposition of calcined danburite concentrate of Ak-Arkhar Deposit was studied as well. The optimal conditions of nitric acid decomposition of calcined danburite concentrate of Ak-Arkhar Deposit, including temperature, process duration, nitric acid concentration and particle size were proposed.

Densification of ∼5 nm-thick SiO{sub 2} layers by nitric acid oxidation

Energy Technology Data Exchange (ETDEWEB)

Choi, Jaeyoung [Department of Energy Engineering, Dankook University, Cheonan 311-16 (Korea, Republic of); Joo, Soyeong [Institute for Advanced Engineering (IAE), Advanced Materials & Processing Center, Youngin 449-863 (Korea, Republic of); Park, Tae Joo [Department of Materials Science and Chemical Engineering, Hanyang University, Ansan 15588 (Korea, Republic of); Kim, Woo-Byoung, E-mail: woo7838@dankook.ac.kr [Department of Energy Engineering, Dankook University, Cheonan 311-16 (Korea, Republic of)

2017-08-15

Highlights: • Leakage current density of the commercial PECVD grown ∼5 nm SiO{sub 2} layer has been decreased about three orders of magnitude by densification. • The densification of SiO{sub 2} layer is achieved by high oxidation ability of O·. • Densities of suboxide, fixed charge (N{sub f}) and defect state (N{sub d}) in SiO{sub 2}/Si interface are decreased by NAOS and PMA. • Tunneling barrier height (Φ{sub t}) is increased because of the increase of atomic density in SiO{sub 2} layer. - Abstract: Low-temperature nitric acid (HNO{sub 3}) oxidation of Si (NAOS) has been used to improve the interface and electrical properties of ∼5 nm-thick SiO{sub 2}/Si layers produced by plasma-enhanced chemical vapor deposition (PECVD). Investigations of the physical properties and electrical characteristics of these thin films revealed that although their thickness is not changed by NAOS, the leakage current density at a gate bias voltage of −1 V decreases by about two orders of magnitude from 1.868 × 10{sup −5} A/cm{sup 2}. This leakage current density was further reduced by post-metallization annealing (PMA) at 250 °C for 10 min in a 5 vol.% hydrogen atmosphere, eventually reaching a level (5.2 × 10{sup −8} A/cm{sup 2}) approximately three orders of magnitude less than the as-grown SiO{sub 2} layer. This improvement is attributed to a decrease in the concentration of suboxide species (Si{sup 1+}, Si{sup 2+} and Si{sup 3+}) in the SiO{sub 2}/Si interface, as well as a decrease in the equilibrium density of defect sites (N{sub d}) and fixed charge density (N{sub f}). The barrier height (Φ{sub t}) generated by a Poole-Frenkel mechanism also increased from 0.205 to 0.371 eV after NAOS and PMA. The decrease in leakage current density is therefore attributed to a densification of the SiO{sub 2} layer in combination with the removal of OH species and increase in interfacial properties at the SiO{sub 2}/Si interface.

Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid

International Nuclear Information System (INIS)

Oji, L.

2014-01-01

The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent of dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min -1 and 1.07E-03 ± 7.51E-05 min -1 . Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is 10.8 hours

Leaching of sodium carbonate cakes by nitric acid

International Nuclear Information System (INIS)

Troyanker, L.S.; Nikonov, V.N.

1977-01-01

The interaction has been studied of soda cakes of fluorite-rare-earth concentrate with nitric acid. The effect of a number of factors on extraction of REE into a nitric solution has been considered: the final acidity of the pulp, the duration of leaching, and the ratio between solid and liquid phases. The effect of adding aluminium nitrate into the pulp has also been studied. It has been shown that three-stage counterflow leaching of soda cakes with nitric acid increases REE extraction approximately by 10%

Investigation of the synergistic effect of alcoholic compounds on the extraction of H3PO4 from Syrian wet phosphoric acid by TBP

International Nuclear Information System (INIS)

Abdulbaki, M. K.; Shino, O.; Wahoud, A.

2006-01-01

This paper studies the synergistic effects of alcoholic compounds such as isoamyl alcohol. Pentanol, hexanol and heptanol on the extraction of H 3 PO 4 from Syrian phosphoric acid by (TBP). The possibility to use these alcoholic compounds as a diluent instead of kerosene was also studied. The results show that the alcoholic compounds has bigger extraction yield than (TBP) diluted in kerosene. The alcoholic compounds has an important synergistic effect, when it was used as a diluent instead of kerosene, on the extraction of H 3 PO 4 by (TBP) and they have a bigger extraction yield and the quicker phase separation comparing with kerosene. Extraction of uranium, fluoride, sulfate and heavy metals is relatively small. (Authors)

Separation of the components of the TBP-H2 MBP-HDBP-H3PO4 mixture

International Nuclear Information System (INIS)

Pires, M.A.F.; Abrao, A.

1981-04-01

Several schemes for the separation of dibutylphosphoric acid (HDBP), monobutylphosphoric acid (H 2 MBP) and orthophosphoric acid (H 3 PO 4 ) as hydrolytic and radiolytic degradation products from tri-n-butylphosphate (TBP) were studied. For the resolution of a HDBP, H 2 MPB and H 3 PO 4 mixture in TBP-diluent, or in TBP-diluent-heavy metal nitrate (U-VI, Th-IV or Zr-IV), techniques such as ion exchange chromatography, ion chromatography and separation onto a chromatographic alumina column were investigated. For the identification, determination and analytical resolution following up for the several systems studied, techniques such as refraction index measurement, electrical conductivity measurement, molecular spectrophotometry and gas chromatography were applied. Special emphasys was given to the separation using alumina column where the HDBP acid was retained and eluted selectively for its separation from TBP-varsol-uranyl nitrate mixtures. This analytical procedure was applied to the samples coming from the Uranium Purification Pilot Plant in operation at the Centro de Engenharia Quimica (IPEN). (Author) [pt

Elution of Uranium and Calculation of Plate Number on the Column of Silica-TBP

International Nuclear Information System (INIS)

Endang Susiantini; Indra Suryawan

2007-01-01

Separation process of 99 Mo resulted of irradiated uranyl nitrate with an accelerator as the neutron source by the chromatographic extraction using column containing kiesel gel-TBP will be developed. Kiesel gel (silica) was used as an inert subpart, TBP as a phase stationary and simulated used natural uranyl nitrate of 200-300 g/l with the acidity of 2 N as the mobile phase. The inert support was made by means of kiesel-gel (silica) hydrophobization to change hydrophilic silica to hydrophobic silica, so that it could be impregnated by TBP. Uranium which has been attached to TBP would be eluted by dilute acid at acidity of 0.05; 0.1; 0.2 N HNO 3 ; Warm DW and cool DW. By using 0.1 N HNO 3 eluent and warm DW the uranium attached to silica-TBP could be eluted perfectly and more quickly than the three others eluent. Uranium concentration which were absorbed and eluted were analysed titrimetrically by using titan method and it was used to calculate Plate Number (N). The value of N obtained for the column which the inert support of 8 cm in height, 1 cm in diameter, 10 drops per minute by using of 0.1 N HNO 3 eluent was 300.6. (author)

Behavior of silicon in nitric media. Application to uranium silicides fuels reprocessing; Comportement du silicium en milieu nitrique. Application au retraitement des combustibles siliciures d'uranium

Energy Technology Data Exchange (ETDEWEB)

Cheroux, L

2001-07-01

Uranium silicides are used in some research reactors. Reprocessing them is a solution for their cycle end. A list of reprocessing scenarios has been set the most realistic being a nitric dissolution close to the classic spent fuel reprocessing. This uranium silicide fuel contains a lot of silicon and few things are known about polymerization of silicic acid in concentrated nitric acid. The study of this polymerization allows to point out the main parameters: acidity, temperature, silicon concentration. The presence of aluminum seems to speed up heavily the polymerization. It has been impossible to find an analytical technique smart and fast enough to characterize the first steps of silicic acid polymerization. However the action of silicic species on emulsions stabilization formed by mixing them with an organic phase containing TBP has been studied, Silicon slows down the phase separation by means of oligomeric species forming complex with TBP. The existence of these intermediate species is short and heating can avoid any stabilization. When non irradiated uranium silicide fuel is attacked by a nitric solution, aluminum and uranium are quickly dissolved whereas silicon mainly stands in solid state. That builds a gangue of hydrated silica around the uranium silicide particulates without preventing uranium dissolution. A small part of silicon passes into the solution and polymerize towards the highly poly-condensed forms, just 2% of initial silicon is still in molecular form at the end of the dissolution. A thermal treatment of the fuel element, by forming inter-metallic phases U-Al-Si, allows the whole silicon to pass into the solution and next to precipitate. The behavior of silicon in spent fuels should be between these two situations. (author)

Estimation of solubility of organo-phosphorus extractants by P determination using molybdovanadophosphoric acid method

International Nuclear Information System (INIS)

Gill, J.S.; Kotekar, M.K.; Singh, H.

2005-01-01

Solvent extraction processes have been found to be suitable for uranium recovery from phosphoric acid. Various extractants like di-2-ethyl hexylphosphoric acid (D2EHPA), di-nonylphenyl phosphoric acid (DNPPA) and synergistic agents like tri-butyl phosphate (TBP), tri-octyl phosphine oxide (TOPO) have been used in liquid-liquid extraction of uranium from phosphoric acid. Contents of these organo-phosphorus compounds in aqueous raffinates need estimation for process requirements. Solubility of Tri-butyl phosphate (TBP) and Di-2-ethylhexyl phosphoric acid (D2EHPA) extractants have been determined in different media of water, oxalic acid (0.6M) and sulphuric acid (3.75M) solutions. These compounds were estimated by determining their phosphorus (P) contents employing molybdovanadophosphoric acid method, after digesting and solubalizing them in nitric and perchloric acid. (author)

The production of rare earth elements group via tributyl phosphate extraction and precipitation stripping using oxalic acid

OpenAIRE

Jorjani, Esmaeil; Shahbazi, Malek

2016-01-01

In this study, solvent extraction and precipitation stripping were used to produce rare earth elements (REEs). Tributyl phosphate (TBP) was used to extract yttrium, lanthanum, cerium, and neodymium from an aqueous solution produced by nitric acid leaching of apatite concentrate. In the extraction stage, the effects of TBP concentration, pH, contact time, temperature, and phase ratio were investigated. The results show that about 95%, 90%, 87% and 80% of neodymium, cerium, lanthanum, and yttri...

Nitric acid recycling and copper nitrate recovery from effluent.

Science.gov (United States)

Jô, L F; Marcus, R; Marcelin, O

2014-01-01

The recycling of nitric acid and copper nitrate contained in an industrial effluent was studied. The experiments conducted on such a medium showed that the presence of copper nitrate significantly improves nitric acid-water separation during distillation in an azeotropic medium. At the temperature of the azeotrope, however, this metal salt starts to precipitate, making the medium pasty, thus inhibiting the nitric acid extraction process. The optimisation of parameters such as column efficiency and adding water to the boiler at the azeotrope temperature are recommended in this protocol in order to collect the various components while avoiding the formation of by-products: NOx compounds. Thus, the absence of column, along with the addition of a small volume of water at a temperature of 118 °C, significantly increases the yield, allowing 94 % nitric acid to be recovered at the end of the process, along with the residual copper nitrate. The resulting distillate, however, is sufficiently dilute to not be used as is. Rectification is required to obtain concentrated nitric acid at 15 mol·l(-1), along with a weakly acidic distillate from the distillation front. This latter is quenched using potassium hydroxide and is used as a fertiliser solution for horticulture or sheltered market gardening. This process thus allows complete recycling of all the medium's components, including that of the distillate resulting from the nitric acid rectification operation.

Studies on the reaction of nitric acid and sugar

International Nuclear Information System (INIS)

MacDougall, C.S.; Bayne, C.K.; Roberson, R.B.

1982-01-01

The design of vessels and off-gas systems for denitrating acidic radioactive process solutions by reacting nitric acid with sugar requires a fairly accurate determination of the rate of the controlling step. Therefore, the reaction of sugar with concentrated nitric acid was closely examined at temperatures of 100 and 110 0 C and in the presence of low levels of iron )0 to 0.2 M Fe(III)). Efficiencies of the sugar destruction by nitric acid ranged from 2.56 to 2.93 mol of acid consumed per mole of carbon added. Product off-gases were examined throughout the reaction. Release of CO was fairly constant throughout the reaction, but amounts of CO 2 increased as the nitric acid began to attack the terminal carboxylic acids produced from the consumption of sucrose. Voluminous quantities of NO 2 were released at the beginning of the reaction, but larger relative concentrations of NO were observed toward the end

76 FR 63878 - New Source Performance Standards Review for Nitric Acid Plants

Science.gov (United States)

2011-10-14

... technologies. Nitric acid production is also one of the industrial sectors for which ``white papers'' were... standards (NSPS) for nitric acid plants. Nitric acid plants include one or more nitric acid production units. These proposed revisions include a change to the nitrogen oxides (NO X ) emission limit, which applies...

Reactivity of Resorcinol Formaldehyde Resin with Nitric Acid

International Nuclear Information System (INIS)

King, William D.; Fondeur, Fernando F.; Wilmarth, William R.; Pettis, Myra E.

2005-01-01

Solid-state infrared spectroscopy, differential scanning calorimetry, and elemental analysis have been used to evaluate the reactivity of resorcinol formaldehyde resin with nitric acid and characterize the solid product. Two distinct reactions were identified within the temperature range 25-55 C. The first reaction is primarily associated with resin nitration, while the second involves bulk oxidation and degradation of the polymer network leading to dissolution and off-gassing. The threshold conditions promoting reaction have been identified. Reaction was confirmed with nitric acid concentrations as low as 3 M at 25 C applied temperature and 0.625 M at 66 C. Although a nitrated resin product can be isolated under appropriate experimental conditions, calorimetry testing indicates no significant hazard associated with handling the dry material

Nitrosation and Nitration of Fulvic Acid, Peat and Coal with Nitric Acid.

Directory of Open Access Journals (Sweden)

Kevin A Thorn

Full Text Available Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples.

Mechanism of nitric acid reduction and kinetic modelling

International Nuclear Information System (INIS)

Sicsic, David; Balbaud-Celerier, Fanny; Tribollet, Bernard

2014-01-01

In France, the recycling of nuclear waste fuels involves the use of hot concentrated nitric acid. The understanding and prediction of the behaviour of the structural materials (mainly austenitic stainless steels) requires the determination and modelling of the nitric acid reduction process. Nitric acid is indirectly reduced by an autocatalytic mechanism depending on the cathodic overpotential and acid concentration. This mechanism has been widely studied. All the authors agree on its autocatalytic nature, characterized by the predominant role of the reduction products. It is also generally admitted that neither nitric acid nor the nitrate ion is the electro-active species. However, the nature of the electro-active species, the place where the catalytic species regenerates and the thermodynamic and kinetic behaviour of the reaction intermediates remain uncertain. The aim of this study was to clarify some of these uncertainties by performing an electrochemical investigation of the reduction of 4 M nitric acid at 40 C at an inert electrode (platinum or gold). An inert electrode was chosen as the working electrode in a first step to avoid its oxidation and focus the research on the reduction mechanism. This experimental work enabled us to suggest a coherent sequence of electrochemical and chemical reactions. Kinetic modelling of this sequence was then carried out for a gold rotating disk electrode. A thermodynamic study at 25 C allowed the composition of the liquid and gaseous phases of nitric acid solutions in the concentration range 0.5-22 M to be evaluated. The kinetics of the reduction of 4 M nitric acid was investigated by cyclic voltammetry and chrono-amperometry at an inert electrode at 40 C. The coupling of chrono-amperometry and FTIR spectroscopy in the gaseous phase led to the identification of the gaseous reduction products as a function of the cathodic overpotential. The results showed that the reduction process is autocatalytic for potentials between 0

Resolution of the mixture TBP-H2 MPB-HDB-PH3PO4

International Nuclear Information System (INIS)

Pires, M.A.F.; Abrao, A.

1980-01-01

Tributylphosphate (TBP) is presently the most used extractant for uranium, thorium and zirconium technologies, both for the purification of these elements from their concentrates and for the recovery of heavy metals in the reprocessing of irradiated fuels. Nevertheless, in the presence of phosphoric acid, some degradation products are formed, such as: di-n-butylphosphoric acid (HDBP), monobutylphosphoric ancd (H 2 MBP) and ortophosphoric acid. The accumulation of these degradation products in the organic phase of the liquid-liquid extraction processes is highly undesirable. In order to avoid this problem, the separation of the mixture HDBP, H 2 MBP and H 3 PO 4 in TBP-dilutent or TBP-diluent-uranyl, thorium of zirconyl nitrate was then studied. Several separation techniques were investigated: adsorption using a cationic resin saturated with U(VI), chromatogtraphy in macroporous polymers, chromatography in alumina columns. Refractive index and condutimetric measurements were carried out to follow up the separation processes. The best results were obtained in an alumina column. (C.L.B.) [pt

High-resolution structure of TBP with TAF1 reveals anchoring patterns in transcriptional regulation.

Science.gov (United States)

Anandapadamanaban, Madhanagopal; Andresen, Cecilia; Helander, Sara; Ohyama, Yoshifumi; Siponen, Marina I; Lundström, Patrik; Kokubo, Tetsuro; Ikura, Mitsuhiko; Moche, Martin; Sunnerhagen, Maria

2013-08-01

The general transcription factor TFIID provides a regulatory platform for transcription initiation. Here we present the crystal structure (1.97 Å) and NMR analysis of yeast TAF1 N-terminal domains TAND1 and TAND2 bound to yeast TBP, together with mutational data. We find that yeast TAF1-TAND1, which in itself acts as a transcriptional activator, binds TBP's concave DNA-binding surface by presenting similar anchor residues to TBP as does Mot1 but from a distinct structural scaffold. Furthermore, we show how TAF1-TAND2 uses an aromatic and acidic anchoring pattern to bind a conserved TBP surface groove traversing the basic helix region, and we find highly similar TBP-binding motifs also presented by the structurally distinct TFIIA, Mot1 and Brf1 proteins. Our identification of these anchoring patterns, which can be easily disrupted or enhanced, provides insight into the competitive multiprotein TBP interplay critical to transcriptional regulation.

Mercury-free dissolution of aluminum-clad fuel in nitric acid

Science.gov (United States)

Christian, Jerry D.; Anderson, Philip A.

1994-01-01

A mercury-free dissolution process for aluminum involves placing the aluminum in a dissolver vessel in contact with nitric acid-fluoboric acid mixture at an elevated temperature. By maintaining a continuous flow of the acid mixture through the dissolver vessel, an effluent containing aluminum nitrate, nitric acid, fluoboric acid and other dissolved components are removed.

Uranium refining by solvent extraction

International Nuclear Information System (INIS)

Kraikaew, J.; Srinuttrakul, W.

2014-01-01

The solvent extraction process to produce higher purity uranium from yellowcake was studied in laboratory scale. Yellowcake, which the uranium purity is around 70% and the main impurity is thorium, was obtained from monazite processing pilot plant of Rare Earth Research and Development Center in Thailand. For uranium re-extraction process, the extractant chosen was Tributylphosphate (TBP) in kerosene. It was found that the optimum concentration of TBP was 10% in kerosene and the optimum nitric acid concentration in uranyl nitrate feed solution was 4 N. An increase in concentrations of uranium and thorium in feed solution resulted in a decrease in the distribution of both components in the extractant. However, the distribution of uranium into the extractant was found to be more than that of thorium. The equilibration study of the extraction system, UO_2(NO_3)/4N HNO_3 – 10%TBP/Kerosene, was also investigated. Two extraction stages were calculated graphically from 100,000 ppm uranium concentration in feed solution input with 90% extraction efficiency and the flow ratio of aqueous phase to organic phase was adjusted to 1.0. For thorium impurity scrubbing process, 10% TBP in kerosene was loaded with uranium and minor thorium from uranyl nitrate solution prepared from yellowcake and was scrubbed with different low concentration nitric acid. The results showed that at nitric acid normality was lower than 1 N, uranium distributed well to aqueous phase. As conclusion, optimum nitric acid concentration for scrubbing process should not less than 1 N and diluted nitric acid or de-ionized water should be applied to strip uranium from organic phase in the final refining process. (author)

Removal of plutonium from nitric acid-oxalic acid solutions using anion exchange method

International Nuclear Information System (INIS)

Kasar, U.M.; Pawar, S.M.; Joshi, A.R.

1999-01-01

An anion exchange method using Amberlyst A-26 (MP) resin was developed for removal of Pu from nitric acid-oxalic acid solutions without destroying oxalate. The method consists of sorption of Pu(IV) on Amberlyst A-26, a macroporous anion exchange resin, from nitric acid-oxalic acid medium in the presence of Al(NO 3 ) 3 . Pu(IV) breakthrough capacity of Amberlyst A-26 using synthetic feed solution was determined. (author)

Distribution and identification of Plutonium(IV) species in tri-n-butyl phosphate/HNO3 extraction system containing acetohydroxamic acid

International Nuclear Information System (INIS)

Tkac, P.; Paulenova, A.; Vandegrift, G.F.; Krebs, J.F.

2009-01-01

There was a significant research progress achieved with the aim to modify conventional PUREX process by stripping of plutonium from the tri-n-butyl phosphate (TBP) extraction product in the form of non-extractable complexes upon addition of back-hold complexation agents. The present paper reports effects of such salt-free complexant, acetohydroxamic acid (HAHA), on distribution ratio of Pu(IV) under wide concentration of nitric acid and additional nitrate. General formula of plutonium species present in the organic phase can be described as Pu(OH) x (AHA) y (NO3) 4-x-y x 2TBP x wHNO 3 . (author)

Uranium, neptunium and plutonium kinetics of extraction by tributylphosphate and trilaurylamine in a centrifugal contactor

International Nuclear Information System (INIS)

Bergeonneau, P.; Jaouen, C.; Germain, M.; Bathellier, A.

1977-01-01

Uranium, plutonium and neptunium kinetics of transfer between various aqueous nitric solutions and solvents have been measured at the laboratory scale, using a centrifugal contactor especially developed in the laboratory. The transfer kinetics of nitric acid, hexavalent U, tetravalent U, Np and Pu from nitric acid solutions into 30% TBP in r-dodecane and 10% trilaurylamine in r-dodecane have been studied. The effects of rotation speed, temperature, initial nitric acid concentration, metal concentration on extraction and stripping kinetics have been investigated. The results obtained show that TBP extraction and stripping are more rapid than trilaurylamine ones. The low activation energies of transfer reactions with TBP suggest that both in extraction and stripping, the transfer rate is limited by the diffusion of the species in the aqueous and organic phases. For trilaurylamine, the transfer mechanism appears more complex

Dissolution behavior of PFBR MOX fuel in nitric acid

International Nuclear Information System (INIS)

Kelkar, Anoop; Kapoor, Y.S.; Singh, Mamta; Meena, D.L.; Pandey, Ashish; Bhatt, R.B.; Behere, P.G.

2017-01-01

Present paper describes the dissolution characteristics of PFBR MOX fuel (U,Pu)O 2 in nitric acid. An overview of batch dissolution experiments, studying the percentage dissolution of uranium and plutonium in (U, Pu)O 2 MOX sintered pellets with different percentage of PuO 2 with reference to time and nitric acid concentration are described. 90% of uranium and plutonium of PFBR MOX gets dissolves in 2 hrs and amount of residue increases with the decrease in nitric acid concentration. Overall variation in percentage residue in PFBR MOX fuel after dissolution test also described. (author)

IR and UV spectroscopic analysis of TBP complexes

International Nuclear Information System (INIS)

Azzouz, A.; Berrak, A.; Seridi, L.; Attou, M.

1985-06-01

The complexity of TBP molecule and the limited number of references stimulated the elaboration of this report. The spectroscopic of TBP and its complexes in the IR and UV fields permitted to elucidate or to confirm certain aspects concerning the solvation phenomenum. In IR spectroscopy, the stretching band of the P→O bond only is characteristic of the complex formed. The position of this band gives sufficient information about the kind and the stability of a complex. The TBP electronic spectra are characterized by two bands (200-220 nm) 1 and (268-290 nm) 2 whose intensity ratio (2/1) is about 0,13. The solvent nature seems to influence the positions of these bands and that of the inflexion point. The band 2 disappears when the TBP is complexed and the position and the intensity of the band 1 depend upon the complex nature

Acute Respiratory Distress Syndrome (ARDS After Nitric Acid Inhalation

Directory of Open Access Journals (Sweden)

Gülay Kır

2014-12-01

Full Text Available Lung injury resulting from inhalation of chemical products continues to be associated with high morbidity and mortality. Concentrated nitric acids are also extremely corrosive fuming chemical liquids. Fumes of nitric acid (HNO3 and various oxides of nitrogen such as nitric oxide (NO and nitrogen dioxide (NO2 may cause fatal illnesses such as severe pulmonary edema and acute respiratory distress syndrome (ARDS when inhaled. Intensive respiratory management including mechanical ventilation with positive end expiratory pressure (PEEP, inverse ratio ventilation, replacement of surfactant and extracorporeal membrane oxygenation (ECMO, steroids and n-acetylcysteine (NAC may improve survival. In this case report we present the diagnosis and successful treatment of a 57 years old male patient who developed ARDS following pulmonary edema due to nitric acid fumes inhalation.

Hydrogen generation in SRAT with nitric acid and late washing flowsheets

International Nuclear Information System (INIS)

Hsu, C.W.

1992-01-01

Recently, SRTC recommended two process changes: (1) a final wash of the tetraphenylborate precipitate feed slurry and (2) the use of nitric acid to neutralize the sludge in the SRAT. The first change produced an aqueous hydrolysis product (PHA) with higher formic acid/formate and copper concentration, and reduced the nitrate content in the PHA by an order of magnitude. The second change is to substitute part of formic acid added to the SRAT with nitric acid, and therefore may reduce the hydrogen generated in the SRAT as well as provide nitrate as an oxidant to balance the redox state of the melter feed. The purpose of this report is to determine the pertinent variables that could affect the hydrogen generation rate with these process changes

THERMAL AND SPECTROSCOPIC ANALYSES OF CAUSTIC SIDE SOLVENT EXTRACTION SOLVENT CONTACTED WITH 16 MOLAR AND 8 MOLAR NITRIC ACID

International Nuclear Information System (INIS)

Fondeur, F; David Hobbs, D; Samuel Fink, S

2007-01-01

Thermal and spectroscopic analyses were performed on multiple layers formed from contacting Caustic Side Solvent Extraction (CSSX) solvent with 1 M or 3 M nitric acid. A slow chemical reaction occurs (i.e., over several weeks) between the solvent and 1 M or 3 M nitric acid as evidenced by color changes and the detection of nitro groups in the infrared spectrum of the aged samples. Thermal analysis revealed that decomposition of the resulting mixture does not meet the definition of explosive or deflagrating material

Recovery of Tin and Nitric Acid from Spent Solder Stripping Solutions

International Nuclear Information System (INIS)

Ahn, Jae-Woo; Ryu, Seong-Hyung; Kim, Tae-young

2015-01-01

Spent solder-stripping solutions containing tin, copper, iron, and lead in nitric acid solution, are by-products of the manufacture of printed-circuit boards. The recovery of these metals and the nitric acid, for re-use has economic and environmental benefits. In the spent solder-stripping solution, a systematic method to determine a suitable process for recovery of valuable metals and nitric acid was developed. Initially, more than 90% of the tin was successfully recovered as high-purity SnO 2 by thermal precipitation at 80 ℃ for 3 hours. About 94% of the nitric acid was regenerated effectively from the spent solutions by diffusion dialysis, after which there remained copper, iron, and lead in solution. Leakage of tin through the anion-exchange membrane was the lowest (0.026%), whereas Pb-leakage was highest (4.26%). The concentration of the regenerated nitric acid was about 5.1 N.

The extraction of rhodium from aqueous nitric acid by dinonylnaphthalene sulphonic acid

International Nuclear Information System (INIS)

Patel, N.M.; Miles, J.H.; Thornback, J.R.

1987-01-01

The extraction of rhodium from aqueous nitric acid using dinonylnaphthalene sulphonic acid has been investigated. The extraction occurs readily from 0.1 M to 1.0 M nitric acid and, since the rhodium is extracted as {Rh(H 2 O) 6 } 3+ into the inverted micelles of the organic solution, equilibration times are less than 5 minutes. Extraction is enhanced by addition of nitrite ion to form {Rh(H 2 O) 5 NO 2 } 2+ as the extracted species. (author)

Development of Acetic Acid Removal Technology for the UREX+Process

International Nuclear Information System (INIS)

Counce, Robert M.; Watson, Jack S.

2009-01-01

It is imperative that acetic acid is removed from a waste stream in the UREX+process so that nitric acid can be recycled and possible interference with downstream steps can be avoided. Acetic acid arises from acetohydrozamic acid (AHA), and is used to suppress plutonium in the first step of the UREX+process. Later, it is hydrolyzed into hydroxyl amine nitrate and acetic acid. Many common separation technologies were examined, and solvent extraction was determined to be the best choice under process conditions. Solvents already used in the UREX+ process were then tested to determine if they would be sufficient for the removal of acetic acid. The tributyl phosphage (TBP)-dodecane diluent, used in both UREX and NPEX, was determined to be a solvent system that gave sufficient distribution coefficients for acetic acid in addition to a high separation factor from nitric acid

Development of Acetic Acid Removal Technology for the UREX+Process

Energy Technology Data Exchange (ETDEWEB)

Robert M. Counce; Jack S. Watson

2009-06-30

It is imperative that acetic acid is removed from a waste stream in the UREX+process so that nitric acid can be recycled and possible interference with downstreatm steps can be avoidec. Acetic acid arises from acetohydrozamic acid (AHA), and is used to suppress plutonium in the first step of the UREX+process. Later, it is hydrolyzed into hydroxyl amine nitrate and acetic acid. Many common separation technologies were examined, and solvent extraction was determined to be the best choice under process conditions. Solvents already used in the UREX+ process were then tested to determine if they would be sufficient for the removal of acetic acid. The tributyl phosphage (TBP)-dodecane diluent, used in both UREX and NPEX, was determined to be a solvent system that gave sufficient distribution coefficients for acetic acid in addition to a high separation factor from nitric acid.

Extraction of uranium from simulated ore by the supercritical carbon dioxide fluid extraction method with nitric acid-TBP complex

International Nuclear Information System (INIS)

Dung, Le Thi Kim; Imai, Tomoki; Tomioka, Osamu; Nakashima, Mikio; Takahashi, Kuniaki; Meguro, Yoshihiro

2006-01-01

The supercritical fluid extraction (SFE) method using CO 2 as a medium with an extractant of HNO 3 -tri-n-butyl phosphate (TBP) complex was applied to extract uranium from several uranyl phosphate compounds and simulated uranium ores. An extraction method consisting of a static extraction process and a dynamic one was established, and the effects of the experimental conditions, such as pressure, temperature, and extraction time, on the extraction of uranium were ascertained. It was found that uranium could be efficiently extracted from both the uranyl phosphates and simulated ores by the SFE method using CO 2 . It was thus demonstrated that the SFE method using CO 2 is useful as a pretreatment method for the analysis of uranium in ores. (author)

Component activities in the system thorium nitrate-nitric acid-water at 25oC

International Nuclear Information System (INIS)

Lemire, R.J.; Brown, C.P.

1982-01-01

The equilibrium composition of the vapor above thorium nitrate-nitric acid-water mixtures has been studied as a function of the concentrations of thorium nitrate and nitric acid using a transpiration technique. At 25 o C, the thorium nitrate concentrations m T ranged from 0.1 to 2.5 molal and the nitric acid concentrations m N from 0.3 to 25 molal. The vapor pressure of the nitric acid was found to increase with increasing thorium nitrate concentration for a constant molality of nitric acid in aqueous solution. At constant m T , the nitric acid vapor pressure was particularly enhanced at low nitric acid concentrations. The water vapor pressures decreased regularly with increasing concentrations of both nitric acid and thorium nitrate. The experimental data were fitted to Scatchard's ion-component model, and to empirical multiparameter functions. From the fitting parameters, and available literature data for the nitric acid-water and thorium nitrate-water systems at 25 o C, expressions were calculated for the variation of water and thorium nitrate activities, as functions of the nitric acid and thorium nitrate concentrations, using the Gibbs-Duhem equation. Calculated values for the thorium nitrate activities were strongly dependent on the form of the function originally used to fit the vapor pressure data. (author)

Mechanism of nitric acid generation on Ag-X Zeolite

International Nuclear Information System (INIS)

Kanazawa, T.; Kishimoto, T.; Haseba, S.; Mitoh, Y.; Itoh, S.; Nakai, I.

1983-01-01

When Ag-X Zeolite is used for the removal of iodine from the off gas streams of nuclear facilities, it is possible that nitric acid is formed on Ag-X Zeolite from co-existing nitrogen dioxide and water vapor. If nitric acid is formed on the surface of Ag-X zeolite, Ag-X zeolite is damaged and is not able to operate for a long time. When Ag-X zeolite is used in NO 2 -O 2 -H 2 O mixture, the nitric acid generation reaction is varied, depending upon the reaction temperature, and concentration of NO 2 and H 2 O. At a temperature of more than 40 deg. C, however, only the surface reaction will be progressed on the zeolite surface. The generation of nitric acid solution on the zeolite can be forecasted through the relationship between the concentration of nitric acid solution, equilibrium vapor pressure of H 2 O, and equilibrium vapor pressure of HNO 3 . Concerning the surface reaction caused on the zeolite, the adsorption water reacts on NO 2 , and the resulting HNO 3 is adsorbed firmly by the zeolite, which is thought to interfere with the surface reaction for generation of the HNO 3 . When the adsorption bed is long, the time required for adsorbed HNO 3 to saturate is increased in proportion to the bed length

Fate of aliphatic compounds in nitric acid processing solutions

International Nuclear Information System (INIS)

Clark, W.E.; Howerton, W.B.

1975-01-01

The reaction of hyperazeotropic iodic acid-saturated nitric acid with short chain aliphatic iodides, nitrates, and acids was studied in order to determine the conditions for complete removal of organic materials from nitric acid systems. The aliphatic iodides are converted to the nitrates and the nitrates in strong HNO 3 are extensively converted into CO 2 and acids. The aliphatic acids are rather stable; acetic acid was unattacked by boiling in 20M HNO 3 and n-butyric acid was 80 percent unattacked. The dibasic acids oxalic and malonic are extensively attacked, but succinic acid is relatively stable. A wet oxidation method is successful in destroying acetic acid in 5 to 8M HNO 3 . (U.S.)

Effect of Nitric Acid Concentrations on Synthesis and Stability of Maghemite Nanoparticles Suspension

Directory of Open Access Journals (Sweden)

Irwan Nurdin

2014-01-01

Full Text Available Maghemite (γ-Fe2O3 nanoparticles have been synthesized using a chemical coprecipitation method at different nitric acid concentrations as an oxidizing agent. Characterization of all samples performed by several techniques including X-ray diffraction (XRD, transmission electron microscopy (TEM, alternating gradient magnetometry (AGM, thermogravimetric analysis (TGA, dynamic light scattering (DLS, and zeta potential. The XRD patterns confirmed that the particles were maghemite. The crystallite size of all samples decreases with the increasing concentration of nitric acid. TEM observation showed that the particles have spherical morphology with narrow particle size distribution. The particles showed superparamagnetic behavior with decreased magnetization values at the increasing concentration of nitric acid. TGA measurement showed that the stability temperature decreases with the increasing concentration of nitric acid. DLS measurement showed that the hydrodynamic particle sizes decrease with the increasing concentration of nitric acid. Zeta potential values show a decrease with the increasing concentration of nitric acid. The increasing concentration of nitric acid in synthesis of maghemite nanoparticles produced smaller size particles, lower magnetization, better thermal stability, and more stable maghemite nanoparticles suspension.

Hydrolytic and radiolytic degradation of TBP in TBP.30% V/V-dodecane/UO2(NO3)2.HNO3.H2O systems

International Nuclear Information System (INIS)

Barreta, L.G.

1980-01-01

The hydrolytic and radiolytic degradation of TBP is investigated in systems of TBP 30% V/V-dodecane/H 2 O . HNO 3 . UO 2 (NO 3 ) 2 by gas chromatographic determination of HDBP. No direct relation between the concentration of HDBP formed and the quantity of HNO 3 extracted by the organic phase is observed in the studies of hydrolysis of TBP. The HDBP concentration is seen to increase non-linearly with the concentration of HNO 3 extracted by the organic phase. Radiolytic studies show that for doses greater than 1 Wh/l, the concentration of HDBP formed increases with the dose absorbed by the system. Whith doses smaller than 1 Wh/l and acid concentration greater than 2 M, two distinct patterns of behavior are observed. The concentration of HDBP as a function of the radiation dose absorbed by the system presents a minimum for uranyl nitrate concentrations smaller than 0.9 M; for uranyl nitrate concentrations greater than 1.3 M the concentration of radiolytic HDBP cannot be calculated because the concentration of the hydrolytic HDBP determined is greater than the sum of the experimental concentrations of hydrolytic and radiolytic HDBP. It is known that the dose absorbed by the process solutions during the reprocessing of light water reactor fuel elements is smaller than one Wh/l. Thus, dose rates between zero and one Wh/l should be studied for this system. (Author) [pt

Kinetic studies on uranium stripping in D2EHPA+TBP/phosphoric acid system

International Nuclear Information System (INIS)

Yadav, K.K.; Singh, D.K.; Kotekar, M.K.; Anitha, M.; Vijayalakshmi, R.; Singh, H.

2010-01-01

Full text: A novel process based on synergistic mixture of 1.5 M D2EHPA (di 2 ethyl hexyl phosphoric acid) + 0.2 M TBP (tri-n-butyl phosphate) to recover uranium from wet process phosphoric acid (WPA) has been developed. Though the equilibrium study for the above process has been investigated in detail its kinetic behavior has not been reported so far. The work presented in the paper is an attempt to study the kinetics of U(VI) stripping from extractant phase to aqueous phase in a constant interfacial area cell (Lewis cell). Kinetic study of the solvent extraction process helps in designing of equipment and optimizing process condition for the better utilization of solvent inventory. Mass transfer kinetics of stripping of U(VI) from loaded 1.5M D2EHPA+ 0.2M TBP with phosphoric acid (AR) has been studied over a wide range of experimental conditions such as stirring speed, interfacial contact area, phosphoric acid concentration, uranium concentration, extractant concentration in organic phase and temperature. Investigation on effect of stirring speed (100-500 rpm) on stripping of U(VI) showed that the rate constant (k) values increases linearly with increase in stirring speeds from 100 to 300 rpm (0.03 to 0.075 cm/min), while the k values were almost constant (0.0819 cm/min) in 300 to 400 rpm range, beyond 450 rpm the k values again increased due to increased turbulence at the interface. The rate constant value (∼0.0814 cm/min) was found to be independent of interfacial contact area (24.6 to 67.02 cm 2 ) available for mass transfer. The rate constants were found to increase with increase in phosphoric acid concentration (6-10M) and temperature (30-60 deg C), the values being in the range of 0.01 to 0.082 cm/min. The slopes of ln-ln plot showed that the stripping of U(VI) has a second order dependence on phosphoric acid concentration (slope∼2) at temperatures ranging from 30 to 60 deg C. The activation energy value for uranium stripping was found to be in the

Light-Induced Acid Generation on a Gatekeeper for Smart Nitric Oxide Delivery.

Science.gov (United States)

Choi, Hyung Woo; Kim, Jihoon; Kim, Jinhwan; Kim, Yonghwi; Song, Hyun Beom; Kim, Jeong Hun; Kim, Kimoon; Kim, Won Jong

2016-04-26

We report herein the design of a light-responsive gatekeeper for smart nitric oxide (NO) delivery. The gatekeeper is composed of a pH-jump reagent as an intermediary of stimulus and a calcium phosphate (CaP) coating as a shielding layer for NO release. The light irradiation and subsequent acid generation are used as triggers for uncapping the gatekeeper and releasing NO. The acids generated from a light-activated pH-jump agent loaded in the mesoporous nanoparticles accelerated the degradation of the CaP-coating layers on the nanoparticles, facilitating the light-responsive NO release from diazeniumdiolate by exposing a NO donor to physiological conditions. Using the combination of the pH-jump reagent and CaP coating, we successfully developed a light-responsive gatekeeper system for spatiotemporal-controlled NO delivery.

Modelling of nitric and nitrous acid chemistry for solvent extraction purposes

Energy Technology Data Exchange (ETDEWEB)

McKenzie, H.; McLachlan, F. [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); MacDonald-Taylor, J. [National Nuclear Laboratory, 5th Floor, Chadwick House, Warrington Road, Birchwood Park, Warrington, WA3 6AE (United Kingdom); Orr, R.; Woodhead, D. [National Nuclear Laboratory, Central Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom)

2016-07-01

Nitric acid plays an integral role in the reprocessing of irradiated fuel. It is well known that nitric acid degrades; its often yellow hue signifies the presence of decomposition products. The decomposition of nitric acid is accelerated by temperature and radiolysis; therefore it is an important consideration in the reprocessing of nuclear fuels. Thermal and radiolytic reactions of nitric acid result in the formation of redox active nitrogen species, of which nitrous acid is of particular concern, largely due to its redox reactions with plutonium and neptunium. Such reactions are important to understand as plutonium and neptunium can exist in a number of oxidation states; the oxidation state has a direct effect on the species extractability. The effect of nitrous acid is exacerbated as it catalyzes its own production and its reactions with actinides are typically autocatalytic; thus even micromolar quantities can have a large effect. A full understanding of solvent extraction requires us to understand actinide valence states which in turn require us to understand what nitrogen species are present and their concentrations. As a first step in the overall objective of enhancing process models, the kinetic data for nitric acid decomposition reactions has been investigated in order to produce an initial dynamic model of decomposition under aqueous conditions. The identification of a set of kinetic reactions suitable for modelling has been the primary focus of this work. A model of nitric acid thermal decomposition will help develop a better understanding of nitric acid decomposition chemistry and enable better prediction of the oxidation states of species in solution. It is intended to later extend the model to include radiolytic reactions and then further to incorporate an organic phase in order to have a model which covers all decomposition routes for nitric acid within a nuclear fuel reprocessing scheme. The model will be used as a sub model for process models

Ultra-low power thin film transistors with gate oxide formed by nitric acid oxidation method

International Nuclear Information System (INIS)

Kobayashi, H.; Kim, W. B.; Matsumoto, T.

2011-01-01

We have developed a low temperature fabrication method of SiO 2 /Si structure by use of nitric acid, i.e., nitric acid oxidation of Si (NAOS) method, and applied it to thin film transistors (TFT). A silicon dioxide (SiO 2 ) layer formed by the NAOS method at room temperature possesses 1.8 nm thickness, and its leakage current density is as low as that of thermally grown SiO 2 layer with the same thickness formed at ∼900 deg C. The fabricated TFTs possess an ultra-thin NAOS SiO 2 /CVD SiO 2 stack gate dielectric structure. The ultrathin NAOS SiO 2 layer effectively blocks a gate leakage current, and thus, the thickness of the gate oxide layer can be decreased from 80 to 20 nm. The thin gate oxide layer enables to decrease the operation voltage to 2 V (cf. the conventional operation voltage of TFTs with 80 nm gate oxide: 12 V) because of the low threshold voltages, i.e., -0.5 V for P-ch TFTs and 0.5 V for N-ch TFTs, and thus the consumed power decreases to 1/36 of that of the conventional TFTs. The drain current increases rapidly with the gate voltage, and the sub-threshold voltage is ∼80 mV/dec. The low sub-threshold swing is attributable to the thin gate oxide thickness and low interface state density of the NAOS SiO 2 layer. (authors)

The study of kinetics of uranyl nitrate extraction and reextraction, di-n-butylphosphoric acid reextraction in the flow mixer in the system aqueous solutions - tri-n-butyl phosphate in diluent

International Nuclear Information System (INIS)

Shchepetil'nikov, N.N.; Timofeev, A.N.; Kharitonov, V.V.

1992-01-01

Kinetics of uranyl nitrate and HNO 3 extraction and reextraction in a flow-type mixer for the system 30 vol.% TBP in extractant dearomatized diluent (EDD) was studied. Kinetics of dibutylphosphate acid reextraction was considered and the influence of uranium and zirconium presence on the process was investigated. It is shown that in laboratory mixer of continuous action in case of phase contact duration of 1 min. in system 30 % solution of TBP in EDD extraction sufficiently similar to equilibrium extraction of uranyl nitrate and nitric acid during their extraction and reextraction is achieved

Photochemical reactions of neptunium in nitric acid solution containing photocatalyst

International Nuclear Information System (INIS)

Fukasawa, Tetsuo; Kawamura, Fumio

1991-01-01

Photochemical oxidation and reduction behaviors of neptunium were preliminarily investigated in 3 mol/l nitric acid solution. Nitric acid of 3 mol/l simulated the high level waste solution from a spent fuel reprocessing process. Concentrations of Np(V), Np(VI) and nitrous acid were determined with a photospectrometer, and solution potential with an electrode. Without additives, Np(VI) was reduced to Np(V) by nitrous acid which was photolytically generated from nitric acid. With a scavenger for nitrous acid, Np(V) was oxidized to extractable Np(VI) by a photolytically generated oxidizing reagent which were predicted by the solution potential measurement. The reduction rate was higher than the oxidation rate because of the larger quantity and higher reactivity of nitrous acid than an oxidizing reagent. Photocatalyst was proved to be effective for the oxidation of Np(V) to Np(VI). (author)

The Consistency of Isotopologues of Ambient Atmospheric Nitric Acid in Passively Collected Samples

Science.gov (United States)

Bell, M. D.; Sickman, J. O.; Bytnerowicz, A.; Padgett, P.; Allen, E. B.

2012-12-01

Anthropogenic sources of nitrogen oxides have previously been shown to have distinctive isotopic signatures of oxygen and nitrogen. Nylon filters are currently used in passive sampling arrays to measure ambient atmospheric nitric acid concentrations and estimate deposition rates. This experiment measured the ability of nylon filters to consistently collect isotopologues of atmospheric nitric acid in the same ratios as they are present in the atmosphere. Samplers were deployed in continuous stirred tank reactors (CSTR) and at field sites across a nitrogen deposition gradient in Southern California. Filters were exposed over a four week period with individual filters being subjected to 1-4 week exposure times. Extracted nitric acid were measured for δ18O and δ15N ratios and compared for consistency based on length of exposure and amount of HNO3 collected. Filters within the CSTRs collected HNO3 at a consistent rate in both high and low concentration chambers. After two weeks of exposure, the mean δ18O values were within 0.5‰ of the δ18O of the source HNO3 solution. The mean of all weekly exposures were within 0.5‰ of the δ15N of the source solution, but after three weeks, the mean δ15N of adsorbed HNO3 was within 0.2‰. As the length of the exposure increased, the variability of measured delta values decreased for both elements. The field samplers collected HNO3 consistent with previously measured values along a deposition gradient. The mean δ18O at high deposition sites was 52.2‰ compared to 35.7‰ at the low deposition sites. Mean δ15N values were similar at all sites across the deposition gradient. Due to precipitation events occurring during the exposure period, the δ15N and δ18O of nitric acid were highly variable at all field sites. At single sites, changes in δ15N and δ18O were negatively correlated, consistent with two-sourcing mixing dynamics, but the slope of the regressions differed between high and low deposition sites. Anthropogenic

The radiolytic formation of nitric acid in argon/air/water systems

International Nuclear Information System (INIS)

May, R.; Stinchcombe, D.; White, H.P.

1992-01-01

The extent of nitric acid formation in the γ-radiolysis of argon/air/water mixtures has been assessed. The yields of nitric acid are found to increase as water vapour pressure is increased but are lower in the presence of a discrete water phase. G values for the formation of nitric acid from argon/air mixtures based on energy absorbed in the air are increased in the presence of argon but the yields in an atmosphere of argon containing small amounts of moist air are smaller than from an atmosphere of moist air alone. The G value for nitric acid formation from pure air in the presence of a distinct water phase is 2, based on energy absorbed in the air. (author)

The oxidation of uranium(IV) ions by nitrous acid in 30% tri-butyl phosphate

International Nuclear Information System (INIS)

Koltunov, V.S.; Marchenko, V.I.; Savilova, O.A.; Dvoeglazov, K.N.; Taylor, R.J.

2004-01-01

The kinetics of the oxidation of U(IV) ions by nitrous acid in a 30% TBP solution have been determined. The rate equation was found to be: - d[U(IV)] / dt = k 2a [U(IV)][HNO 2 ][HNO 3 ][H 2 O] / [HNO 3 ] 2 + β 3 [HNO 3 ][H 2 O] + β 4 [H 2 O] 2 , where, k 2a = 0.405 ± 0.055 M -1 min -1 at 55 C (β 3 ∼ 0.08; β 4 ∼ 0.007) and the activation energy was E = 112 ± 17 kJ mol -1 . The reaction mechanism appeared to involve interaction with the 1 st hydrolysis product of U(IV)-UOH 3+ . The data is compared with a previous study of the nitric acid oxidation of U(IV) in 30% TBP. This reaction is autocatalytic due to the formation of nitrous acid during the reaction. The kinetics of the decomposition of HNO 2 in 30% TBP (in the absence of U(IV)) have also been reported. (orig.)

Method of improving the decontaminating efficiency of ruthenium in evaporating treatment of nitric acid

International Nuclear Information System (INIS)

Kubota, Kanya; Yamana, Hajime; Takeda, Seiichiro.

1984-01-01

Purpose: To significantly improve the ruthenium removing efficiency in a nitric acid solution in an acid recovery system for the recovery of nitric acid from nitric acid liquid wastes through evaporating condensation. Method: Upon evaporating treatment of nitric acid solution containing ruthenium by supplying and heating the solution to a nitric acid evaporating device, hydrazine is previously added to the nitric acid solution. Hydrazine and intermediate reaction product of hydrazine such as azide causes a reduction reaction with intermediate reaction product of ruthenium tetraoxide to suppress the oxidation of ruthenium and thereby improve the decontaminating efficiency of ruthenium. The amount of hydrazine to be added is preferably between 20 - 500 mg/l and most suitably between 200 - 2000 mg/l per one liter of the liquid in the evaporating device. (Seki, T.)

Modeling of Pu(IV) extraction and HNO3 speciation in nuclear fuel reprocessing

International Nuclear Information System (INIS)

De-Sio, S.

2012-01-01

The PUREX process is a solvent extraction method dedicated to the reprocessing of irradiated nuclear fuel in order to recover pure uranium and plutonium from aqueous solutions of concentrated nitric acid. The tri-n-butylphosphate (TBP) is used as the extractant in the organic phase. The aim of this thesis work was to improve the modeling of liquid-liquid extraction media in nuclear fuel reprocessing. First, Raman and 14 N NMR measurements, coupled with theoretical calculations based on simple solutions theory and BIMSA modeling, were performed in order to get a better understanding of nitric acid dissociation in binary and ternary solutions. Then, Pu(IV) speciation in TBP after extraction from low nitric acid concentrations was investigated by EXAFS and vis-NIR spectroscopies. We were able to show evidence of the extraction of Pu(IV) hydrolyzed species into the organic phase. A new structural study was conducted on An(VI)/TBP and An(IV)/TBP complexes by coupling EXAFS measurements with DFT calculations. Finally, extraction isotherms modeling was performed on the Pu(IV)/HNO 3 /H 2 O/TBP 30%/dodecane system (with Pu at tracer scale) by taking into account deviation from ideal behaviour in both organic and aqueous phases. The best modeling was obtained when considering three plutonium (IV) complexes in the organic phase: Pu(OH) 2 (NO 3 ) 2 (TBP) 2 , Pu(NO 3 ) 4 (TBP) 2 and Pu(NO 3 ) 4 (TBP) 3 . (author) [fr

On hydrazine oxidation in nitric acid media

International Nuclear Information System (INIS)

Zil'berman, B.Ya.; Lelyuk, G.A.; Mashkin, A.N.; Yasnovitskaya, A.L.

1988-01-01

Yield of products of radiolytic ( 60 Co gamma radiation) and chemical hydrazine (HZ) oxidation in nitric acid media is studied. Under radiolyte HZ oxidation by nitric acid hydrazoic acid, ammonia and nitrogen appear to be the reaction products. HN 3 yield maximum under HZN oxidation makes up ∼ 0.35 mol per a mol of oxiduzed HZN. Under chemical oxidation HZN is oxidized by HNO 3 according to reaction catalysed by technetium HN 3 yield makes up ∼ 0.35 mol per a mol of oxidized HZN. Radiation-chemical oxidation of HN 3 proceeds up to its complete decomposition, decomposition rate is comparable with HZ oxidation rate. Under the chemical oxidation HN 3 is more stable, it is slowly decomposed after complete HZ decomposition

Extraction of uranium with TBP in an electrostatic apparatus

International Nuclear Information System (INIS)

Kalbasi, M.

1980-10-01

An experimental investigation into the utilization of electrostatic energy for solvent extraction of metallic species has been made. Drops were formed at a single nozzle and charged electrically by applying a high d.c. voltage to the nozzle which was arranged to form part of a parallel disc electrode system. After the drops left this electrode zone they travelled through a metallic pipe the purpose of which was to screen the drops from the external electrostatic forces. The liquid system employed in the present work was aqueous uranyl nitrate solution as a dispersed phase and organic tri-n-butyl phosphate (TBP)-diluent as a continuous phase. Uncharged drops were studied in the presence and absence of nitric acid salting agent and in addition both discrete and spray regimes were examined with charged drops. Size, velocity, oscillation motion, charge leakage, actual potential gradient and mass transfer coefficients (reaction rate constants) were studied. A cine camera was used to study the velocity and oscillatory motion of the charged drops moving in the continuous phase in the presence and absence of an electric field. The results of this work suggest that both hydrodynamic and electrostatic forces are responsible for the liquid-liquid extraction rate increase. (author)

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

Science.gov (United States)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

Determination of tributyl phosphate (TBP) by precision densimetry : TBP-varsol-HNO3 system

International Nuclear Information System (INIS)

Matsuda, H.T.; Araujo, B.F. de; Araujo, J.A. de

1980-01-01

A simple and rapid method for TBP direct determination is presented, based on precision densimetry, aiming to control solvent concentration in the TBP-Varsol system during the reprocessing of irradiated uranium. The method comprises the determination of the density of liquids or gases by electronic measurement of the variation in the frequency (f) or period (T = 1/f) of a glass oscillator containing the liquid or the gas. (C.L.B.) [pt

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M.

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V{sub SHE} and between 0,5 V{sub SHE} and 1 V{sub SHE}. The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V{sub SHE}, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Behaviour of Pu-IV with various ion exchangers in solutions containing nitric acid and oxalates

International Nuclear Information System (INIS)

Walter, E.; Ali, S.A.

1982-02-01

The distribution of Pu-IV on the ion exchangers Dowex 50W-X8, Dowex 1-X8 und Dowex Chelating Resin Al-X8 in the presence of various concentrations of nitric acid and oxalate were investigated. The results indicate that nitric acid and oxalic acid influence each other during complexation of Pu-IV with oxalate ions solutions containing nitric acid it is not possible to neglect the formation of Pu-IV nitrate complexes. The complex Pu(IV) (C 2 O 4 ) 3 2 - only is formed in solutions containing low nitric acid and high oxalic acid concentrations. The separation of Pu-IV in Dowex Chelating Resin from nitric acid solution in the presence of higher oxalate concentrations is possible, provided that the nitric acid concentration is lower than 0.25 molar [fr

Purification of degraded TBP solvent using macroreticular anion exchange resin

International Nuclear Information System (INIS)

Kartha, P.K.S.; Kutty, P.V.E.; Janaradanan, C.; Ramanujam, A.; Dhumwad, R.K.

1989-01-01

Tri-n-butyl phosphate (TBP) diluted with a suitable diluent is commonly used for solvent extraction in Purex process for the recovery of uranium and plutonium from irradiated nuclear fuels. This solvent gets degraded due to various factors, the main degradation product being dibutyl phosphoric acid (HDBP). A solvent cleanup step is generally incorporated in the process for removing the degradation products from the used solvent. A liquid-liquid cleanup system using sodium carbonate or sodium hydroxide solution is routinely used. Considering certain advantages, like the possibility of loading the resin almost to saturation capacity and the subsequent disposal of the spent resin by incineration and the feasibility of adopting it to the process, a liquid-solid system has been tried as an alternate method, employing various available macroreticular anion exchange resins in OH - form for the sorption of HDBP from TBP. After standardizing the various conditions for the satisfactory removal of HDBP from TBP using synthetic mixtures, resins were tested with process solvent in batch contacts. The parameters studied were (1) capacity of different resins for HDBP sorption (2) influence of acidity, uranium and HDBP on the sorption behaviour of the latter (3) removal of fission products from the solvent by the resin and (4) regeneration and recycling of the resin. (author). 2 figs., 13 tabs., 17 refs

Formation of nitric acid hydrates - A chemical equilibrium approach

Science.gov (United States)

Smith, Roland H.

1990-01-01

Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

Alternative to Nitric Acid Passivation

Science.gov (United States)

Kessel, Kurt R.

2016-01-01

Corrosion is an extensive problem that affects the National Aeronautics and Space Administration (NASA) and European Space Agency (ESA). The deleterious effects of corrosion result in steep costs, asset downtime affecting mission readiness, and safety risks to personnel. It is vital to reduce corrosion costs and risks in a sustainable manner. The primary objective of this effort is to qualify citric acid as an environmentally-preferable alternative to nitric acid for passivation of stainless steel alloys.

Use of extractive distillation to produce concentrated nitric acid

International Nuclear Information System (INIS)

Campbell, P.C.; Griffin, T.P.; Irwin, C.F.

1981-04-01

Concentrated nitric acid (> 95 wt %) is needed for the treatment of off-gases from a fuels-reprocessing plant. The production of concentrated nitric acid by means of extractive distillation in the two-pot apparatus was studied to determine the steady-state behavior of the system. Four parameters, EDP volume (V/sub EDP/) and temperature (T/sub EDP/), acid feed rate, and solvent recycle, were independently varied. The major response factors were percent recovery (CPRR) and product purity (CCP). Stage efficiencies also provided information about the system response. Correlations developed for the response parameters are: CPRR = 0.02(V/sub EDP/ - 800 cc) + 53.5; CCP = -0.87 (T/sub EDP/ - 140 0 C) + 81; eta/sub V,EDP/ = 9.1(F/sub feed/ - 11.5 cc/min) - 0.047(V/sub EDP/ - 800 cc) - 2.8(F/sub Mg(NO 3 ) 2 / - 50 cc/min) + 390; and eta/sub L,EDP/ = 1.9(T/sub EDP/ - 140 0 C) + 79. A computer simulation of the process capable of predicting steady-state conditions was developed, but it requires further work

The observation of nitric acid-containing particles in the tropical lower stratosphere

Directory of Open Access Journals (Sweden)

P. J. Popp

2006-01-01

Full Text Available Airborne in situ measurements over the eastern Pacific Ocean in January 2004 have revealed a new category of nitric acid (HNO3-containing particles in the tropical lower stratosphere. These particles are most likely composed of nitric acid trihydrate (NAT. They were intermittently observed in a narrow layer above the tropopause (18±0.1 km and over a broad geographic extent (>1100 km. In contrast to the background liquid sulfate aerosol, these particles are solid, much larger (1.7-4.7 µm vs. 0.1µm in diameter, and significantly less abundant (-4 cm-3 vs. 10 cm-3. Microphysical trajectory models suggest that the NAT particles grow over a 6-14 day period in supersaturated air that remains close to the tropical tropopause and might be a common feature in the tropics. The small number density of these particles implies a highly selective or slow nucleation process. Understanding the formation of solid NAT particles in the tropics could improve our understanding of stratospheric nucleation processes and, therefore, dehydration and denitrification.

X-ray photoelectron spectroscopy and Auger electron spectroscopy studies on the passivation behavior of plasma-nitrided low alloy steel in nitric acid

Energy Technology Data Exchange (ETDEWEB)

Chyou, S.D.; Shih, H.C. (Dept. of Materials Science and Engineering, National Tsing Hua Univ., Hsinchu (Taiwan))

1991-12-14

Nitrided SAE 4140 steel has been passivated by concentrated nitric acid. The resulting film was characterized using a combination of surface-analytical techniques, such as X-ray photoelectron spectroscopy (XPS) to evaluate the chemical composition of the passive film. Auger electron spectroscopy (AES) combined with ion etching was used to determine the composition depth profiles of nitrided surface. It was found that preferential dissolution of iron leads to enhanced nitrogen and chromium concentrations within the oxynitrided layer. A dense protective oxynitrided layer was found to be formed on the nitrided surface when the concentration of nitric acid was as high as 8 M. The results of X-ray diffraction, XPS and AES analyses conclude that the protective nitride layer is composed of (Fe,Cr){sub 4}N, (Fe,Cr){sub 2-3}N and CrN in the inner layer, Fe{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} and remnant nitrides in the middle layer and nitrides accompanying Cr(OH){sub 3}.H{sub 2}O and {gamma}'-FeOOH in the outermost layer. (orig.).

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Direction du Cycle du Combustible

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V{sub S}HE and 0.3 V{sub S}HE and O.5 V{sub S}HE and 1 V{sub S}HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V{sub S}HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Corrosion of stainless steels and nickel-base alloys in solutions of nitric acid and hydrofluoric acid

International Nuclear Information System (INIS)

Horn, E.M.; Renner, M.

1992-01-01

Reactions involving nitric acid may always result in the contamination of this acid with fluorides. In highly concentrted nitric acid, the presence of small amounts of HF will substantially reduce the corrosion of metallic materials. Mixtures consisting of hydrofluoric acid and hypo-azeotropic nitric acid on the other hand will strongly attack: the metal loss will markedly increase with increasing HNO 3 and HF concentrations as well as with rising temperatures. The investigation covered 12 stainless steel grades and nickel-base alloys. With constant HNO 3 content, corrosion rates will rise linearly when increasing the HF concentration. With constant HF concentration (0,25 M), corrosion rates will increase rapidly with increasing nitric acid concentration (from 0.3 M to 14.8 M). This can best be described by superimposing a linear function and a hyperbolic function that is reflecting the change in the HNO 3 content. Alloys containing as much chromium as possible (up to 46 wt.%) will exhibit the best corrosion resistance. Alloy NiCr30FeMo (Hastelloy alloy G-30) proved to be well suitable in this investigation. (orig.) [de

In situ synthesis carbonated hydroxyapatite layers on enamel slices with acidic amino acids by a novel two-step method.

Science.gov (United States)

Wu, Xiaoguang; Zhao, Xu; Li, Yi; Yang, Tao; Yan, Xiujuan; Wang, Ke

2015-09-01

In situ fabrication of carbonated hydroxyapatite (CHA) remineralization layer on an enamel slice was completed in a novel, biomimetic two-step method. First, a CaCO3 layer was synthesized on the surface of demineralized enamel using an acidic amino acid (aspartic acid or glutamate acid) as a soft template. Second, at the same concentration of the acidic amino acid, rod-like carbonated hydroxyapatite was produced with the CaCO3 layer as a sacrificial template and a reactant. The morphology, crystallinity and other physicochemical properties of the crystals were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX), respectively. Acidic amino acid could promote the uniform deposition of hydroxyapatite with rod-like crystals via absorption of phosphate and carbonate ions from the reaction solution. Moreover, compared with hydroxyapatite crystals coated on the enamel when synthesized by a one-step method, the CaCO3 coating that was synthesized in the first step acted as an active bridge layer and sacrificial template. It played a vital role in orienting the artificial coating layer through the template effect. The results show that the rod-like carbonated hydroxyapatite crystals grow into bundles, which are similar in size and appearance to prisms in human enamel, when using the two-step method with either aspartic acid or acidic glutamate (20.00 mmol/L). Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of tributyl phosphate (TBP) by precision densimetry : TBP-varsol-HNO/sub 3/ system

Energy Technology Data Exchange (ETDEWEB)

Matsuda, H T; Araujo, B.F. de; Araujo, J.A. de [Instituto de Pesquisas Energeticas e Nucleares, Sao Paulo (Brazil). Centro de Engenharia Quimica

1980-01-01

A simple and rapid method for TBP direct determination is presented, based on precision densimetry, aiming to control solvent concentration in the TBP-Varsol system during the reprocessing of irradiated uranium. The method comprises the determination of the density of liquids or gases by electronic measurement of the variation in the frequency (f) or period (T = 1/f) of a glass oscillator containing the liquid or the gas.

Bibliographic report on the synthesis, the chemical and physical properties and the applications of the TBP phosphate

International Nuclear Information System (INIS)

Azzouz, A.; Attou, M.

1985-02-01

This work consists of a bibliographic synthesis concerning the tri-n-butylphosphate (TBP) technology. It gathers briefly in 56 references on a table, the multiple applications of TBP such as extraction, spectroscopy and various other uses. Then, it deals with chemical instability different causes of this substance as well as its physical and chemical properties. In this way, for instance, the thermal degradation occurs well before the TBP boiling point. It comes out of this, several decomposition products such as the mono-n-butyl-phosphate (MBP), the di-n-butylphosphate (DBP) and some olefins. The acids and some impurities are known to have effects on TBP degradation. Later on, some processes of the TBP synthesis and their principles are stated. In the major cases, the POCl 3 process seems to be the best way, probably because of convenient efficiencies and moderate conditions of its making. Some purification processes according to the TBP use are also invoqued. In this case as well, Alcock et al. method is often stated in the literature. Moreover, five analysis methods corresponding to the most common situations are described

4.3. Decomposition of danburite concentrate of Ak-Arkar Deposit by nitric acid

International Nuclear Information System (INIS)

Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

2015-01-01

Present article is devoted to decomposition of danburite concentrate of Ak-Arkar Deposit by nitric acid. The influence of temperature on reaction process was studied. The dependence of extraction rate of oxides (B 2 O 3 , Al 2 O 3 , Fe 2 O 3 and Ca O) at nitric acid processing on temperature ranges from 25 to 95 deg C was defined. The dependence of extraction rate of oxides (B 2 O 3 , Al 2 O 3 , Fe 2 O 3 and Ca O) at nitric acid processing on process duration (5-60 minutes) was defined as well. The optimal conditions of decomposition of danburite concentrate by nitric acid were proposed.

Extraction-wet oxidation process using sulphuric acid for treatment of TBP-dodecane wastes

International Nuclear Information System (INIS)

Deshingkar, D.S.; Kartha, P.K.S.

1998-03-01

In the nuclear fuel reprocessing plants, 30% n-tributyl phosphate in hydrocarbon diluent is used for extraction of uranium and plutonium from the spent fuel by Purex process. When TBP-dodecane can no longer be purified from its degradation products, it is discarded as alpha bearing, intermediate level wastes containing plutonium and ruthenium-106. To overcome shortcomings of extraction-pyrolysis and saponification processes, studies were undertaken to find the suitability of H 2 SO 4 as an alternative extractant for TBP. Oxidation of TBP to H 3 PO 4 using H 2 O 2 was also explored as H 3 PO 4 can be treated by known procedures for removal of plutonium and ruthenium-106. The experiments were conducted with aged spent solvent wastes discharged from reprocessing plant at Trombay using H 2 SO 4 and H 2 SO 4 - H 3 PO 4 mixture. The decontamination factors (DFs) for alpha activity were found to be satisfactory. The DFs for ruthenium were lower as compared to those obtained in experiments with simulated degraded waste. The gas chromatographic analysis of separated diluent revealed high branched alkane content and low n-dodecane content of separated diluent. It is very much different from that of diluent currently in use. Hence incineration of separated diluent is recommended. (author)

The development of 126Sn separation procedure by means of TBP resin

International Nuclear Information System (INIS)

Andris, Boris; Bena, Jozef

2016-01-01

Separation possibilities of 126 Sn with a new extraction-chromatographic material TBP Resin were studied. Suitable conditions for tin separation were determined in hydrochloric acid medium. 126 Sn was concentrated on TBP resin from 6 mol L -1 HCl and was eluted with 0.1 mol L -1 HCl. A purification step to remove 137 Cs with AMP-PAN column was necessary to obtain sufficiently purified samples which were directly measured with gamma spectrometry for 126 Sn activity. Separation of 126 Sn from a raw sludge sample was done according to proposed procedure, 126 Sn was detected and its activity was determined. (author)

Molecular Cloning of a cDNA Encoding for Taenia solium TATA-Box Binding Protein 1 (TsTBP1) and Study of Its Interactions with the TATA-Box of Actin 5 and Typical 2-Cys Peroxiredoxin Genes.

Science.gov (United States)

Rodríguez-Lima, Oscar; García-Gutierrez, Ponciano; Jiménez, Lucía; Zarain-Herzberg, Ángel; Lazzarini, Roberto; Landa, Abraham

2015-01-01

TATA-box binding protein (TBP) is an essential regulatory transcription factor for the TATA-box and TATA-box-less gene promoters. We report the cloning and characterization of a full-length cDNA that encodes a Taenia solium TATA-box binding protein 1 (TsTBP1). Deduced amino acid composition from its nucleotide sequence revealed that encodes a protein of 238 residues with a predicted molecular weight of 26.7 kDa, and a theoretical pI of 10.6. The NH2-terminal domain shows no conservation when compared with to pig and human TBP1s. However, it shows high conservation in size and amino acid identity with taeniids TBP1s. In contrast, the TsTBP1 COOH-terminal domain is highly conserved among organisms, and contains the amino acids involved in interactions with the TATA-box, as well as with TFIIA and TFIIB. In silico TsTBP1 modeling reveals that the COOH-terminal domain forms the classical saddle structure of the TBP family, with one α-helix at the end, not present in pig and human. Native TsTBP1 was detected in T. solium cysticerci´s nuclear extract by western blot using rabbit antibodies generated against two synthetic peptides located in the NH2 and COOH-terminal domains of TsTBP1. These antibodies, through immunofluorescence technique, identified the TBP1 in the nucleus of cells that form the bladder wall of cysticerci of Taenia crassiceps, an organism close related to T. solium. Electrophoretic mobility shift assays using nuclear extracts from T. solium cysticerci and antibodies against the NH2-terminal domain of TsTBP1 showed the interaction of native TsTBP1 with the TATA-box present in T. solium actin 5 (pAT5) and 2-Cys peroxiredoxin (Ts2-CysPrx) gene promoters; in contrast, when antibodies against the anti-COOH-terminal domain of TsTBP1 were used, they inhibited the binding of TsTBP1 to the TATA-box of the pAT5 promoter gene.

A study on electrochemical redox behavior of nitric acid by using a glassy carbon fiber column electrode system

International Nuclear Information System (INIS)

Kim, K. W.; Song, K. C.; Lee, I. H.; Choi, I. K.; You, J. H.

1999-01-01

Electrochemical redox behaviors of nitric acid were studied by using a glassy carbon fiber column electrode system, and its reaction mechanism was analyzed in several ways. The electrochemical reaction in less than 2.0 M nitric acid was not observed, but in more than 2.0 M nitric acid, the reduction rate of nitric acid to produce nitrous acid was slow so that the nitric acid solution had to be contacted with electrode enough in order for a apparent reduction current of nitric acid to nitrous acid be to observed. The nitrous acid generated in more than 2.0 M nitric acid was rapidly and easily reduced to NOx through an autocatalytic reaction. Sulfamic acid was confirmed to be effective to destroy the nitrous acid. The sulfamic acid of at least 0.05M was necessary to remove the nitrous acid generated in 3.5 M nitric acid

Thermodynamic and kinetic modelling of the reduction of concentrated nitric acid

International Nuclear Information System (INIS)

Sicsic, David

2011-01-01

This research thesis aimed at determining and quantifying the different stages of the reduction mechanism in the case of concentrated nitric acid. After having reported the results of a bibliographical study on the chemical and electrochemical behaviour of concentrated nitric media (generalities, chemical equilibriums, NOx reactivity, electrochemical reduction of nitric acid), the author reports the development and discusses the results of a thermodynamic simulation of a nitric environment at 25 C. This allowed the main species to be identified in the liquid and gaseous phases of nitric acid solutions. The author reports an experimental electrochemical investigation coupled with analytic techniques (infrared and UV-visible spectroscopy) and shows that the reduction process depends on the cathodic overvoltage, and identifies three potential areas. A kinetic modelling of the stationary state and of the impedance is then developed in order to better determine, discuss and quantify the reduction process. The application of this kinetic model to the preliminary results of an electrochemical study performed on 304 L steel is then discussed [fr

DISSOLUTION OF METAL OXIDES AND SEPARATION OF URANIUM FROM LANTHANIDES AND ACTINIDES IN SUPERCRITICAL CARBON DIOXIDE

Energy Technology Data Exchange (ETDEWEB)

Donna L. Quach; Bruce J. Mincher; Chien M. Wai

2013-10-01

This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

Simulation of technetium extraction behavior in UO2 (NO3)2-TcO4--HNO3-H2O/TBP-kerosene system

International Nuclear Information System (INIS)

Zhang Chunlong; He Hui; Chen Yanxin; Tang Hongbin

2012-01-01

By comparing and analyzing lots of reported data of technetium with the computing results, a modification function P(c 0 (U), t) was introduced to the existing distribution coefficient model of technetium, and a new mathematical model for simulating technetium extraction behavior in the system of UO 2 (NO 3 ) 2 -TcO 4 -HNO 3 -H 2 O/TBP- kerosene was established, as well as a computer program. The reliability of the program was verified by 179 sets of distribution coefficient data, and the results were found to agree well with experimental data. By comparing the reported data of technetium with the computing results, an evaluation was made to test the performance of the revised model. It turned out that the calculation results of the new model were more reliable than that of the one reported previously. The revised model and program can be the foundation to simulating technetium extraction behavior in the system of UO 2 (NO 3 ) 2 - TcO 4 - -HNO 3 -H 2 O/TBP-kerosene with the temperature scope from 10 to 60℃, U concentration from 0 to 280 g/L, and nitric acid concentration from 0.1 to 5 mol/L. (authors)

In situ synthesis carbonated hydroxyapatite layers on enamel slices with acidic amino acids by a novel two-step method

International Nuclear Information System (INIS)

Wu, Xiaoguang; Zhao, Xu; Li, Yi; Yang, Tao; Yan, Xiujuan; Wang, Ke

2015-01-01

In situ fabrication of carbonated hydroxyapatite (CHA) remineralization layer on an enamel slice was completed in a novel, biomimetic two-step method. First, a CaCO 3 layer was synthesized on the surface of demineralized enamel using an acidic amino acid (aspartic acid or glutamate acid) as a soft template. Second, at the same concentration of the acidic amino acid, rod-like carbonated hydroxyapatite was produced with the CaCO 3 layer as a sacrificial template and a reactant. The morphology, crystallinity and other physicochemical properties of the crystals were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX), respectively. Acidic amino acid could promote the uniform deposition of hydroxyapatite with rod-like crystals via absorption of phosphate and carbonate ions from the reaction solution. Moreover, compared with hydroxyapatite crystals coated on the enamel when synthesized by a one-step method, the CaCO 3 coating that was synthesized in the first step acted as an active bridge layer and sacrificial template. It played a vital role in orienting the artificial coating layer through the template effect. The results show that the rod-like carbonated hydroxyapatite crystals grow into bundles, which are similar in size and appearance to prisms in human enamel, when using the two-step method with either aspartic acid or acidic glutamate (20.00 mmol/L). - Graphical abstract: FESEM images of enamel slices etched for 60 s and repaired by the two-step method with Glu concentration of 20.00 mmol/L. (A) The boundary (dotted line) of the repaired areas (b) and unrepaired areas (a). (Some selected areas of etched enamel slices were coated with a nail polish before the reaction, which was removed by acetone after the reaction); (B) high magnification image of Ga, (C) high magnification image of Gb. In situ fabrication of carbonated

In situ synthesis carbonated hydroxyapatite layers on enamel slices with acidic amino acids by a novel two-step method

Energy Technology Data Exchange (ETDEWEB)

Wu, Xiaoguang [Department of Pediatric Dentistry, The Hospital of Stomatology, Jilin University, Changchun 130021 (China); Zhao, Xu [College of Chemistry, Jilin University, Changchun 130021 (China); Li, Yi, E-mail: lyi99@jlu.edu.cn [Department of Pediatric Dentistry, The Hospital of Stomatology, Jilin University, Changchun 130021 (China); Yang, Tao [Department of Stomatology, Children' s Hospital of Changchun, 130051 (China); Yan, Xiujuan; Wang, Ke [Department of Pediatric Dentistry, The Hospital of Stomatology, Jilin University, Changchun 130021 (China)

2015-09-01

In situ fabrication of carbonated hydroxyapatite (CHA) remineralization layer on an enamel slice was completed in a novel, biomimetic two-step method. First, a CaCO{sub 3} layer was synthesized on the surface of demineralized enamel using an acidic amino acid (aspartic acid or glutamate acid) as a soft template. Second, at the same concentration of the acidic amino acid, rod-like carbonated hydroxyapatite was produced with the CaCO{sub 3} layer as a sacrificial template and a reactant. The morphology, crystallinity and other physicochemical properties of the crystals were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX), respectively. Acidic amino acid could promote the uniform deposition of hydroxyapatite with rod-like crystals via absorption of phosphate and carbonate ions from the reaction solution. Moreover, compared with hydroxyapatite crystals coated on the enamel when synthesized by a one-step method, the CaCO{sub 3} coating that was synthesized in the first step acted as an active bridge layer and sacrificial template. It played a vital role in orienting the artificial coating layer through the template effect. The results show that the rod-like carbonated hydroxyapatite crystals grow into bundles, which are similar in size and appearance to prisms in human enamel, when using the two-step method with either aspartic acid or acidic glutamate (20.00 mmol/L). - Graphical abstract: FESEM images of enamel slices etched for 60 s and repaired by the two-step method with Glu concentration of 20.00 mmol/L. (A) The boundary (dotted line) of the repaired areas (b) and unrepaired areas (a). (Some selected areas of etched enamel slices were coated with a nail polish before the reaction, which was removed by acetone after the reaction); (B) high magnification image of Ga, (C) high magnification image of Gb. In situ fabrication of

Extractive behavior of U(VI) in the paraffin soluble ionic liquid

International Nuclear Information System (INIS)

Rama, R.; Kumaresan, R.; Venkatesan, K.A.; Antony, M.P.; Vasudeva Rao, P.R.

2013-01-01

An Aliquat-336 based ionic liquid namely, tri-n-octylmethylammonium bis(2-ethylhexyl)phosphate ((A3636) + (DEHP) - ) was prepared and studied for the extraction of U(VI) from nitric acid medium. Since the ionic liquid, (A336) + (DEHP) - , was miscible in n-dodecane (n-DD), the extraction of U(VI) in the solution of tri-n-butylphosphate (TBP) in n-DD, was investigated in the presence of small concentrations of ionic liquid. The distribution ratio of U(VI) in 0.3 M (A336) + (DEHP) - /n-DD decreased with increase in the concentration of nitric acid. The effect of concentration of TBP, ionic liquid nitric acid and nitrate ion on the extraction of U(VI) in ionic liquid medium was studied. The mechanistic aspect of extraction was investigated by the slope analysis of the extraction data. The studies indicated the feasibility of modifying the extractive properties of U(VI) in TBP/n-DD using ionic liquid. (author)

Extraction with tributyl phosphate (TBP) from ferric nitrate solutions

International Nuclear Information System (INIS)

Kolarik, Z.; Grudpan, K.

1985-01-01

Ferric nitrate acts as a strong salting-out agent in the extraction of thorium(IV), uranyl, europium(III), samarium(III) and zirconium(IV) nitrates as well as of nitric acid with tributyl phosphate in dodecane. Nitric acid, if present in the extraction system together with large amounts of ferric nitrate, markedly suppresses the extraction of thorium(IV) and lanthanides(III) but significantly supports the extraction of zirconium(IV). Separation factors of different metal pairs are presented as functions of the concentrations of ferric nitrate and nitric acid

The Effect of Acid Pre-Treatment using Acetic Acid and Nitric Acid in The Production of Biogas from Rice Husk during Solid State Anaerobic Digestion (SS-AD)

Science.gov (United States)

Nugraha, Winardi Dwi; Syafrudin; Keumala, Cut Fadhila; Matin, Hasfi Hawali Abdul; Budiyono

2018-02-01

Pretreatment during biogas production aims to assist in degradation of lignin contained in the rice husk. In this study, pretreatment which is used are acid and biological pretreatment. Acid pretreatment was performed using acetic acid and nitric acid with a variety levels of 3% and 5%. While biological pretreatment as a control variable. Acid pretreatment was conducted by soaking the rice straw for 24 hours with acid variation. The study was conducted using Solid State Anaerobic Digestion (SS-AD) with 21% TS. Biogas production was measured using water displacement method every two days for 60 days at room temperature conditions. The results showed that acid pretreatment gave an effect on the production of biogas yield. The yield of the biogas produced by pretreatment of acetic acid of 5% and 3% was 43.28 and 45.86 ml/gr.TS. While the results without pretreatment biogas yield was 29.51 ml/gr.TS. The results yield biogas produced by pretreatment using nitric acid of 5% and 3% was 12.14 ml/gr.TS and 21.85 ml/gr.TS. Results biogas yield with acetic acid pretreatment was better than the biogas yield results with nitric acid pretreatment.

Investigations on the oxidation of nitric acid plutonium solutions with ozone

International Nuclear Information System (INIS)

Boehm, M.

1983-01-01

The reaction of ozone with nitric acid Pu solutions was studied as a function of reaction time, acid concentration and Pu concentration. Strong nitric acid Pu solutions are important in nuclear fuel element production and reprocessing. The Pu must be converted into hexavalent Pu before precipitation from the homogeneous solution together with uranium-IV, ammonia and CO 2 in the form of ammonium uranyl/plutonyl carbonate (AUPuC). Formation of a solid phase during ozonation was observed for the first time. The proneness to solidification increases with incrasing plutonium concentrations and with decreasing acid concentrations. If the formation of a solid phase during ozonation of nitric acid Pu solutions cannot be prevented, the PU-IV oxidation process described is unsuitable for industrial purposes as Pu solutions in industrial processes have much higher concentrations than the solutions used in the present investigation. (orig./EF) [de

Behaviour of solvent extraction of niobium in nitric acid

International Nuclear Information System (INIS)

Lin Cansheng; Huang Meixin; Zhang Xianzi; Zhang Chonghai

1988-01-01

The behaviour of solvent extraction of niobium is discussed. The expractants, includding TBP, HDBP, H 2 MBP, TBP irradiated, HDEHP, TTA and Aliquat-7402, are used. The special influence of molybdenum and zirconium on solvent extraction of niobium and the extraction behaviur of niobium with TBP irradiated are described. The effect of fluorine and uranium in aqueous phase on extraction of niobium is mentioned. It is observed that the interfacial crud has not relevance to D Nb , but niobium-95 can be absorbed on it. The species of extractable niobium, extraction mechanism, and the reason brought niobum into organic phase are discussed. Finally, the idea of increasing decontamination factor for niobium is suggested

Acute chemical pneumonitis caused by nitric acid inhalation: case report

Energy Technology Data Exchange (ETDEWEB)

Choe, Hyung Shim; Lee, In Jae; Ko, Eun Young; Lee, Jae Young; Kim, Hyun Beom; Hwang, Dae Hyun; Lee, Kwan Seop; Lee, Yul; Bae, Sang Hoon [Hallym University Sacred Heart Hospital, Anyang (Korea, Republic of)

2003-06-01

Chemical pneumonitis induced by nitric acid inhalation is a rare clinical condition. The previously reported radiologic findings of this disease include acute permeability pulmonary edema, delayed bronchiolitis obliterans, and bronchiectasis. In very few published rare radiologic reports has this disease manifested as acute alveolar injury; we report a case of acute chemical pneumonitis induced by nitric acid inhalation which at radiography manifested as bilateral perihilar consolidation and ground-glass attenuation, suggesting acute alveolar injury.

Hydrothermal decomposition of TBP and fixation of its decomposed residue by HHP technique

International Nuclear Information System (INIS)

Yamasaki, N.; Fujiki, M.; Nishioka, M.; Ioku, K.; Yanagisawa, K.; Kozai, N.; Muraoka, S.

1991-01-01

The tributyl phosphate (TBP) used for the fuel reprocessing by Purex process is discharged as spent solvent because of the chemical decomposition and the damage due to radiation. Alkaline hydrothermal treatment in oxygen which is the reaction in a closed system is effective for the decomposition of TBP as it can transform organic materials to stable inorganic ions. Hydrothermal hot pressing technique has been applied to the immobilization of various radioactive wastes. This work deals with the continuous treatment process for the decomposition of TBP waste and the immobilization of its decomposed residue under hydrothermal condition. These processes are outlined. The experiment and the results are reported. TBP was completely decomposed above 200degC, and COD value showed the maximum at 250degC. The reaction process consists of two steps of the hydrolysis of TBP and the oxidation of the formed organic material. (K.I.)

Evaporation and NARS Nitric Acid Mass Balance Summary: 2000--2005

International Nuclear Information System (INIS)

Kreutzberg, B.D.; Ames, R.L.; Hansel, K.M.

2005-01-01

A compilation of the historical nitric acid processing data for the evaporation and nitric acid recycle system (NARS) in TA-55 has provided general acid mass balance trends, as well as the location of missing information in both the evaporation system and NARS data logs. The data were accumulated during the calendar years 2000 to 2005. After making a number of processing assumptions, the empirical system information was used to create an interactive spreadsheet that predicts, with moderate accuracy, some of the various stream variables for the combined evaporation and acid recycle processes. Empirical data and interactive calculations were compared to an Aspen Plus(trademark) simulation of the process

Buffering effects on electrograining of aluminium in nitric acid

International Nuclear Information System (INIS)

Koroleva, E.V.; Thompson, G.E.; Skeldon, P.; Hollrigl, G.; Lockwood, S.; Smith, G.

2005-01-01

Electrograining of a binary Al-Si alloy has been undertaken in nitric acid based electrolytes, with the resultant surfaces examined by scanning and transmission electron microscopies. Depending on electrograining conditions, the pit appearance varies from hemispherical to large lateral pits, with the latter favoured in relatively acidic electrolytes. The conditions prevailing in the pit have been explored through use of aluminium ion additions to the nitric acid electrolyte as well as additions of species which influence the precipitation and dissolution of aluminium hydroxide. These confirm that control of the pit solution pH, through hydroxide generation, as a result of the selected electrograining conditions and consequent anodic and cathodic polarisation, enables tailoring of the resultant electrograined surface appearance

Study of the tributyl phosphate - 30% dodecane solvent

International Nuclear Information System (INIS)

Leroy, P.

1967-01-01

This study, originating mainly from a literature survey, gives the principal chemical and physical features of the tributyl-phosphate (TBP) agent diluted at 30 volumes per cent in dodecane. The mixture is a very commonly used extractant in nuclear fuel processing. In this paper, the main following points are reported: -) the components (TBP and diluents) -) the TBP-diluents systems (non-loaded), -) the TBP-diluents-water systems, -) TBP-diluents-water-nitric acid systems, and -) industrial solvents. (author) [fr

Control of instability in nitric acid evaporators for plutonium processing

International Nuclear Information System (INIS)

1998-03-01

Improved control of the nitric acid process evaporators requires the detection of spontaneously unstable operating conditions. This process reduces the volume of contaminated liquid by evaporating nitric acid and concentrating salt residues. If a instability is identified quickly, prompt response can avert distillate contamination. An algorithm applied to the runtime data was evaluated to detect this situation. A snapshot of data from a histogram in the old process control software was captured during the unstable conditions and modeled

Quantify Water Extraction by TBP/Dodecane via Molecular Dynamics Simulations

International Nuclear Information System (INIS)

Khomami, Bamin; Cui, Shengting; De Almeida, Valmor F.

2013-01-01

The purpose of this project is to quantify the interfacial transport of water into the most prevalent nuclear reprocessing solvent extractant mixture, namely tri-butyl- phosphate (TBP) and dodecane, via massively parallel molecular dynamics simulations on the most powerful machines available for open research. Specifically, we will accomplish this objective by evolving the water/TBP/dodecane system up to 1 ms elapsed time, and validate the simulation results by direct comparison with experimentally measured water solubility in the organic phase. The significance of this effort is to demonstrate for the first time that the combination of emerging simulation tools and state-of-the-art supercomputers can provide quantitative information on par to experimental measurements for solvent extraction systems of relevance to the nuclear fuel cycle. Results: Initially, the isolated single component, and single phase systems were studied followed by the two-phase, multicomponent counterpart. Specifically, the systems we studied were: pure TBP; pure n-dodecane; TBP/n-dodecane mixture; and the complete extraction system: water-TBP/n-dodecane two phase system to gain deep insight into the water extraction process. We have completely achieved our goal of simulating the molecular extraction of water molecules into the TBP/n-dodecane mixture up to the saturation point, and obtained favorable comparison with experimental data. Many insights into fundamental molecular level processes and physics were obtained from the process. Most importantly, we found that the dipole moment of the extracting agent is crucially important in affecting the interface roughness and the extraction rate of water molecules into the organic phase. In addition, we have identified shortcomings in the existing OPLS-AA force field potential for long-chain alkanes. The significance of this force field is that it is supposed to be optimized for molecular liquid simulations. We found that it failed for dodecane and

The production of rare earth elements group via tributyl phosphate extraction and precipitation stripping using oxalic acid

Directory of Open Access Journals (Sweden)

Esmaeil Jorjani

2016-11-01

Full Text Available In this study, solvent extraction and precipitation stripping were used to produce rare earth elements (REEs. Tributyl phosphate (TBP was used to extract yttrium, lanthanum, cerium, and neodymium from an aqueous solution produced by nitric acid leaching of apatite concentrate. In the extraction stage, the effects of TBP concentration, pH, contact time, temperature, and phase ratio were investigated. The results show that about 95%, 90%, 87% and 80% of neodymium, cerium, lanthanum, and yttrium, respectively, can be extracted in optimum conditions of extraction. Hot, deionized water was used to scrub the impurities from the loaded organic phase. The results showed that three stages of scrubbing with a phase ratio (Va/Vo of five removed about 80%, 30%, 27%, and 15% of Ca, Mg, Fe, and P, respectively, from loaded TBP, while less than 9% of total REEs was lost. The effects on precipitation stripping of oxalic acid concentration, contact time, and phase ratio were investigated. The results showed that precipitation stripping is a viable alternative to traditional acid stripping in the REEs production process. Mixed REEs oxide with an assay of about 90% can be achieved as a final product.

Simultaneous Measurement of Nitrous Acid,Nitric Acid, and Nitrogen Dioxide by Means \

Czech Academy of Sciences Publication Activity Database

Vichi, F.; Mašková, Ludmila; Frattoni, M.; Imperiali, A.; Smolík, Jiří

2016-01-01

Roč. 4, FEB 22 (2016), s. 4 ISSN 2050-7445. [International Conference on Indoor Air Quality in Heritage and Historic Environments /11./. Prague, 13.04.2014-16.04.2014] Institutional support: RVO:67985858 Keywords : diffusive sampling * nitrous acid * nitric acid Subject RIV: CF - Physical ; Theoretical Chemistry

Nitric-phosphoric acid oxidation of solid and liquid organic materials

International Nuclear Information System (INIS)

Pierce, R.A.; Smith, J.R.; Poprik, D.C.

1995-01-01

Nitric-phosphoric acid oxidation has been developed specifically to address issues that face the Savannah River Site, other defense-related facilities, private industry, and small-volume generators such as university and medical laboratories. Initially tested to destroy and decontaminate SRS solid, Pu-contaminated job-control waste, the technology has also exhibited potential for remediating hazardous and mixed-hazardous waste forms. The process is unique to Savannah River and offers a valuable alternative to other oxidation processes that require extreme temperatures and/or elevated pressures. To address the broad categories of waste, many different organic compounds which represent a cross-section of the waste that must be treated have been successfully oxidized. Materials that have been quantitatively oxidized at atmospheric pressure below 180 degrees C include neoprene, cellulose, EDTA, tributylphosphate, and nitromethane. More stable compounds such as benzoic acid, polyethylene, oils, and resins have been completely decomposed below 200 degrees C and 10 psig. The process uses dilute nitric acid in a concentrated phosphoric acid media as the main oxidant for the organic compounds. Phosphoric acid allow nitric acid to be retained in solution well above its normal boiling point. The reaction forms NOx vapors which can be reoxidized and recycled using air and water. The addition of 0.001M Pd(II) reduces CO generation to near 1% of the released carbon gases. The advantages of this process are that it is straightforward, uses relatively inexpensive reagents, operates at relatively low temperature and pressure, and produces final solutions which are compatible with stainless steel equipment. For organic wastes, all carbon, hydrogen, and nitrogen are converted to gaseous products. If interfaced with an acid recovery system which converts NOx back to nitric acid, the net oxidizer would be oxygen from air

Removal of fluoride from aqueous nitric acid

International Nuclear Information System (INIS)

Pruett, D.J.; Howerton, W.B.; Mailen, J.C.

1981-06-01

Several methods for removing fluoride from aqueous nitric acid were investigated and compared with the frequently used aluminum nitrate-calcium nitrate (Ca 2+ -Al 3+ ) chemical trap-distillation system. Zirconium oxynitrate solutions were found to be superior in preventing volatilization of fluoride during distillation of the nitric acid, producing decontamination factors (DFs) on the order of 2 x 10 3 (vs approx. 500 for the Ca 2+ -Al 3+ system). Several other metal nitrate systems were tested, but they were less effective. Alumina and zirconia columns proved highly effective in removing HF from HF-HNO 3 vapors distilled through the columns; fluoride DFs on the order of 10 6 and 10 4 , respectively, were obtained. A silica gel column was very effective in adsorbing HF from HF-HNO 3 solutions, producing a fluoride DF of approx. 10 4

Citric Acid Alternative to Nitric Acid Passivation

Science.gov (United States)

Lewis, Pattie L. (Compiler)

2013-01-01

The Ground Systems Development and Operations GSDO) Program at NASA John F. Kennedy Space Center (KSC) has the primary objective of modernizing and transforming the launch and range complex at KSC to benefit current and future NASA programs along with other emerging users. Described as the launch support and infrastructure modernization program in the NASA Authorization Act of 2010, the GSDO Program will develop and implement shared infrastructure and process improvements to provide more flexible, affordable, and responsive capabilities to a multi-user community. In support of the GSDO Program, the purpose of this project is to demonstratevalidate citric acid as a passivation agent for stainless steel. Successful completion of this project will result in citric acid being qualified for use as an environmentally preferable alternative to nitric acid for passivation of stainless steel alloys in NASA and DoD applications.

Transportation impact analysis for the shipment of Low Specific Activity Nitric Acid

International Nuclear Information System (INIS)

Green, J.R.

1994-01-01

This document was written in support of the Plutonium-Uranium Extraction (PUREX) Facility Low Specific Activity (LSA) Nitric Acid Shipment Environmental Assessment. It analyzes the potential toxicological and radiological risks associated with the transportation of PUREX Facility LSA Nitric Acid from the Hanford Site in Washington State to three Eastern ports

Characterization of condensed phase nitric acid particles formed in the gas phase

Institute of Scientific and Technical Information of China (English)

Long Jia; Yongfu Xu

2011-01-01

The formation of nitric acid hydrates has been observed in a chamber during the dark reaction of NO2 with O3 in the presence of air.The size of condensed phase nitric acid was measured to be 40-100 nm and 20-65 nm at relative humidity (RH) ≤ 5％ and RH = 67％ under our experimental conditions, respectively.The nitric acid particles were collected on the glass fiber membrane and their chemical compositions were analyzed by infrared spectrum.The main components of nitric acid hydrates in particles are HNO3·3H2O and NO3-·xH2O (x≥ 4) at low RH, whereas at high RH HNO3·H2O, HNO3·2H2O, HNO3·3H2O and NO3-·xH2O (x≥ 4) all exist in the condensed phase.At high RH HNO3·xH2O (x ≤ 3) collected on the glass fiber membrane is greatly increased, while NO3-·xH2O (x ≥4) decreased, compared with low RH.To the best of our knowledge, this is the first time to report that condensed phase nitric acid can be generated in the gas phase at room temperature.

Equilibrium and kinetics of co-extraction of U(VI) and HNO3 using tri-n-butyl phosphate and tri-iso-amyl phosphate in paraffin

International Nuclear Information System (INIS)

Das, Diptendu; Juvekar, V.A.; Biswas, Sujoy; Roy, S.B.; Bhattacharya, R.

2014-01-01

Tri-n-butyl phosphate (TBP) is versatile solvent for recovery of actinides as it is cheaper and the extracted actinides can be stripped from the loaded organic phase using plain water. However there are inherent problems associated TBP such as i) formation of the third phase ii) high solubility in aqueous phase iii) radiolytic hydrolysis at high radiation environment and iv) high propensity for extraction of mineral acids. The last mentioned property makes it less suitable for liquid emulsion membrane (LEM) extraction where acid transport to the strip phase drastically reduces extraction efficiency. Therefore there is need to replace TBP with an extractant which has lesser propensity for acid extraction. Many researcher reported Tri-iso-amyl phosphate (TiAP) as an alternative extractant which can sustain high radiation environment without chemical/radiative degradation. However there are no studies available on co-extraction of U(VI) and mineral acids by TiAP. In this research paper equilibrium and kinetics of co-extraction of U(VI) and HNO 3 from nitric acid medium into a hydrocarbon phase (paraffin) using Tri n- butyl phosphate (TBP), Tri-iso-amyl phosphate (TiAP) has been studied. Relative rates of extraction of uranium(VI) and HNO 3 by TiAP and TBP were measured simultaneously using bulk-liquid membrane (BLM) system. Study reveals although TiAP is less efficient in extracting U(IV), than TBP, it transfers lesser quantity of nitric acid to organic phase. Hence TiAP is more suitable as a carrier for LEM extraction than TBP

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum

International Nuclear Information System (INIS)

Cames, B.

1997-01-01

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media (≤ 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 ≤ E ≤ 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

Speciation of platinum(IV) in nitric acid solutions.

Science.gov (United States)

Vasilchenko, Danila; Tkachev, Sergey; Baidina, Iraida; Korenev, Sergey

2013-09-16

The speciation of platinum(IV) ions in nitric acid (6-15.8 M) solutions of H2[Pt(OH)6] has been studied by (195)Pt NMR and Raman spectroscopy. Series of aqua-hydroxo-nitrato complexes [Pt(L)(x)(NO3)(6-x)] (L = H2O or OH(-); x = 0, ..., 6) were found to exist in such solutions. The pair additivity model of chemical shifts and statistical theory were used to assign signals in NMR spectra to particular [Pt(L)(x)(NO3)(6-x)] species. Mononuclear hexanitratoplatinates(IV) have been isolated in solid state in substantial yield as pyridinium salt (PyH)2[Pt(NO3)6] and characterized by single-crystal X-ray diffraction. Aging of the platinum nitric acid solutions for more than 5-6 h results in oligomerization of [Pt(L)(x)(NO3)(6-x)] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH(-) and NO3(-) bridging ligands. Oligomeric platinum(IV) complexes with two and four nuclei were unambiguously detected by NMR on (195)Pt -enriched samples. Oligomers with even higher nuclearity were also detected. Dimeric anions [Pt2(μ-OH)2(NO3)8](2-) have been isolated as single crystals of tetramethylammonium salt and characterized by X-ray diffraction.

Electroreduction of nitric acid to hydroxylamine

International Nuclear Information System (INIS)

Haque, I.U.; Saima, W.

2008-01-01

This article reviews recent studies concerned with the synthesis of hydroxylamine Hydroxylamine plays a significant role in agriculture, photographic developing, as a component in liquid propellants and as a reducing agent etc. In this regard modification of carbon electrode surface greatly increases hydrogen overpotential in nitric acid solutions and allows electrochemical generation of hydroxylamine with good current efficiency. (author)

Mutations on the DNA binding surface of TBP discriminate between yeast TATA and TATA-less gene transcription.

Science.gov (United States)

Kamenova, Ivanka; Warfield, Linda; Hahn, Steven

2014-08-01

Most RNA polymerase (Pol) II promoters lack a TATA element, yet nearly all Pol II transcription requires TATA binding protein (TBP). While the TBP-TATA interaction is critical for transcription at TATA-containing promoters, it has been unclear whether TBP sequence-specific DNA contacts are required for transcription at TATA-less genes. Transcription factor IID (TFIID), the TBP-containing coactivator that functions at most TATA-less genes, recognizes short sequence-specific promoter elements in metazoans, but analogous promoter elements have not been identified in Saccharomyces cerevisiae. We generated a set of mutations in the yeast TBP DNA binding surface and found that most support growth of yeast. Both in vivo and in vitro, many of these mutations are specifically defective for transcription of two TATA-containing genes with only minor defects in transcription of two TATA-less, TFIID-dependent genes. TBP binds several TATA-less promoters with apparent high affinity, but our results suggest that this binding is not important for transcription activity. Our results are consistent with the model that sequence-specific TBP-DNA contacts are not important at yeast TATA-less genes and suggest that other general transcription factors or coactivator subunits are responsible for recognition of TATA-less promoters. Our results also explain why yeast TBP derivatives defective for TATA binding appear defective in activated transcription. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Physiological responses of lichens to factorial fumigations with nitric acid and ozone

Science.gov (United States)

J. Riddell; P.E. Padgett; T. Nash

2012-01-01

This paper addresses the effects of gaseous nitric acid (HNO3) and ozone (O3), two important air pollutants, on six lichen species with different morphological, ecological, and biological characteristics. The treatment chambers were set up in a factorial design consisting of control chambers, chambers fumigated with HNO

Study of the tributyl phosphate - 30% dodecane solvent; Etude du solvant phosphate tributylique - 30 % dodecane

Energy Technology Data Exchange (ETDEWEB)

Leroy, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses. Centre d' Etudes Nucleaires, 92 (France)

1967-07-01

This study, originating mainly from a literature survey, gives the principal chemical and physical features of the tributyl-phosphate (TBP) agent diluted at 30 volumes per cent in dodecane. The mixture is a very commonly used extractant in nuclear fuel processing. In this paper, the main following points are reported: -) the components (TBP and diluents) -) the TBP-diluents systems (non-loaded), -) the TBP-diluents-water systems, -) TBP-diluents-water-nitric acid systems, and -) industrial solvents. (author) [French] Cette etude, d'origine bibliographique, regroupe les caracteristiques physico-chimiques essentielles du phosphate tributylique (TBP) dilue a 30% en volume dans du dodecane. Ce melange constitue un agent d'extraction tres utilise dans le traitement des combustibles nucleaires. Les principaux points traites sont les suivants: -) les constituants (TBP et diluants), -) les systemes TBP-diluants non charges, -) les systemes TBP-diluants-eau, -) les systemes TBP-diluants-eau-acide nitrique, et -) les solvants industriels. (auteur)

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-09-30

The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

Critical evaluation of pressurized microwave-assisted digestion efficiency using nitric acid oxidizing systems (M7)

International Nuclear Information System (INIS)

Matusiewicz, H.

2002-01-01

Full text: The possibilities of enhancement of a medium-pressure microwave-assisted digestion system for sample preparation in trace element analysis of biological material was investigated. Based on optimal digestion conditions for oxidizing systems with nitric acid, different digestion procedures were examined to minimize residual carbon. The substitution of nitric acid and the addition of hydrogen peroxide and ozone to nitric acid was evaluated. The residual carbon content of the digestate was determined coulometrically. Addition of hydrogen peroxide during organic oxidation reactions does not lower the resolved carbon in the solution. Ozone was tested as an additional, potentially non-contaminating, digestion/oxidation system to the nitric acid used in the sample preparation method. (author)

Extraction studies of actinides by diamylbutyl phosphonate

International Nuclear Information System (INIS)

Brahmananda Rao, C.V.S.; Jayalakshmi, S.; Subramaniam, S.; Sabharwal, K.N.; Sivaraman, N.; Vasudeva Rao, P.R.

2014-01-01

The extraction ability of a monodentate organophosphorus extractant depends on the basicity of the phosphoryl oxygen atom and the nature of the substituents attached to the phosphorus atom. The basicity on the phosphoryl oxygen in the neutral organophosphorus extractant series increases in the order, phosphates 1 H, 13 C and 31 P NMR spectra. Extraction of U(VI) by 1.1 M DABP/n-dodecane as a function of nitric acid was studied using 233 U tracer. Th(IV) extraction behaviour as a function of nitric acid was studied using Arsenazo-III as chromogenic agent. 5 mL of the 1.1 M DABP solution in the diluent (n-dodecane) was equilibrated with 5mL of saturated thorium nitrate in an equilibration tube using a magnetic stirring bar. The organic and aqueous phases were analysed by complexometry using DTPA as titrant and xylenol orange as indicator. The LOC values were determined as a function of nitric acid concentration. The extraction of U(VI) and Th(IV) by 1.1M DABP along with TBP in n-dodecane at 303 K as a function of equilibrium nitric acid concentration are shown. The DABP shows higher distribution ratios for U(VI) and Th(IV) in the entire range of nitric acid concentrations studied compared to TBP. The steep rise in the distribution ratio is attributed to the higher basicity of phosphoryl group in phosphonates compared to the less basic nature of phosphates. The third phase formation of thorium as function of nitric acid concentration with 1.1 M DABP at 303 K are given. The LOC values for DABP system were higher throughout the nitric acid concentration compared to the TBP system. (author)

Corrosion mechanism of Z3 CN18.10 stainless steel in the presence of nitric acid condensates

International Nuclear Information System (INIS)

Balbaud, Fanny

1998-01-01

In installations handling concentrated boiling nitric acid, a severe intergranular corrosion can sometimes occur in condensation zones constituted of non-sensitized Z3 CN 18.10 stainless steel. Corrosion tests in reactors and in a specific loop, CIRCE, allowed to specify the conditions of occurrence of this type of corrosion and showed the similitude with the corrosion in non-renewed liquid nitric acid: the specific parameters linked to the condensate phase are the high ratio metallic surface area to volume of condensate and the low renewing rate which induce a concentration of oxidation products of the metal and of reduction products of nitric acid. The initiation of the intergranular corrosion is attributed to the increase in the reduction rate of nitric acid by an autocatalytic mechanism which was demonstrated by electrochemical measurements on platinum and on stainless steel. The reduction mechanism involves a charge transfer step where nitrous acid, the electro-active species, is reduced into nitrogen monoxide and a chemical regeneration reaction of nitrous acid. The thermodynamic study led to a representation of the chemical and electrochemical properties of nitric acid. This study allowed also to determine the Gibbs free energy of formation of nitrous acid in solution in concentrated nitric acid at 100 deg. C. The diagram, constructed in coordinates log(P O 2 ) / [-log(P HNO 3 )] or E eXperimental / [-log(P HNO 3 )], shows that the final reduction product of nitric acid depends on the concentration of nitric acid: at 100 deg. C, NO is obtained for concentrations lower than 8 mol.L -1 and NO 2 is obtained for higher concentrations. All these results allowed to propose a corrosion mechanism of Z3 CN 18.10 stainless steel in the presence of nitric acid condensates. [fr

Nonnuclear hydrometallurgical applications of TBP

International Nuclear Information System (INIS)

Ritcey, G.M.; Pouskouleli, G.

1987-01-01

This chapter on the nonnuclear solvent extraction applications of tri-n-butyl phosphate (TBP) has been assembled from information in the analytical, chemical, and metallurgical literature. There are actually few operating plants, or, in fact, process flowsheets designed for the use of TBP in the extraction of nonnuclear metals and other materials. Perhaps one of the main reasons for this is that TBP operates through a solvating mechanism of extraction, and, therefore, extraction is highly dependent upon, the ionic strength of the anion. Many developments in process metallurgy utilizing solvent extraction involve extraction from a sulfate medium. Very few plants have gone on-stream employing chloride or nitrate systems, even though TBP is an excellent extractant from aqueous chloride or nitrate media. It is very likely that in the future we shall see many hydrometallurgical processes developed and plants designed in which the aqueous medium is chloride. With this in mind, we have included analytical and chemical techniques as possible guides to future design trends. The chapter includes most of the elements in the Periodic Table and covers all the various groups in the table. The chemistry of metals within the same group is, of course, quite similar, and this is evident in the comparison of extraction properties. For the convenience of the reader we have put the various metals into groups found within the Periodic Table, or in other appropriate groups that show chemical relationships. The literature surveyed in this chapter covers the period 1966 to 1984

Molecular dynamics of TBP and DBP studied by neutron transmission

International Nuclear Information System (INIS)

Salles Filho, J.B.V.; Refinetti, M.E.; Fulfaro, R.; Vinhas, L.A.

1984-04-01

Differences between the properties of TBP and DBP, concerning the uranium extraction processes, may be related to certain characteristics of the molecular dynamics of each compound. In order to investigate the dynamical behaviour of hydrogen in these molecules, neutron transmission of TBP and DBP has been measured as a function of neutron wavelenght in the range 4.0 - 6.0 A, at room temperature. Scattering cross sections per hydrogen atom have been obtained. From the comparison with results previously obtained for n-butanol, similar dynamical behaviour of butyl radicals in these compounds could be observed. This similarity indicates that the presence of two or three butyl radicals in butylphosphate molecules does not exert influence in the hydrogen motion of methyl and methylene groups. This suggests that the different chemical behaviour between TBP and DBP is related to the dynamics of the hydrogen directly bound to the DBP phosphate group.(Author) [pt

Physiological responses of lichens to factorial fumigations with nitric acid and ozone

International Nuclear Information System (INIS)

Riddell, J.; Padgett, P.E.; Nash, T.H.

2012-01-01

This paper addresses the effects of gaseous nitric acid (HNO 3 ) and ozone (O 3 ), two important air pollutants, on six lichen species with different morphological, ecological, and biological characteristics. The treatment chambers were set up in a factorial design consisting of control chambers, chambers fumigated with HNO 3 , with O 3 , and with HNO 3 and O 3 , together. Each species showed a different sensitivity to the fumigations, reflecting the physiological variation among species. Our results clearly indicate that HNO 3 is a strong phytotoxin to many lichens, and that O 3 alone has little effect on the measured parameters. The combined fumigation effects of HNO 3 and O 3 were not significantly different from HNO 3 alone. - Highlights: ► We fumigated 6 lichen species with factorial combinations of nitric acid (HNO 3 ) and ozone (O 3 ). ► Some species were highly sensitive to HNO 3 while others were tolerant. ► No species responded significantly to O 3 . ► The combined fumigation effects of HNO 3 and O 3 were not significantly different from HNO 3 alone. ► HNO 3 may play an important role in lichen community composition in areas with high HNO 3 pollution. - Nitric acid can be highly toxic to lichens through several physiological mechanisms. Ozone is relatively non-toxic to fumigated lichens.

Study of precipitation behaviour of Mo and Zr in nitric acid solution

International Nuclear Information System (INIS)

Lin Cansheng; Wang Xiaoying; Zhang Chonghai

1992-01-01

The precipitation behaviour of Mo and Zr which depends on the concentrations of Mo, Zr, nitric acid and temperature is studied. Precipitation, post-precipitation and ultracentrifugation experiments are made at 100 deg C, 80 deg C, 60 deg C, 40 deg C and room temperatures in the range of 0.6-6.0 mol/1 nitric acid. The experimental feeds are made up of molybdenum labelled with 99 Mo, zirconium labelled with 95 Zr and nitric acid solution. The feed is allowed to stand at constant temperature for some time for the observation of precipitation behaviour. The filtered precipitate and ultracentrifuged liquid is to be measured with HP (Ge)-multichannel analyser in order to determine the content of Mo, Zr and their mole ration in the precipitate and to find out whether there is colloid in the liquid. The results show that the mixed solution of Mo and Zr can produce precipitate and post-precipitate in nitric acid. If the filtrated liquid is allowed to stand for some time, precipitate can be produced again, until the concentration of Mo and Zr in the feed is too low to form precipitate, such as 2.5 x 10 -3 mol/1. If the concentration of nitric acid is less than 4.0 mol/1, the precipitation is produced easily and more precipitate is formed. Precipitation is slower in solutions which are more than 4.0 mol/1 in HNO 3 . The mole-ratio of Mo to Zr in the precipitate is 2 to 1 and it is not dependent on that ratio in the system

Rapid cycling of reactive nitrogen in the marine boundary layer.

Science.gov (United States)

Ye, Chunxiang; Zhou, Xianliang; Pu, Dennis; Stutz, Jochen; Festa, James; Spolaor, Max; Tsai, Catalina; Cantrell, Christopher; Mauldin, Roy L; Campos, Teresa; Weinheimer, Andrew; Hornbrook, Rebecca S; Apel, Eric C; Guenther, Alex; Kaser, Lisa; Yuan, Bin; Karl, Thomas; Haggerty, Julie; Hall, Samuel; Ullmann, Kirk; Smith, James N; Ortega, John; Knote, Christoph

2016-04-28

Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A 'renoxification' process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.

Extraction behaviour of Am(III) and Eu(III) from nitric acid medium in CMPO-HDEHP impregnated resins

Energy Technology Data Exchange (ETDEWEB)

Saipriya, K.; Kumar, T. [Bhabha Atomic Research Centre Facilities (India). Kalpakkam Reproscessing Plants; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Center for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

2016-05-01

Chromatographic resin containing extractants such as octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) or bis-(2-ethylhexyl)phosphoric acid (HDEHP) or mixture of extractants (CMPO + HDEHP) in an acrylic polymer matrix was prepared and studied for the extraction of Am(III) and Eu(III) over a range of nitric acid concentration. The effect of various parameters such as concentration of nitric acid in aqueous phase and the concentration of CMPO and HDEHP in the resin phase was studied. The distribution coefficient of Am(III) and Eu(III) in the impregnated resin increased with increased in the concentration of nitric acid for CMPO-impregnated resin, whereas a reverse trend was observed in HDEHP impregnated resin. In case of resin containing both the extractants, synergism was observed at low nitric acid concentration and antagonism at high nitric acid concentration. The mechanism of extraction was probed by slope analysis method at 0.01 and 2 M nitric acid concentrations. Citrate-buffered DTPA was used for the selective separation of Am(III), and a separation factor of 3-4 was obtained at pH 3.

Mechanism of the extraction of nitric acid and water by organic solutions of tertiary alkyl-amines

International Nuclear Information System (INIS)

Gourisse, D.

1966-06-01

The micellar aggregation of tri-alkyl-ammonium nitrates in low polarity organic solvents has been verified by viscosity, conductivity and sedimentation velocity measurements. The aggregation depends upon the polarity of solvent, the length of the alkyl radicals and the organic concentration of the various constituents (tri-alkyl-ammonium nitrate, tri-alkyl-amine, nitric acid, water). The amine salification law has been established and the excess nitric acid and water solubilities in the organic solutions have been measured. Nitric acid and water are slightly more soluble in micellar organic solutions than in molecular organic solutions. A description of excess nitric acid containing tri-alkyl-ammonium nitrate solutions is proposed. (author) [fr

Wet Chemical Oxidation of Organic Waste Using Nitric-Phosphoric Acid Technology

Energy Technology Data Exchange (ETDEWEB)

Pierce, R.A.

1998-10-06

Experimental progress has been made in a wide range of areas which support the continued development of the nitric-phosphoric acid oxidation process for combustible, solid organic wastes. An improved understanding of the overall process operation has been obtained, acid recovery and recycle systems have been studied, safety issues have been addressed, two potential final waste forms have been tested, preliminary mass flow diagrams have been prepared, and process flowsheets have been developed. The flowsheet developed is essentially a closed-loop system which addresses all of the internally generated waste streams. The combined activities aim to provide the basis for building and testing a 250-400 liter pilot-scale unit. Variations of the process now must be evaluated in order to address the needs of the primary customer, SRS Solid Waste Management. The customer is interested in treating job control waste contaminated with Pu-238 for shipment to WIPP. As a result, variations for feed preparation, acid recycle, and final form manufacturing must be considered to provide for simpler processing to accommodate operations in high radiation and contamination environments. The purpose of this program is to demonstrate a nitric-phosphoric acid destruction technology which can treat a heterogeneous waste by oxidizing the solid and liquid organic compounds while decontaminating noncombustible items.

Nitric-phosphoric acid oxidation of organic waste materials

International Nuclear Information System (INIS)

Pierce, R.A.; Smith, J.R.

1995-01-01

A wet chemical oxidation technology has been developed to address issues facing defense-related facilities, private industry, and small-volume generators such as university and medical laboratories. Initially tested to destroy and decontaminate a heterogenous mixture of radioactive-contaminated solid waste, the technology can also remediate other hazardous waste forms. The process, unique to Savannah River, offers a valuable alternative to incineration and other high-temperature or high-pressure oxidation processes. The process uses nitric acid in phosphoric acid; phosphoric acid allows nitric acid to be retained in solution well above its normal boiling point. The reaction converts organics to carbon dioxide and water, and generates NO x vapors which can be recycled using air and water. Oxidation is complete in one to three hours. In previous studies, many organic compounds were completely oxidized, within experimental error, at atmospheric pressure below 180 degrees C; more stable compounds were decomposed at 200 degrees C and 170 kPa. Recent studies have evaluated processing parameters and potential throughputs for three primary compounds: EDTA, polyethylene, and cellulose. The study of polyvinylchloride oxidation is incomplete at this time

NASA and ESA Collaboration on Alternative to Nitric Acid Passivation: Parameter Optimization of Citric Acid Passivation for Stainless Steel Alloys

Science.gov (United States)

Kessel, Kurt R.

2016-01-01

National Aeronautics and Space Administration (NASA) Headquarters chartered the Technology Evaluation for Environmental Risk Mitigation Principal Center (TEERM) to coordinate agency activities affecting pollution prevention issues identified during system and component acquisition and sustainment processes. The primary objectives of NASA TEERM are to: Reduce or eliminate the use of hazardous materials or hazardous processes at manufacturing, remanufacturing, and sustainment locations. Avoid duplication of effort in actions required to reduce or eliminate hazardous materials through joint center cooperation and technology sharing. Corrosion is an extensive problem that affects the National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA). The damaging effects of corrosion result in steep costs, asset downtime affecting mission readiness, and safety risks to personnel. Consequently, it is vital to reduce corrosion costs and risks in a sustainable manner. NASA and ESA have numerous structures and equipment that are fabricated from stainless steel. The standard practice for protection of stainless steel is a process called passivation. Passivation is defined by The American Heritage Dictionary of the English Language as to treat or coat (a metal) in order to reduce the chemical reactivity of its surface. Passivation works by forming a shielding outer (metal oxide) layer that reduces the impact of destructive environmental factors such as air or water. Consequently, this process necessitates a final product that is very clean and free of iron and other contaminants. Typical passivation procedures call for the use of nitric acid; however, there are a number of environmental, worker safety, and operational issues associated with its use. Citric acid is an alternative to nitric acid for the passivation of stainless steels. Citric acid offers a variety of benefits including increased safety for personnel, reduced environmental impact, and

Stabilization and Solidification of Nitric Acid Effluent Waste at Y-12

Energy Technology Data Exchange (ETDEWEB)

Singh, Dileep [Argonne National Lab. (ANL), Argonne, IL (United States); Lorenzo-Martin, Cinta [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-12-16

Consolidated Nuclear Security, LLC (CNS) at the Y-12 plant is investigating approaches for the treatment (stabilization and solidification) of a nitric acid waste effluent that contains uranium. Because the pH of the waste stream is 1-2, it is a difficult waste stream to treat and stabilize by a standard cement-based process. Alternative waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the nitric acid effluent wastes.

Recovery of actinides from TBP-Na2Co3 scrub-waste solutions: the ARALEX process

International Nuclear Information System (INIS)

Horwitz, E.P.; Bloomquist, C.A.A.; Mason, G.W.; Leonard, R.A.; Ziegler, A.A.

1979-08-01

A flowsheet for the recovery of actinides from TBP-Na 2 CO 3 scrub-waste solutions has been developed, based on batch extraction data, and tested, using laboratory-scale countercurrent extraction techniques. The process, called the ARALEX process, uses 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H 2 MBP) from acidified Na 2 CO 3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds, which also diminish the ability of the HDBP and H 2 MBP to complex actinides. Thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds (e.g., detergents) that interfere with conventional actinide ion exchange and liquid-liquid extraction procedures. 20 figures, 6 tables

Transportation impact analysis for the shipment of low specific activity nitric acid. Revisison 1

International Nuclear Information System (INIS)

Green, J.R.

1995-01-01

This is in support of the Plutonium-Uranium Extraction (PUREX) Facility Low Specific Activity (LSA) Nitric Acid Shipment Environmental Assessment. It analyzes potential toxicological and radiological risks associated with transportation of PUREX Facility LSA Nitric Acid from the Hanford Site to Portsmouth VA, Baltimore MD, and Port Elizabeth NJ

Transportation impact analysis for the shipment of low specific activity nitric acid. Revisison 1

Energy Technology Data Exchange (ETDEWEB)

Green, J.R.

1995-05-16

This is in support of the Plutonium-Uranium Extraction (PUREX) Facility Low Specific Activity (LSA) Nitric Acid Shipment Environmental Assessment. It analyzes potential toxicological and radiological risks associated with transportation of PUREX Facility LSA Nitric Acid from the Hanford Site to Portsmouth VA, Baltimore MD, and Port Elizabeth NJ.

Extraction behaviour of Am(III) and Eu(III) from nitric acid medium in TEHDGA-HDEHP impregnated resins

Energy Technology Data Exchange (ETDEWEB)

Saipriya, G.; Kumar, T. [Bhabha Atomic Research Centre Facilities, Kalpakkam (India). Kalpakkam Reprocessing Plant; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Center for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

2016-07-01

The extraction behaviour of Am(III) and Eu(III) from nitric acid medium was studied in the solvent impregnated resins containing extractants such as tetra-bis(2-ethylhexyl)diglycolamide (TEHDGA) or bis-(2-ethylhexyl)phosphoric acid (HDEHP) or mixture of TEHDGA+HDEHP. The rate of extraction of Am(III) and Eu(III) from 1 M nitric acid and the effect of various parameters, such as the concentration of nitric acid in aqueous phase and concentration of TEHDGA and HDEHP in resin phase, on the distribution coefficient of Am(III) and Eu(III) was studied. The distribution coefficient of Am(III) and Eu(III) in HDEHP-impregnated resin decreased and that in TEHDGA-impregnated resin increased, with increase in the concentration of nitric acid. However, in (TEHDGA+HDEHP) - impregnated resin, synergic extraction was observed at lower nitric acid concentration and antagonism at higher nitric acid concentration. The mechanism of Am(III) and Eu(III) extraction in the combined resin was investigated by slope analysis method. The extraction of various metal ions present in the fast reactor simulated high-level liquid waste was studied. The separation factor of Am(III) over Eu(III) was studied using citrate-buffered diethylenetriaminepentaacetic acid (DTPA) solution.

15N NMR spectroscopic investigation of nitrous and nitric acids in sulfuric acid solutions of varying acidities

International Nuclear Information System (INIS)

Prakash, G.K.S.; Heiliger, L.; Olah, G.A.

1990-01-01

Both nitrous and nitric acids were studied in sulfuric acid solutions of varying acid strengths by 15 N NMR spectroscopy. The study gives new insights into the nature of intermediates present at different acid strengths. Furthermore, we have also discovered a novel redox reaction between NO 2 + and NO + ions involving the intermediacy of their respective acids. A mechanism is proposed to explain the observed results. 13 refs., 2 figs., 1 tab

Spectrophotometric determination of uranium and plutonium in nitric acid solutions at their co-presence

International Nuclear Information System (INIS)

Levakov, B.I.; Mishenev, V.B.; Nezgovorov, N.Yu.; Ryazanova, G.K.; Timofeev, G.A.

1986-01-01

The method of spectrophotometric determination of uranium (6) and plutonium (4) in nitric acid solutions is described. Uranium is determined by light absorption of the complex with arsenazo 3 in 0.05 mol/l nitric acid at λ=654 nm, plutonium - by light absorption of the complex with xylenol orange in 0.1 mol/l nitric acid at λ=540 nm. To disguise plutonium, tetravalent and certain trivalent elements DTPA is introduced into photometered solution for uranium determination. The relative root-mean square deviation of determination results does not exceed 0.03 in uranium concenration ranges 0.5-5 μg/ml, of plutonium -1-3 μg/ml

Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

Energy Technology Data Exchange (ETDEWEB)

Ames, Richard L. [Colorado School of Mines, Golden, CO (United States)

2004-09-01

Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate

Aluminium dissolution for spray pulverization with nitric acid

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

1977-01-01

A comparative study of the nitric acid dissolution of aluminium, by immersion and spray pulverization has been carried out in laboratory scale. As a result, the optimum operation conditions to control reaction in the plant are fixed. Operation costs are also evaluated. (author) [es

Investigations into co-transport phenomena in PUREX relevant solutions by use of an analytical ultracentrifuge

International Nuclear Information System (INIS)

Gauglitz, R.; Marx, G.

1991-01-01

The diffusion of the elements uranium, neodymium, chromium, iron, ruthenium was studied in aqueous and aqueous nitric acid solutions. The diffusion of these elements was measured not only under a concentration gradient but also with respect to simultanious nitric and diffusion. Measurements with schlierenoptics and with uv/vis.-optic were carried out at the same time. Besides the diffusion of metal nitrates and potassium dichromate also nitric acid diffusion was investigated. Also in this case apparent diffusion coefficients were determined under concentration gradients and under the influence of superposing element gradients. The diffusion of the elements uranium, neodymium, ruthenium, neptunium and plutonium was also determined in organic systems. At first the transport of the elements was measured under an element gradient, in presence of various amounts of water and nitric acid. These experiments were followed by those on simultanious diffusion of water of nitric acid and elements in TBP/dodecane mixture. Furthermore TBP/dodecane solutions were oxidized with potassium dichromate. This oxidation was measured using a gaschromatograph. From the obtained results the formation rate for the oxidation products could be calculated which proved that higher nitric acid concentrations increased the rate. (orig.) With 16 refs., 100 tabs., 120 figs [de

Crack propagation behavior of Ti-5Ta alloy in boiling nitric acid solution

International Nuclear Information System (INIS)

Motooka, Takafumi; Kiuchi, Kiyoshi

1999-05-01

The crack propagation behavior of Ti-5Ta alloy both in boiling nitric acid solution and in air at room temperature has been investigated. The crack growth rate of Ti-5Ta alloy was measured as a function of the stress intensity factor range. After the tests, the fracture surface morphology was observed by a scanning electron microscope and the crystallographic orientation was examined by X-ray diffraction analysis. Difference in the crack growth behavior was not observed in both environments. The crack growth rate in boiling nitric acid solution was similar to that in air at room temperature. Moreover, the crystallographic orientation of Ti-5Ta alloy had little effect on the fatigue behavior, because this alloy does not have the susceptibility to SCC in nitric acid solution. (author)

Extraction of antimony from nitric acid solutions using tributyl phosphate. II. Tributyl phosphate-antimony(V)-nitric acid system

International Nuclear Information System (INIS)

Lakaev, V.S.; Smelov, V.S.

1989-01-01

The extraction of pentavalent antimony from nitric acid solutions using tributyl phosphate has been investigated. A possible mechanism for the extraction of antimony(V) has been determined and the (pre)concentration constant for the process has been calculated. The composition of the extracted antimony(V) complex has been deduced. A negative effect of temperature on the distribution coefficient for antimony(V) has also been demonstrated

Overview of ''Red Oil'' Frequency Analyses for F-Canyon

International Nuclear Information System (INIS)

Lux, C.R.

2000-01-01

A very small potential exists in the Savannah River Site (SRS) separations operations for an uncontrolled reaction between tri-n-butyl phosphate (TBP) and nitric acid that could result in unacceptable damage to separations facilities and a significant release of radioactive materials. The recent ''red oil'' (TBP and nitric acid) accident in Tomsk, Russia, resulted in considerable damage and radioactive release. Explosions have also occurred at SRS during the early years of operations. While the SRS separations facilities have operated without incident for many years, it is prudent to revisit the SRS defense-in-depth approach to preventing such an accident and to upgrade preventive procedures and hardware as appropriate

Corrosion behavior of ODS steels with several chromium contents in hot nitric acid solutions

Science.gov (United States)

Tanno, Takashi; Takeuchi, Masayuki; Ohtsuka, Satoshi; Kaito, Takeji

2017-10-01

Oxide dispersion strengthened (ODS) steel cladding tubes have been developed for fast reactors. Tempered martensitic ODS steels with 9 and 11 wt% of chromium (9Cr-, 11Cr-ODS steel) are the candidate material in research being carried out at JAEA. In this work, fundamental immersion tests and electrochemical tests of 9 to 12Cr-ODS steels were systematically conducted in various nitric acid solutions at 95 °C. The corrosion rate decreased exponentially with effective solute chromium concentration (Creff) and nitric acid concentration. Addition of vanadium (V) and ruthenium (Ru) also decreased the corrosion rate. The combination of low Creff and dilute nitric acid could not avoid the active mass dissolution during active domain at the beginning of immersion, and the corrosion rate was high. Higher Creff decreased the partial anodic current during the active domain and assisted the passivation of the surface of the steel. Concentrated nitric acid and addition of Ru and V increased partial cathodic current and shifted the corrosion potential to noble side. These effects should have prevented the active mass dissolution and decreased the corrosion rate.

OPTIMAL CONTROL OF AUTOCLAVE START MODE IN THE PRODUCTION OF NITRIC ACID

OpenAIRE

Ладієва, Леся Ростиславівна; Ширма, А. В.

2015-01-01

The algorithm of optimal control of autoclave start mode in the production of nitric acid is proposed. By optimality criterion is selected minimum time-autoclave at preset mode with the restriction on the concentration of nitric acid. End time start mode is entered on the terminal part of the cost function. The method of penalties and a gradient procedure is used to solve the problem. The applied algorithm is allowed to bring an autoclave at a given technological regime.Keywords: production o...

Corrosion resistance of zirconium: general mechanisms, behaviour in nitric acid

International Nuclear Information System (INIS)

Pinard Legry, G.

1990-01-01

Corrosion resistance of zirconium results from the strong affinity of this metal for oxygen; as a result a thin protective oxide film is spontaneously formed in air or aqueous media, its thickness and properties depending on the physicochemical conditions at the interface. This film passivates the underlying metal but obviously if the passive film is partially or completely removed, localised or generalised corrosion phenomena will occur. In nitric acid, this depassivation may be chemical (fluorides) or mechanical (straining, creep, fretting). In these cases it is useful to determine the physicochemical conditions (concentration, temperature, potential, stress) which will have to be observed to use safely zirconium and its alloys in nitric acid solutions [fr

The Function of Thioredoxin-Binding Protein-2 (TBP-2 in Different Diseases

Directory of Open Access Journals (Sweden)

Jianghua Hu

2018-01-01

Full Text Available Thioredoxin-binding protein-2 (TBP-2 has an important role in the redox system, but it plays a different role in many different diseases (e.g., various cancers, diabetes mellitus (DM, cardiovascular disease, and cataracts by influencing cell proliferation, differentiation, apoptosis, autophagy, and metabolism. Distinct transcription factors (TFs stimulated by different factors combine with binding sites or proteins to upregulate or downregulate TBP-2 expression, in order to respond to the change in the internal environment. Most research disclosed that the main function of TBP-2 is associating with thioredoxin (Trx to inhibit the antioxidant capacity of Trx. Furthermore, the TBP-2 located in tissues, whether normal or abnormal, has the ability to cause the dysfunctioning of cells and even death through different pathways, such as shortening the cell cycle and inducing apoptosis or autophagy. Through these studies, we found that TBP-2 promoted the development of diseases which are involved in inflammatory and oxidative damage. To a certain extent, we believe that there is some hidden connection between the biological functions which TBP-2 participates in and some distinct diseases. This review presents only a summary of the roles that TBP-2 plays in cancer, DM, cataracts, and so on, as well as its universal mechanisms. Further investigations are needed for the cell signaling pathways of the effects caused by TBP-2. A greater understanding of the mechanisms of TBP-2 could produce potential new targets for the treatment of diseases, including cancer and diabetes, cardiovascular disease, and cataracts.

Disposition of PUREX contaminated nitric acid the role of stakeholder involvement

International Nuclear Information System (INIS)

Jasen, W.G.; Duncan, R.A.

1996-01-01

What does the United States space shuttle and the Hanford PUREX facility's contaminated nitric acid have in common. Both are reusable. The PUREX Transition Project has achieved success and, minimized project expenses and waste generation by looking at excess chemicals not as waste but as reusable substitutes for commercially available raw materials. This philosophy has helped PUREX personnel to reuse or recycle more than 2.5 million pounds of excess chemicals, a portion of which is the slightly contaminated nitric acid. After extensive public review, the first shipment of contaminated acid was made in May 1995. Removal of the acid was completed on November 6, 1995 when the fiftieth shipment left the Hanford site. This activity, which avoided dispositioning the contaminated acid as a waste, generated significantly more public input and concern than was expected. One of the lessons learned from this process is to not underestimate public perceptions regarding the reuse of contaminated materials

Pervaporation dehydration of ethanol by hyaluronic acid/sodium alginate two-active-layer composite membranes.

Science.gov (United States)

Gao, Chengyun; Zhang, Minhua; Ding, Jianwu; Pan, Fusheng; Jiang, Zhongyi; Li, Yifan; Zhao, Jing

2014-01-01

The composite membranes with two-active-layer (a capping layer and an inner layer) were prepared by sequential spin-coatings of hyaluronic acid (HA) and sodium alginate (NaAlg) on the polyacrylonitrile (PAN) support layer. The SEM showed a mutilayer structure and a distinct interface between the HA layer and the NaAlg layer. The coating sequence of two-active-layer had an obvious influence on the pervaporation dehydration performance of membranes. When the operation temperature was 80 °C and water concentration in feed was 10 wt.%, the permeate fluxes of HA/Alg/PAN membrane and Alg/HA/PAN membrane were similar, whereas the separation factor were 1130 and 527, respectively. It was found that the capping layer with higher hydrophilicity and water retention capacity, and the inner layer with higher permselectivity could increase the separation performance of the composite membranes. Meanwhile, effects of operation temperature and water concentration in feed on pervaporation performance as well as membrane properties were studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

Energy Technology Data Exchange (ETDEWEB)

Rustenholtz Farawila, A

2005-06-15

Supercritical fluid carbon dioxide (SF-CO{sub 2}) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO{sub 2}. A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO{sub 2} phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO{sub 2}. For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO{sub 2}. These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO{sub 2} for the extraction of uranium from ash. (author)

Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

International Nuclear Information System (INIS)

Rustenholtz Farawila, A.

2005-06-01

Supercritical fluid carbon dioxide (SF-CO 2 ) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO 2 . A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO 2 phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO 2 . For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO 2 . These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO 2 for the extraction of uranium from ash. (author)

NOx generation method from recovered nitric acid by electrolysis

International Nuclear Information System (INIS)

Suzuki, Y.; Shimizu, H.; Inoue, M.; Fujiso, M.; Shibuya, M.; Iwamoto, F.; Outou, Y.; Ochi, E.; Tsuyuki, T.

1998-01-01

An R and D has been conducted on an electrolytic NO x generation process utilizing recovered nitric acid from a PUREX reprocessing plant. The purpose of the study is to drastically reduce the amount of low-level-liquid waste(LLW). The research program phase-1, constituting mainly of electrochemical reaction mechanism study, material balance evaluation and process design study, finished in 1995. The results were presented in the previous papers). The research program phase-2 has started in 1995. The schedule is as follows: FY 1991-1994: Research program phase-1 Basic study using electrolysis equipment with 100-700 cm 2 electrodes FY 1995-1999: Research program phase-2 Process performance test by larger scale electrolysis equipment with 3.6 m 2 electrodes - pilot plant design (FY 1995) - pilot plant construction (FY 1996) - engineering data acquisition (FY 1997-1999). The process consists of many unit operations such as electrolysis, oxidation, nitric acid concentration, NO x compression and storage, NO x recovery, off-gas treatment and acid supplier. This paper outlines the pilot test plant. (author)

Safety confirmation study of TRUEX solvent by accelerating rate calorimeter (ARC)

International Nuclear Information System (INIS)

Sato, Yoshihiko; Hirumachi, Suguru; Takeda, Shinso; Kanazawa, Yoshito; Sasaya, Shinji

1999-02-01

In order to confirm the engineering safety on the TRUEX solvent (mixed solvent of CMPO/TBP/n-dodecane) for separating the transuranics from high-level activity liquid waste in advanced nuclear fuel recycling technological R and D, thermal behavior and pressure behavior in heating PUREX solvent (mixed solvent of 30% TBP-n-dodecane), TRUEX solvent and in the exothermic reaction of TRUEX solvent etc. and nitric acid in sealed adiabatic system which was severer condition than actual plant were measured by using accelerating rate calorimeter (ARC). The Arrhenius parameters (activation energy and frequency factor) which are necessary for the evaluation of reaction rate was examined from the measurement data in ARC. Analytical method and analysis condition of reaction products were examined in order to clarify chemical form of reaction products in exothermic reaction between solvent and nitric acid in ARC, and the qualitative evaluation was carried out. Main results are shown in the following. 1) TBP, CMPO, n-dodecane and 10 M nitric acid hardly exothermed in the simple substance. 2) On the solvent phase after the solvent contacted with 10 M nitric acid and the equilibrium has been attained (single-phase sample), the heat quantity per unit sample weight of the TRUEX solvent tended to be bigger than that of the PUREX solvent when heat quantity was evaluated in ARC. However, on the mixed sample of solvent and 10 M nitric acid enclosed in a sample container simultaneously (two phase system sample), the heat quantity per unit solvent weight was almost equivalent for PUREX solvent and TRUEX solvent. 3) The kinetic analysis was carried out, and on the TBP-10 M nitric acid single-phase sample, the activation energy of the reaction was evaluated to be 118 kJ/mol. Its activation energy was approximately equal to 112 kJ/mol by Nichols. The reaction rate constant was calculated, and it was shown that reaction rate constants of PUREX solvent-10 M nitric acid single-phase sample and

Nitric acid treated multi-walled carbon nanotubes optimized by Taguchi method

Energy Technology Data Exchange (ETDEWEB)

Shamsuddin, Shahidah Arina; Hashim, Uda; Halim, Nur Hamidah Abdul [Institute of Nano Electronic Engineering, Universiti Malaysia Perlis, 01000, Kangar, Perlis (Malaysia); Derman, Mohd Nazree, E-mail: nazree@unimap.edu.my; Tahir, Muhammad Faheem Mohd [Centre of Excellence Geopolymer & Green Technology (CEGeoGTech), School of Material Engineering, Universiti Malaysia Perlis, 01000, Kangar, Perlis (Malaysia); Kashif, Muhammad [Faculty of Engineering, Universiti Malaysia Sarawak, 94300, Kota Samarahan, Sarawak (Malaysia); Adam, Tijjani [Faculty of Engineering Technology, Universiti Malaysia Perlis, 02100, Padang Besar, Perlis (Malaysia)

2016-07-19

Electron transfer rate (ETR) of CNTs can be enhanced by increasing the amounts of COOH groups to their wall and opened tips. With the aim to achieve the highest production amount of COOH, Taguchi robust design has been used for the first time to optimize the surface modification of MWCNTs by nitric acid oxidation. Three main oxidation parameters which are concentration of acid, treatment temperature and treatment time have been selected as the control factors that will be optimized. The amounts of COOH produced are measured by using FTIR spectroscopy through the absorbance intensity. From the analysis, we found that acid concentration and treatment time had the most important influence on the production of COOH. Meanwhile, the treatment temperature will only give intermediate effect. The optimum amount of COOH can be achieved with the treatment by 8.0 M concentration of nitric acid at 120 °C for 2 hour.

Nitric acid treated multi-walled carbon nanotubes optimized by Taguchi method

International Nuclear Information System (INIS)

Shamsuddin, Shahidah Arina; Hashim, Uda; Halim, Nur Hamidah Abdul; Derman, Mohd Nazree; Tahir, Muhammad Faheem Mohd; Kashif, Muhammad; Adam, Tijjani

2016-01-01

Electron transfer rate (ETR) of CNTs can be enhanced by increasing the amounts of COOH groups to their wall and opened tips. With the aim to achieve the highest production amount of COOH, Taguchi robust design has been used for the first time to optimize the surface modification of MWCNTs by nitric acid oxidation. Three main oxidation parameters which are concentration of acid, treatment temperature and treatment time have been selected as the control factors that will be optimized. The amounts of COOH produced are measured by using FTIR spectroscopy through the absorbance intensity. From the analysis, we found that acid concentration and treatment time had the most important influence on the production of COOH. Meanwhile, the treatment temperature will only give intermediate effect. The optimum amount of COOH can be achieved with the treatment by 8.0 M concentration of nitric acid at 120 °C for 2 hour.

Disposition and transportation of surplus radioactive low specific activity nitric acid. Volume 1, Environmental Assessment

International Nuclear Information System (INIS)

1995-05-01

DOE is deactivating the PUREX plant at Hanford; this will involve the disposition of about 692,000 liters (183,000 gallons) of surplus nitric acid contaminated with low levels of U and other radionuclides. The nitric acid, designated as low specific activity, is stored in 4 storage tanks at PUREX. Five principal alternatives were evaluated: transfer for reuse (sale to BNF plc), no action, continued storage in Hanford upgraded or new facility, consolidation of DOE surplus acid, and processing the LSA nitric acid as waste. The transfer to BNF plc is the preferred alternative. From the analysis, it is concluded that the proposed disposition and transportation of the acid does not constitute a major federal action significantly affecting the quality of the human environment within the meaning of NEPA; therefore an environmental impact statement is not required

Functional Layer-by-Layer Thin Films of Inducible Nitric Oxide (NO) Synthase Oxygenase and Polyethylenimine: Modulation of Enzyme Loading and NO-Release Activity.

Science.gov (United States)

Gunasekera, Bhagya; Abou Diwan, Charbel; Altawallbeh, Ghaith; Kalil, Haitham; Maher, Shaimaa; Xu, Song; Bayachou, Mekki

2018-03-07

Nitric oxide (NO) release counteracts platelet aggregation and prevents the thrombosis cascade in the inner walls of blood vessels. NO-release coatings also prevent thrombus formation on the surface of blood-contacting medical devices. Our previous work has shown that inducible nitric oxide synthase (iNOS) films release NO fluxes upon enzymatic conversion of the substrate l-arginine. In this work, we report on the modulation of enzyme loading in layer-by-layer (LbL) thin films of inducible nitric oxide synthase oxygenase (iNOSoxy) on polyethylenimine (PEI). The layer of iNOSoxy is electrostatically adsorbed onto the PEI layer. The pH of the iNOSoxy solution affects the amount of enzyme adsorbed. The overall negative surface charge of iNOSoxy in solution depends on the pH and hence determines the density of adsorbed protein on the positively charged PEI layer. We used buffered iNOSoxy solutions adjusted to pHs 8.6 and 7.0, while saline PEI solution was used at pH 7.0. Atomic force microscopy imaging of the outermost layer shows higher protein adsorption with iNOSoxy at pH 8.6 than with a solution of iNOSoxy at pH 7.0. Graphite electrodes with PEI/iNOSoxy films show higher catalytic currents for nitric oxide reduction mediated by iNOSoxy. The higher enzyme loading translates into higher NO flux when the enzyme-modified surface is exposed to a solution containing the substrate and a source of electrons. Spectrophotometric assays showed higher NO fluxes with iNOSoxy/PEI films built at pH 8.6 than with films built at pH 7.0. Fourier transform infrared analysis of iNOSoxy adsorbed on PEI at pH 8.6 and 7.0 shows structural differences of iNOSoxy in films, which explains the observed changes in enzymatic activity. Our findings show that pH provides a strategy to optimize the NOS loading and enzyme activity in NOS-based LbL thin films, which enables improved NO release with minimum layers of PEI/NOS.

High pressure Raman spectroscopic study of the effects of n-ethylamines and water on the 2-nitropropane/Nitric acid system

Energy Technology Data Exchange (ETDEWEB)

Gobin, Cedric; Petitet, Jean Pierre [Laboratoire d' Ingenierie des Materiaux et des Hautes Pressions, CNRS, Institut Galilee, Universite Paris XIII, 99 av. J-B Clement, 93430 Villetaneuse (France)

2005-12-01

High pressure Raman spectroscopy measurements in a diamond anvil cell (0-10 GPa) on 2-nitropropane/nitric acid/X (X=triethylamine, diethylamine, and water) ternary systems and 2-nitropropane/nitric acid/water/Y (Y=triethylamine and diethylamine) quaternary systems are reported. The modifications of the chemical behavior of the 2-nitropropane/nitric acid model system, induced by the presence of triethylamine, diethylamine, and/or water, were studied at ambient and high pressure. At ambient pressure, the ionization of the nitric acid has been observed with each of the additives. Moreover, in the case of ethylamines, new peaks have been observed and the hypothesis of a 2-nitropropane/ethylamine complex is advanced. At high pressure, the decomposition of the 2-nitropropane/nitric acid system, with an oxygen balance near zero, has been observed only in presence of triethylamine. The role of each additive to the 2-nitropropane/nitric acid system in the modification of the respective reducing and oxidizing character of the components, and in the reactivity of the system, is discussed. Several hypotheses are advanced concerning the sensitizing effect of the additives on the 2-nitropropane/nitric acid system. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

Structure of the oxide film on Ti–6Ta alloy after immersion test in 8 mol/L boiling nitric acid medium

Energy Technology Data Exchange (ETDEWEB)

Guo, Dizi, E-mail: diziguo@126.com; Yang, Yingli; Wu, Jinping; Zhao, Bin; Zhao, Hengzhang; Su, Hangbiao; Lu, Yafeng

2013-08-15

Highlights: •Structure of the oxide film on Ti–6Ta alloy is studied by depth profile XPS. •TiO{sub 2} and Ta{sub 2}O{sub 5} are found in the top layer of the oxide film. •High valence oxide evolutes form Ti{sub 2}O{sub 3} and TaO. •Shielding effect of Ta{sub 2}O{sub 5} leads to the enhanced corrosion resistance of Ti–Ta alloy. -- Abstract: By using X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD) and scanning electron microscopy (SEM), we investigate the corrosion behavior and the structure of the oxide film of Ti–6Ta alloy that is subjected to the immersion corrosion test in 8 mol/L boiling nitric acid for 432 h. Based on the phase constitution indentified by depth profile XPS, the oxide film could be divided into three sub-layers along its thickness direction: the chemical stable TiO{sub 2} and Ta{sub 2}O{sub 5} are present in layer I; the sub-oxide Ti{sub 2}O{sub 3} and TaO are present in the layer II and layer III, and the high valence oxide evolutes from their sub-oxide gradually. Owing to the shielding effect of Ta{sub 2}O{sub 5}, the corrosion rate of the Ti–6Ta alloy decreases from 0.051 mm/y to 0.014 mm/y with increasing immersion time, showing an excellent corrosion resistance in 8 mol/L boiling nitric acid.

Alternative to Nitric Acid for Passivation of Stainless Steel Alloys

Science.gov (United States)

Lewis, Pattie L.; Kolody, Mark; Curran, Jerry

2013-01-01

Corrosion is an extensive problem that affects the Department of Defense (DoD) and National Aeronautics and Space Administration (NASA). The deleterious effects of corrosion result in steep costs, asset downtime affecting mission readiness, and safety risks to personnel. Consequently, it is vital to reduce corrosion costs and risks in a sustainable manner. The DoD and NASA have numerous structures and equipment that are fabricated from stainless steel. The standard practice for protection of stainless steel is a process called passivation. Typical passivation procedures call for the use of nitric acid; however, there are a number of environmental, worker safety, and operational issues associated with its use. Citric acid offers a variety of benefits including increased safety for personnel, reduced environmental impact, and reduced operational cost. DoD and NASA agreed to collaborate to validate citric acid as an acceptable passivating agent for stainless steel. This paper details our investigation of prior work developing the citric acid passivation process, development of the test plan, optimization of the process for specific stainless steel alloys, ongoing and planned testing to elucidate the process' resistance to corrosion in comparison to nitric acid, and preliminary results.

Identification of a domain within human TAF(I)48, a subunit of Selectivity Factor 1, that interacts with helix 2 of TBP.

Science.gov (United States)

Xu, Shuping; Hori, Roderick T

2004-09-01

RNA polymerase I transcription in human cells requires Selectivity Factor 1, a multisubunit complex composed of the TATA-box-binding protein (TBP) and three TBP-associated factors (TAFs) called TAF(I)48, TAF(I)63 and TAF(I)110. Each of the Selectivity Factor 1 subunits binds directly to the other three components, but these interactions have not been characterized. This study is the initial identification and analysis of a TBP-binding domain within a Selectivity Factor 1 TAF. The interaction between human TBP and human TAF(I)48 was initially examined using the yeast two-hybrid assay, and a TBP-binding domain was identified in the carboxyl-terminus of human (h)TAF(I)48. Consistent with this result, the hTAF(I)48 carboxyl-terminus was able to bind directly to TBP in protein-protein interaction assays. When mutations were introduced into the hTAF(I)48 carboxyl-terminus, we identified changes in uncharged and positive residues that affect its interaction with TBP. By examining TBP mutants, residues within and adjacent to helix 2 of TBP, previously demonstrated to interact with subunits of other TBP-containing complexes [Transcription Factor IID (TFIID) and TFIIIB] were also found to diminish its affinity for the carboxyl-terminus of hTAF(I)48. The regions of hTAF(I)48 and TBP that interact are compared to those identified within other complexes containing TBP.

Determination of free nitric acid in uranyl nitrate solution

International Nuclear Information System (INIS)

Mayankutty, P.C.; Ravi, S.; Nadkarni, M.N.

1981-01-01

Potentiometric titration of uranyl nitrate solution with sodium hydroxide exhibits two peaks. The first peak characterises the following reaction, UO 2 (C 2 O 4 )+NaOH Na[UO 2 (C 2 O 4 )(OH)]. This reaction, indicating the partial hydrolysis of uranyl oxalate complex, appears to be complete at pH9. If the titration is carried out to this end-point pH, the total alkali consumed can be equated to the sum of uranium content and the free acidity present in the sample volume. Based on this, a method was standardised to determine the free acidity in uranyl nitrate solution. The sample, taken in a solution of potassium oxalate previously adjusted to pH9, is titrated to this pH with standard sodium hydroxide. The free acidity in the sample can be computed by subtracting the alkali reacted with uranium from the total alkali consumed. Analyses of several synthetic samples containing uranium and nitric acid in a wide range of combinations indicate that the free acidity can be accurately determined by this method, if uranium concentration in the sample is known. The results are compared to those obtained by two other widely used methods, viz., (i) titration of pH7 in the presence of neutral potassium oxalate to suppress hydrolysis and (ii) separation of hydrolyzable ions on a cationic resin and alkali titration of the free acid released. The advantages of and the precision obtained with the present method over the above two methods are discussed. (author)

Study of plutonium IV elution from macromolecular anion exchange resin by 0.5 M nitric acid

International Nuclear Information System (INIS)

Nadkarni, M.N.; Mayankutty, P.C.; Pillai, N.S.; Shinde, S.S.

1976-01-01

Preliminary studies indicated that macroreticular resins possess more or less the same capacities and absorption characteristics for thorium, uranium and plutonium from nitric acid solutions as the conventional resins. Detailed studies were, then, conducted. It was found that Pu(IV) can be loaded on the macroreticular anion exchange resin, Amberlyst A-26 from 7.2 M nitric acid in much the same way as Dowex 1x4. It was also observed that the elution of Pu(IV) from Amberlyst A-26 by 0.5 M nitric acid is much more rapid and quantitative than from Dowex 1x4. (author)

Recovery of plutonium from oxalate bearing solutions using a mixture of CMPO and TBP

International Nuclear Information System (INIS)

Mathur, J.N.; Murali, M.S.; Rizvi, G.H.; Iyer, R.H.; Badheka, L.P.; Banerji, A.; Michael, K.M.; Kapoor, S.C.; Dhumwad, R.K.

1993-01-01

A simple and efficient procedure has been developed to quantitatively recover Pu from oxalate bearing solutions using a mixture of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane. Pu(IV) in the range of 6.9 to 34.6 mg/1 was quantitatively extracted into 0.2 M CMPO+ 1.2 M TBP in dodecane from an aqueous solution containing 3.0 M HNO 3 and 0.1 M H 2 C 2 O 4 . At such low concentrations of Pu, the distribution ratio (D) did not change but the increase in oxalic acid concentration drastically reduced these values. The variation in HNO 3 concentration at a fixed concentration of 0.2 M CMPO + 1.2 M TBP has shown a dramatic increase in the D values, being 0.3 at 1.0 M and > 10 4 at 7.5 M. The extraction was almost quantitative even at the aqueous to organic ratio of 10:1. Plutonium could be quantitatively recovered (i) by stripping with 0.5 M acetic acid and (ii) by coprecipitating it directly from the organic phase with 0.3 M oxalic acid + 0.3 M calcium nitrate + sodium nitrite. ∼ 92% of the Pu was found in the precipitate and ∼7% in the supernatant. Using this procedure Pu, in a concentrated form (∼50 times), could be recovered from the oxalate bearing solutions without recourse to the destruction of oxalate ion. The slope of 2 from the nitrate ion as well as CMPO variation experiments suggest the species in the organic phase to be PuC 2 O 4 (NO 3 ) 2 .2CMPO. The absorption spectral study of Pu(IV) confirmed the above species in the organic phase. (author). 19 refs., 5 figs., 9 tabs

Simulated dry deposition of nitric acid near forest edges

NARCIS (Netherlands)

DeJong, JJM; Klaassen, W; Jong, J.J.M. de

1997-01-01

Dry deposition is simulated to understand and generalize observations of enhanced deposition of air pollution near forest edges. Nitric acid is taken as an example as its deposition velocity is often assumed to be determined by turbulent transport only. The simulations are based on the

Determination of dibutylphosphate and monobutylphosphate in TBP by ion chromatography

International Nuclear Information System (INIS)

Siva Kumar, B.; Vijayalakshmi, S.; Sankaran, K.; Ganesan, V.

2012-01-01

Tri-n-butyl phosphate (TBP) is used as solvent in the PUREX (Plutonium Uranium Refining by Extraction) process of nuclear fuel reprocessing. TBP undergoes chemical and radiological degradation to give DBP and MBP which in turn extracts the heavy metal such as U, Pu thereby affecting the performance of the extraction process. Analytical method using ion chromatography (IC) was developed for the determination of dibutyl phosphate (DBP) and monobutyl phosphate (MBP) in TBP. In this method, DBP and MBP were extracted from tri-n-butyl phosphate using carbonate-bicarbonate mixture of eluent composition and the aqueous phase was analyzed using suppressed ion chromatography employing carbonate as eluent. Standardization of extraction was carried out by standard addition studies. The detection limits for both DBP and MBP are found to be in sub ppm level. This method was applied to the analysis of TBP supplied by different suppliers

Observation of gaseous nitric acid production at a high-energy proton accelerator facility

CERN Document Server

Kanda, Y; Nakajima, H

2005-01-01

High-energy protons and neutrons produce a variety of radionuclides as well as noxious and oxidative gases, such as ozone and nitric acid, in the air mainly through the nuclear spallation of atmospheric elements. Samples were collected from the surfaces of magnets, walls, and floors in the neutrino beamline tunnel and the target station of the KEK 12-GeV proton synchrotron facility by wiping surfaces with filter paper. Considerably good correlations were found between the amounts of nitrate and tritium and between those of nitrate and /sup 7/Be. This finding gives evidence that at high-energy proton facilities, nitric acid is produced in the radiolysis of air in beam- loss regions. Also, the nitric acid on the surfaces was found to be desorbed and tended to be more uniform throughout the tunnel due to air circulation. The magnitude of diminishing from the surfaces was in the order of tritium>nitrate>/sup 7/Be1).

Material compatibility evaluation for DWPF nitric-glycolic acid-literature review

Energy Technology Data Exchange (ETDEWEB)

Mickalonis, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Skidmore, E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2013-06-01

Glycolic acid is being evaluated as an alternative for formic and nitric acid in the DWPF flowsheet. Demonstration testing and modeling for this new flowsheet has shown that glycolic acid and glycolate has a potential to remain in certain streams generated during the production of the nuclear waste glass. A literature review was conducted to assess the impact of glycolic acid on the corrosion of the materials of construction for the DWPF facility as well as facilities downstream which may have residual glycolic acid and glycolates present. The literature data was limited to solutions containing principally glycolic acid.

The pitting resistance of AISI 316 stainless steel passivated in diluted nitric acid

International Nuclear Information System (INIS)

Barbosa, M.A.

1983-01-01

The pitting resistance of AISI 316 stainless steel after passivation in diluted nitric acid was studied in comparison with that of non-passivated specimens. The passivation treatment increased the pitting potential but decreased the resistance to crevice corrosion under open circuit conditions in aerated sea water. Immersion in the nitric acid solution was found to remove the sulphide inclusions from the metal surface, thus eliminating the most susceptible sites for attack. In the absence of sulphide particles pitting nucleated at aluminium-rich oxides. (author)

Detection of nitric acid and nitric oxides in the terrestrial atmosphere in the middle-infrared spectral region

Directory of Open Access Journals (Sweden)

M. I. Blecka

1996-11-01

Full Text Available A proposal for combined space and ground-based observations of the vertical distributions and the column densities of nitric acid and nitric oxide concentrations in the earth's atmosphere is discussed. We focus on the aspects that are particular to the idea of correlative measurements: geometrical considerations, simulations of the solar absorption spectra in the middle-infrared region corresponding to the different observational geometries, and the associated retrieval methods. These studies are done specifically for the Belgian-French experiment MIRAS (MIR Infrared Atmospheric Spectrometer onboard the Russian Space Station MIR and correlative ground-based FTIR measurements in the Tatra mountains.

Effect of Nitric and Oxalic Acid Addition on Hard Anodizing of AlCu4Mg1 in Sulphuric Acid

Directory of Open Access Journals (Sweden)

Maximilian Sieber

2018-02-01

Full Text Available The anodic oxidation process is an established means for the improvement of the wear and corrosion resistance of high-strength aluminum alloys. For high-strength aluminum-copper alloys of the 2000 series, both the current efficiency of the anodic oxidation process and the hardness of the oxide coatings are significantly reduced in comparison to unalloyed substrates. With regard to this challenge, recent investigations have indicated a beneficial effect of nitric acid addition to the commonly used sulphuric acid electrolytes both in terms of coating properties and process efficiency. The present work investigates the anodic oxidation of the AlCu4Mg1 alloy in a sulphuric acid electrolyte with additions of nitric acid as well as oxalic acid as a reference in a full-factorial design of experiments (DOE. The effect of the electrolyte composition on process efficiency, coating thickness and hardness is established by using response functions. A mechanism for the participation of the nitric acid additive during the oxide formation is proposed. The statistical significance of the results is assessed by an analysis of variance (ANOVA. Eventually, scratch testing is applied in order to evaluate the failure mechanisms and the abrasion resistance of the obtained conversion coatings.

[Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

Science.gov (United States)

Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

1998-04-01

In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

Isolation of nitrosylruthenium nitrato complexes by ion exchange and extraction chromatography

International Nuclear Information System (INIS)

Huang, H.; Liu, L.

TBP Levextrel and cation exchange resins were used to separate RuNO nitrato complexes of different nitric acid concentrations. 7402 quaternary ammonium salt Levextrel was used instead of an anionic exchange resin to separate anionic and neutral complex ions. The results indicated that D 3 and D 4 , which can easily be extracted by TBP, were anionic and neutral complex ions

Corrosion resistance of Ultra-Low-Carbon 19% Cr-11% Ni stainless steel for nuclear fuel reprocessing plants in nitric acid

International Nuclear Information System (INIS)

Ariga, Tamako; Takagi, Yoshio; Inazumi, Toru; Masamura, Katsumi; Sukekawa, M.

1995-01-01

An Ultra-Low-Carbon 19% Cr-11% Ni Stainless Steels used in nuclear fuel reprocessing plants where highly corrosion resistance in nitric acid is required has been developed. This steel has optimized the chemistry composition to decrease inclusions and deformation-induced martensitic transformation. The formation of deformation-induced martensite has the potential danger of accelerating corrosion in nitric acid. In this paper, effects of cold reduction and martensitic transformation on corrosion resistance of Ultra-Low-Carbon Stainless Steels in nitric acid are discussed. The developed steel showed excellent corrosion resistance during long-term exposure to nitric acid. (author)

Impact of scaling on the nitric-glycolic acid flowsheet

Energy Technology Data Exchange (ETDEWEB)

Lambert, D. [Savannah River Site (SRS), Aiken, SC (United States)

2016-02-01

Savannah River Remediation (SRR) is considering using glycolic acid as a replacement for formic acid in Sludge Receipt and Adjustment Tank (SRAT) processing in the Defense Waste Processing Facility (DWPF). Catalytic decomposition of formic acid is responsible for the generation of hydrogen, a potentially flammable gas, during processing. To prevent the formation of a flammable mixture in the offgas, an air purge is used to dilute the hydrogen concentration below the 60% of the Composite Lower Flammability Limit (CLFL). The offgas is continuously monitored for hydrogen using Gas Chromatographs (GCs). Since formic acid is much more volatile and toxic than glycolic acid, a formic acid spill would lead to the release of much larger quantities to the environment. Switching from formic acid to glycolic acid is expected to eliminate the hydrogen flammability hazard leading to lower air purges, thus downgrading of Safety Significant GCs to Process Support GCs, and minimizing the consequence of a glycolic acid tank leak in DWPF. Overall this leads to a reduction in process operation costs and an increase in safety margin. Experiments were completed at three different scales to demonstrate that the nitric-glycolic acid flowsheet scales from the 4-L lab scale to the 22-L bench scale and 220-L engineering scale. Ten process demonstrations of the sludge-only flowsheet for SRAT and Slurry Mix Evaporator (SME) cycles were performed using Sludge Batch 8 (SB8)-Tank 40 simulant. No Actinide Removal Process (ARP) product or strip effluent was added during the runs. Six experiments were completed at the 4-L scale, two experiments were completed at the 22-L scale, and two experiments were completed at the 220-L scale. Experiments completed at the 4-L scale (100 and 110% acid stoichiometry) were repeated at the 22-L and 220-L scale for scale comparisons.

Third phase formation revisited: the U(VI), HNO3 - TBP, n-dodecane system

International Nuclear Information System (INIS)

Chiarizia, R.; Jensen, M.P.; Borkowski, M.; Ferraro, J.R.; Thiyagarajan, P.; Littrell, K.C.

2003-01-01

In this work, the system U(VI), HNO 3 -tri-n-butylphosphate (TBP), n-dodecane has been revisited with the objective of gaining information on the coordination chemistry and structural evolution of the species formed in the organic phase before and after third phase formation. Chemical analyses, spectroscopic and EXAFS data indicate that U(VI) is extracted as the UO 2 (NO 3 ) 2 ·2TBP adduct, while the third phase species have the average composition UO 2 (NO 3 ) 2 ·2TBP·HNO 3 . Small-angle neutron scattering (SANS) measurements on TBP solutions loaded with only HNO 3 or with increasing amounts of U(VI) have revealed the presence, before phase splitting, of ellipsoidal aggregates with the major and minor axes up to about 64 and 15 A, respectively. The formation of these aggregates, very likely of the reverse micelle-type, is observed in all cases, that is, when only HNO 3 , only UO 2 (NO 3 ) 2 , or both HNO 3 and UO 2 (NO 3 ) 2 are extracted by the TBP solution. Upon third phase formation, the SANS data reveal the presence of smaller aggregates in the light organic phase, while the heavy organic phase contains pockets of diluent, each with an average of about two molecules of n-dodecane.

A bibliographical review on the radiolysis of uranyl nitrate solutions in nitric acid medium

International Nuclear Information System (INIS)

Siri, Sandra; Mondino, Angel V.

2004-01-01

A bibliographical study on the effects of ionizing radiation on uranyl nitrate solutions in nitric acid medium was performed, and the state of knowledge on this subject is presented. The main experimental and theoretical results on water, nitric acid and uranium solutions radiolysis are reviewed and critically evaluated. This paper provides a collection of references as an aid to the development of practical applications, and to stimulate new research on fundamental processes in these systems. (author) [es

Nitric Acid Revamp and Upgrading of the Alarm & Protection Safety System at Petrokemija, Croatia

Directory of Open Access Journals (Sweden)

Hoško, I.

2012-04-01

Full Text Available Every industrial production, particularly chemical processing, demands special attention in conducting the technological process with regard to the security requirements. For this reason, production processes should be continuously monitored by means of control and alarm safety instrumented systems. In the production of nitric acid at Petrokemija d. d., the original alarm safety system was designed as a combination of an electrical relay safety system and transistorized alarm module system. In order to increase safety requirements and modernize the technological process of nitric acid production, revamping and upgrading of the existing alarm safety system was initiated with a new microprocessor system. The newly derived alarm safety system, Simatic PCS 7, links the function of "classically" distributed control (DCS and logical systems in a common hardware and software platform with integrated engineering tools and operator interface to meet the minimum safety standards with safety integrity level 2 (SIL2 up to level 3 (SIL3, according to IEC 61508 and IEC 61511. This professional paper demonstrates the methodology of upgrading the logic of the alarm safety system in the production of nitric acid in the form of a logical diagram, which was the basis for a further step in its design and construction. Based on the mentioned logical diagram and defined security requirements, the project was implemented in three phases: analysis and testing, installation of the safety equipment and system, and commissioning. Developed also was a verification system of all safety conditions, which could be applied to other facilities for production of nitric acid. With the revamped and upgraded interlock alarm safety system, a new and improved safety boundary in the production of nitric acid was set, which created the foundation for further improvement of the production process in terms of improved analysis.

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides

International Nuclear Information System (INIS)

Condamines, N.

1990-03-01

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO 3 , UO 2 2+ , Pu 4+ , Th 4+ are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO 3 )L 2 , (HNO 3 )L, (HNO 3 ) 2 L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing [fr

Multivariate Analysis for Quantification of Plutonium(IV) in Nitric Acid Based on Absorption Spectra

Energy Technology Data Exchange (ETDEWEB)

Lines, Amanda M. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Adami, Susan R. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Sinkov, Sergey I. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Lumetta, Gregg J. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Bryan, Samuel A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

2017-08-09

Development of more effective, reliable, and fast methods for monitoring process streams is a growing opportunity for analytical applications. Many fields can benefit from on-line monitoring, including the nuclear fuel cycle where improved methods for monitoring radioactive materials will facilitate maintenance of proper safeguards and ensure safe and efficient processing of materials. On-line process monitoring with a focus on optical spectroscopy can provide a fast, non-destructive method for monitoring chemical species. However, identification and quantification of species can be hindered by the complexity of the solutions if bands overlap or show condition-dependent spectral features. Plutonium (IV) is one example of a species which displays significant spectral variation with changing nitric acid concentration. Single variate analysis (i.e. Beer’s Law) is difficult to apply to the quantification of Pu(IV) unless the nitric acid concentration is known and separate calibration curves have been made for all possible acid strengths. Multivariate, or chemometric, analysis is an approach that allows for the accurate quantification of Pu(IV) without a priori knowledge of nitric acid concentration.

White Paper on Potential Hazards Associated with Contaminated Cheesecloth Exposed to Nitric Acid Solutions

Energy Technology Data Exchange (ETDEWEB)

Hypes, Philip A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-09-20

This white paper addresses the potential hazards associated with waste cheesecloth that has been exposed to nitric acid solutions. This issue was highlighted by the cleanup of a 100 ml leak of aqueous nitric acid solution containing Heat Source (HS) plutonium on 21 June 2016. Nitration of cellulosic material is a well-understood process due to industrial/military applications of the resulting material. Within the Department of Energy complex, nitric acids have been used extensively, as have cellulosic wipes. If cellulosic materials are nitrated, the cellulosic material can become ignitable and in extreme cases, reactive. We have chemistry knowledge and operating experience to support the conclusion that all current wastes are safe and compliant. There are technical questions worthy of further experimental evaluation. An extent of condition evaluation has been conducted back to 2004. During this time period there have been interruptions in the authorization to use cellulosic wipes in PF-4. Limited use has been authorized since 2007 (for purposes other than spill cleanup), so our extent of condition includes the entire current span of use. Our evaluation shows that there is no indication that process spills involving high molarity nitric acid were cleaned up with cheesecloth since 2007. The materials generated in the 21 June leak will be managed in a safe manner compliant with all applicable requirements.

Brightening of the global cloud field by nitric acid and the associated radiative forcing

Directory of Open Access Journals (Sweden)

R. Makkonen

2012-08-01

Full Text Available Clouds cool Earth's climate by reflecting 20% of the incoming solar energy, while also trapping part of the outgoing radiation. The effect of human activities on clouds is poorly understood, but the present-day anthropogenic cooling via changes of cloud albedo and lifetime could be of the same order as warming from anthropogenic addition in CO₂. Soluble trace gases can increase water condensation to particles, possibly leading to activation of smaller aerosols and more numerous cloud droplets. We have studied the effect of nitric acid on the aerosol indirect effect with the global aerosol-climate model ECHAM5.5-HAM2. Including the nitric acid effect in the model increases cloud droplet number concentrations globally by 7%. The nitric acid contribution to the present-day cloud albedo effect was found to be −0.32 W m⁻² and to the total indirect effect −0.46 W m⁻². The contribution to the cloud albedo effect is shown to increase to −0.37 W m⁻² by the year 2100, if considering only the reductions in available cloud condensation nuclei. Overall, the effect of nitric acid can play a large part in aerosol cooling during the following decades with decreasing SO₂ emissions and increasing NO_x and greenhouse gases.

Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

International Nuclear Information System (INIS)

Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K.; Rao, C.V.S. Brahmmananda; Jayalakshmi, S.

2015-01-01

The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

Liquid-Phase Heat-Release Rates of the Systems Hydrazine-Nitric Acid and Unsymmetrical Dimethylhydrazine-Nitric Acid

Science.gov (United States)

Somogyi, Dezso; Feiler, Charles E.

1960-01-01

The initial rates of heat release produced by the reactions of hydrazine and unsymmetrical dimethylhydrazine with nitric acid were determined in a bomb calorimeter under conditions of forced mixing. Fuel-oxidant weight ratio and injection velocity were varied. The rate of heat release apparently depended on the interfacial area between the propellants. Above a narrow range of injection velocities representing a critical amount of interfacial area, the rates reached a maximum and were almost constant with injection velocity. The maximum rate for hydrazine was about 70 percent greater than that for unsymmetrical dimethylhydrazine. The total heat released did not vary with mixture ratio over the range studied.

Safe venting of ''red oil'' runaway reactions

International Nuclear Information System (INIS)

Paddleford, D.F.; Fauske, H.K.

1994-01-01

Calorimetry testing of Tri-n-butyl phosphate (TBP) saturated with strong nitric acid was performed to determine the relationship between vent size and pressure buildup in the event of a runaway reaction. These experiments show that runaway can occur in an open system, but that even when runaway is induced in the TBP/HN0 3 system, dangerous pressure buildup will be prevented with practical vent size

Evaporation of iodine from nitric acid with the aid of peroxide

International Nuclear Information System (INIS)

Cathers, G.I.; Shipman, C.J.

1975-01-01

Traces of radioactive iodine with a concentration of 5 x 10 -4 M or less that remained in nitric acid solution after reprocessing of nuclear fuels can, without great apparatus effort, be distilled off as hydrogen iodide by continuous addition of hydrogen peroxide to the solution boiling at about 105 0 C to 1,15 0 C, and then be separated as elementary iodine. Starting from a 4 to 6 molecular nitric acid solution, the H 2 O 2 -concentration amounts to 0.012 percentage by weight and is kept at this level during the entire distillation process. The iodine concentration is also profitably kept at the level of the starting solution by adding non-radioactive iodine, since an isotopec exchange of radioactive iodine bound in organic impurities is advanced in that way. (UWI) [de

Comparative evaluation of DHDECMP [dihexyl-N,N-diethylcarbamoyl-methylphosphonate] and CMPO [octylphenyl-N,N,-diisobutylcarbamoylmethylphosphine oxide] as extractants for recovering actinides from nitric acid waste streams

International Nuclear Information System (INIS)

Marsh, S.F.; Yarbro, S.L.

1988-02-01

Certain neutral, bifunctional organophosphorous compounds are of special value to the nuclear industry. Dihexyl-N,N-diethylcarbomoylmethylphosphonate (DHDECMP) and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) are highly selective extractants for removing actinide and lanthanide elements from nitric acid. We obtained these two extractants from newly available commercial sources and evaluated them for recovering Am(III), Pu(IV), and U(VI) from nitric acid waste streams of plutonium processing operations. Variables included the extractant (DHSECMP or CMPO), extractant/tributylphosphate ratio, diluent, nitrate concentration, nitrate salt/nitric acid ratio, fluoride concentration, and contact time. Based on these experimental data, we selected DHDECMP as the perferred extractant for this application. 18 refs., 30 figs

Destruction of nitric acid in purex process streams by formaldehyde treatment

International Nuclear Information System (INIS)

Kumar, S.V.; Nadkarni, M.N.; Mayankutty, P.C.; Pillai, N.S.; Shinde, S.S.

1974-01-01

Efficiency of destruction of nitric acid in purex process streams with formaldehyde has been studied as a function of initial acidity, uranium concentration, rate of addition of formaldehyde and temperature in the range 6 - 0.5M acid. Guidelines are suggested for the accurate calculations of the volume of formaldehyde needed to effect the required change of acidity at 100degC. Sodium nitrite has been established as a 'key' to initiate the reaction and water as an effective scrubber for collecting the acid fumes emanating from the reaction vessel. (author)

Americium removal from nitric acid waste streams

International Nuclear Information System (INIS)

Muscatello, A.C.; Navratil, J.D.

1986-01-01

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, 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, O0D (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 1.0M acidity and iron(III) is complexed with 0.20M oxalic acid. 3 figs

The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

Directory of Open Access Journals (Sweden)

M. Ammann

2008-09-01

Full Text Available Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO₃, an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO₃ on deliquesced NaCl aerosol was measured in a flow reactor using HNO₃ labelled with the short-lived radioactive isotope ¹³N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO₃(g. The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond had a detectable effect on the rate of HNO₃ uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO₃ uptake. Fatty acids (C18 and C15, which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO₃ uptake, while monolayers of shorter-chain fatty acids (C9, C12 and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO₃ uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO₃ uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

Material Compatibility Evaluation for DWPF Nitric-Glycolic Acid - Literature Review

Energy Technology Data Exchange (ETDEWEB)

Mickalonis, J. I. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Skidmore, T. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2015-09-30

Glycolic acid is being evaluated as an alternative for formic and nitric acid in the DWPF flowsheet. Demonstration testing and modeling for this new flowsheet has shown that glycolic acid and glycolate has a potential to remain in certain streams generated during the production of the nuclear waste glass. A literature review was conducted to assess the impact of glycolic acid on the corrosion of the materials of construction for the DWPF facility as well as facilities downstream which may have residual glycolic acid and glycolates present. The literature data was limited to solutions containing principally glycolic acid. The reported corrosion rates and degradation characteristics have shown the following for the materials of construction.

Solvent extraction of titanium (IV) from sulphuric acid media by cyanex 921 and tri-butylphosphate

International Nuclear Information System (INIS)

Nayl, A.A.; Aly, H.F.

2009-01-01

titanium and its compounds found different useful applications in the nuclear and radioactive waste treatment fields. extraction behavior of titanium (IV) from sulfuric acid by commercial tri-octylphosphine oxide (CYANEX 921) and tributylphosphate (TBP)has been investigated. effects of contact time, sulfuric acid concentration in the aqueous phase, the extractants concentration in the organic phase, and the temperature on the extraction of titanium by the two systems were studied. it is found that extraction equilibrium of titanium is reached after 10-15 min and 4 min for CYANEX 921 and TBP, respectively . the extraction of Ti(IV) by 0.15 M CYANEX 921 in kerosene increases with the increase in sulfuric acid concentration to reach a maximum extraction of 91% at 7.0 m acid concentration. for the TBP system, the maximum extraction of titanium was 79% using 1.0 M TBP in kerosene from 4.0 m H 2 SO 4 solution . the effect of temperature was also evaluated. Na 2 CO 3 was used as a good stripping agent compared with other reagents. the interaction of Ti(IV) in sulfate medium and different sulfate species in sulfuric acid are reviewed. within the literature survey together with analysis of the extraction results , it can be concluded that titanium extracted by CYANEX 921 as Ti O (HSO 4 ) 2 .2 CYANEX 921 whereby in case of TBP, the extracted species is TiOSO 4 .2 TBP

Recovery of plutonium from nitric acid containing oxalate and fluoride by a macroporous bifunctional phosphinic acid resin (MPBPA)

International Nuclear Information System (INIS)

Venugopal Chetty, K.; Godbole, A.G.; Swarup, R.; Vaidya, V.N.; Venugopal, V.; Vasudeva Rao, P.R.

2006-01-01

The sorption of Pu from nitric acid solutions containing oxalate/fluoride was studied using an indigenously available macroporous bifunctional phosphinic acid (MPBPA) resin. Batch experiments were carried out to obtain the distribution data of Pu(IV) with a view to optimize conditions for its recovery from nitric acid waste solutions containing oxalate or fluoride ions. The measurements showed high distribution ratio (D) values even in the presence of strong complexing ions, like oxalate and fluoride, indicating the possibility of recovery of Pu from these types of waste solution. Column studies were carried out using this resin to recover Pu from the oxalate supernatant waste solution, which showed that up to 99% of Pu could be adsorbed on the resin. Elution of Pu loaded on the resin was studied using different eluting agents. (author)

Kinetics, mechanism, and stoicheiometry of the oxidation of hydroxylamine by nitric acid

International Nuclear Information System (INIS)

Pembridge, J.R.; Stedman, G.

1979-01-01

Hydroxylamine is oxidised by nitric acid to form dinitrogen monoxide and nitrous acid, the proportions varying with reaction conditions. (The chemistry of hydroxylamine in nitric acid is of potential technological interest, since it has been proposed as a reagent for the reduction of Pu(IV) to Pu(III).) The yield [HNO 2 ]infinity/ [NH 3 OH + ] 0 is a maximum at ca. 4 to 5 mol dm -3 HNO 3 , and is also a function of the hydroxylamine concentration. In 5 mol dm -3 HNO 3 the limiting yield is ca. 0.85 at very low initial hydroxylamine concentrations, but decreases towards zero at higher values of [NH 3 OH + ] 0 . Reaction is only observed at sufficiently high nitric acid concentrations; at 25 0 C the cut-off point is ca. 2.5 mol dm -3 HNO 3 . The reaction is characterised by an induction period, followed by a rapid autocatalytic process. Addition of nitrite eliminates the induction period, while addition of nitrite scavengers completely prevents any reaction. Nitrous acid is an essential catalyst for the reaction, and the initial rate of reaction obeys the equation d[HNO 2 ]/dt = V 0 = k[HNO 2 ][NH 3 OH + ]. Isotopic experiments, using 15 N-enriched hydroxylamine show that virtually all of the N 2 O arises from reaction between HNO 2 and hydroxylamine. The mechanism suggested involves oxidation of un-protonated hydroxylamine by N 2 O 4 to form the nitroxyl diradical HNO; this is then further oxidised to HNO 2 , which reacts with hydroxylamine to form N 2 O. (author)

A study on the safety of TBP(150A) with forming analysis and strength test

International Nuclear Information System (INIS)

Lee, Sung Ho; Kim, Hei Song

2008-01-01

For this study, the forming analyses and body strength tests of TBP were performed on the main pipe size 150A(KS D3507, KS D 3576 10S). The branched pipe sizes utilized were 25A, 32A, 40A, 50A, 65A, 80A, 100A and 125A. A general FEM program, ABAQUS, was used as the forming analyses method of TBP. Using the results, the strength of TBP was then tested in order to determine the safety of TBP when the working pressure was applied. The results indicate that TBP may be safely used in water-based fire protection pipe systems in terms of the strength

Kinetic study of dilute nitric acid treatment of corn stover at relatively high temperature

Energy Technology Data Exchange (ETDEWEB)

Zhang, R.; Lu, X.; Liu, Y.; Wang, X.; Zhang, S. [Tianjin University, School of Environmental Science and Technology, Tianjin (China)

2011-03-15

Corn stover was hydrolyzed using dilute nitric acid at 150 C. Several concentrations of HNO{sub 3} (0.2, 0.4 and 0.6 wt-%) and reaction times (0-60 min) were evaluated. The kinetic parameters of mathematical models for predicting the concentrations of xylose, glucose, arabinose, acetic acid, and furfural in the hydrolysates were determined. The hydrolysates obtained from corn stover can be used to produce methane by an anaerobic fermentation process. Thus, the hydrolysis process of corn stover using dilute nitric acid can be conceived as the first stage of an integrated strategy for corn stover utilization. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Nitric Acid-Treated Carbon Fibers with Enhanced Hydrophilicity for Candida tropicalis Immobilization in Xylitol Fermentation

Directory of Open Access Journals (Sweden)

Le Wang

2016-03-01

Full Text Available Nitric acid (HNO3-treated carbon fiber (CF rich in hydrophilic groups was applied as a cell-immobilized carrier for xylitol fermentation. Using scanning electron microscopy, we characterized the morphology of the HNO3-treated CF. Additionally, we evaluated the immobilized efficiency (IE of Candida tropicalis and xylitol fermentation yield by investigating the surface properties of nitric acid treated CF, specifically, the acidic group content, zero charge point, degree of moisture and contact angle. We found that adhesion is the major mechanism for cell immobilization and that it is greatly affected by the hydrophilic–hydrophilic surface properties. In our experiments, we found 3 hto be the optimal time for treating CF with nitric acid, resulting in an improved IE of Candida tropicalis of 0.98 g∙g−1 and the highest xylitol yield and volumetric productivity (70.13% and 1.22 g∙L−1∙h−1, respectively. The HNO3-treated CF represents a promising method for preparing biocompatible biocarriers for multi-batch fermentation.

Fully-differential spectrophotometry determination of trace thorium in uranium-containing waste water separated by CL-TBP levextrel resin

International Nuclear Information System (INIS)

You Jiannan

2000-01-01

A method for separation by CL-TBP levextrel resin and determination of trace thorium in uranium-containing waste water by fully-differential spectrophotometry is developed. In 4 mol/L HNO 3 medium, in presence of tartaric acid, CL-TBP levextrel resin is used for adsorption of thorium and separating from other elements. The thorium on the resin is stripped by 4 mol/L HCl, with oxalic acid and urea as screening agent, thorium forms red complex with arsenazo III. The maximum absorption of the complex is at 668 nm, and the molar absorptivity is 1.27 x 10 5 L/(mol·cm) . The complex can be steady for 2.5 h. By regulating micro-current of differential spectrophotometry, the method can realize determination with high precision. Sensitivity of this method increase 10 times than usual spectrophotometry. The relative standard deviation is better than +- 5% and recovery of thorium is 99%-107%

Edge-carboxylated graphene nanoflakes from nitric acid oxidised arc-discharge material

OpenAIRE

NICOLOSI, VALERIA

2010-01-01

PUBLISHED Graphene nanoflakes (GNFs) with average diameters of 30 nm have been prepared by a single-step oxidation procedure using single-wall carbon nanotube arc-discharge material and nitric acid. The GNFs are predominately single sheets containing a small number of internal defects. The edges are decorated with primarily carboxylic acid groups which allow facile chemical functionalisation and cross-linking of the fragments using multivalent cations

Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO{sub 2}/Si and SiO{sub 2}/SiC structures

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, H., E-mail: koba771@ybb.ne.jp [Institute of Scientific and Industrial Research, Osaka University, and CREST, Japan Science and Technology Agency, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Imamura, K.; Kim, W.-B.; Im, S.-S.; Asuha [Institute of Scientific and Industrial Research, Osaka University, and CREST, Japan Science and Technology Agency, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)

2010-07-15

We have developed low temperature formation methods of SiO{sub 2}/Si and SiO{sub 2}/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO{sub 3} aqueous solutions at 120 deg. C), an ultrathin (i.e., 1.3-1.4 nm) SiO{sub 2} layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 deg. C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 deg. C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO{sub 2} gap-state density, and (iii) high band discontinuity energy at the SiO{sub 2}/Si interface arising from the high atomic density of the NAOS SiO{sub 2} layer. For the formation of a relatively thick (i.e., {>=}10 nm) SiO{sub 2} layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in {approx}40 wt% HNO{sub 3} and azeotropic HNO{sub 3} aqueous solutions, respectively. In this case, the SiO{sub 2} formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO{sub 2} layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO{sub 2} layer is slightly higher than that for thermal oxide. When PMA at 250 deg. C in hydrogen is performed on the two-step NAOS SiO{sub 2} layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 deg. C. A relatively thick (i.e., {>=}10 nm) SiO{sub 2} layer can also be formed on SiC at 120 deg. C by use of the two-step NAOS method. With no treatment before the NAOS method

Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

International Nuclear Information System (INIS)

Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

2015-01-01

Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

Adsorption mechanism of 2,4-dichlorophenoxyacetic acid onto nitric-acid-modified activated carbon fiber.

Science.gov (United States)

Li, Qun; Sun, Jie; Ren, Tianhao; Guo, Lin; Yang, Zhilin; Yang, Qi; Chen, Hai

2018-04-01

Adsorption by carbon materials is one of the relatively fast methods in present research, which is widely used in emergency events. Activated carbon fiber (ACF) modified by nitric acid (N-ACF) was studied in this research to determine the adsorption performance for 2,4-dichlorophenoxyacetic acid (2,4-D). Subsequently, influence factors, adsorption isotherm models, kinetics and thermodynamic were investigated in a batch system to realize this adsorption. Experimental results showed that ACF modified by 0.1M nitric acid had a better removal ability than 2,4-D. Removal rate of 2,4-D by N-ACF was greatly influenced by pH with the optimum pH at 2. The superiority of the Langmuir isotherm model in describing the adsorption equilibrium was revealed by correlation coefficients R2 (R 2  ≥ 0.997). Furthermore, adsorption kinetics was well described by pseudo-second-order model. The results of thermodynamic showed that adsorption was a spontaneous, endothermic process with randomness increasing. Additionally, surface structure properties of adsorbent were characterized by Scanning electron microscopy, Fourier transform infrared spectroscopy, Specific surface area analysis of Brunauer, Emmett and Teller and Boehm's titration. It turned out that the micropore structure and functional groups on N-ACF all can contribute to the removal of 2,4-D.

Process chemistry of neptunium. Part II

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, N.; Ramaniah, M. V.; Patil, S. K.; Ramakrishna, V. V.; Swarup, R.; Chadha, A.; Avadhany, G. V.N.

1974-07-01

The oxidation state analysis of neptunium in the aqueous feed solution from the Plutonium Plant at Trombay was carried out and it was found that neptunium existed mainly as Np(V) in the feed solution. Batch extraction data for Np(IV) and Np(VI) into 30% TBP/Shell Sol T at different aqueous nitric acid concentration and uranium saturation of the organic phase were obtained at 45 deg C and 60 deg C and the results are summarized. The distribution coefficients of Np(IV) and Np(VI) were obtained as a function of TBP concentration and the data are reported. The effect of nitrous acid on the extraction of neptunium, present in the aqueous phase as Np(IV) and Np(V), by 30% TBP was studied and the data obtained are given. The data on the rate of reduction of NP(VI) and Np(V) to Np(IV) by U(IV) were obtained for different U(IV) and nitric acid concentrations. Some redox reactions involving Np(IV), Pu(IV) and V(V) were investigated and their possible application in the purex process for neptunium recovery were explored. (auth)

Acid digestion of organic liquids

International Nuclear Information System (INIS)

Partridge, J.A.; Bosuego, G.P.

1980-10-01

Laboratory studies on the destruction of liquid organic wastes by acid digestion are discussed. A variety of liquid waste types was tested, including those encountered in the nuclear industry as well as some organic liquids representative of non-nuclear industrial wastes. The liquids tested were vacuum pump oil, tri-n-butyl phosphate (TBP), normal paraffin hydrocarbon solvent (NPH), a mixture of 30 vol% TBP in NPH, carbon tetrachloride (CCl 4 ), trichloroethane, toluene, hexone (methyl isobutyl ketone), a mixture of hexone and NPH, polychlorobiphenyl (PCB), isopropanol, normal-decane, and two waste organic solutions from Hanford radioactive waste tanks. The tests demonstrated that several types of organic liquids can be destroyed by the acid digestion process. 8 figures, 19 tables

Influence of nitric acid concentration on the characteristics of active carbons obtained from a mineral coal

Energy Technology Data Exchange (ETDEWEB)

Khelifi, A.; Temdrara, L.; Addoun, A. [Laboratoire d' Etude Physicochimique des Materiaux et Application a l' Environnement, Faculte de Chimie, USTHB, BP. 32 El Alia, Bab Ezzouar 16111, Algiers (Algeria); Almazan-Almazan, M.C.; Perez-Mendoza, M.; Domingo-Garcia, M.; Lopez-Garzon, F.J [Departamento de Quimica Inorganica, Facultad de Ciencias, 18071 Granada (Spain); Lopez-Domingo, F.J. [Departamento de CCIA, ETS de Ingenieria Informatica y Telecomunicacion, Granada, 18071 (Spain)

2010-10-15

This paper deals with the effect of the concentration of nitric acid solutions on the properties of activated carbons obtained by the oxidation of a parent activated carbon. For this purpose a mineral coal from Algeria has been used as raw material to prepare the parent active carbon AC. This was further treated with nitric acid solutions. The analysis of the samples includes the chemical and textural characterization. The former was carried out by selective titrations and FTIR spectroscopy. The latter, by nitrogen and carbon dioxide adsorption at 77 and 273 K, respectively, and by adsorption of organic probes (benzene, dichloromethane, cyclohexane and 2,2-dimethyl butane) at 303 K. The nitrogen adsorption isotherms have been analysed by using the BET equation, {alpha}{sub s}-method and molecular simulation. The Dubinin-Radushkevich approach has been applied to the carbon dioxide and vapours adsorption data. The results show that the treatment with 2 N nitric acid solution is very appropriate because it introduces a large amount of oxygen containing groups with a small change of the textural characteristics of the parent AC. More concentrated nitric acid solutions change in large extent the textural properties although they also introduce large amount of chemical groups. (author)

Raman spectroscopic study of the aging and nitration of actinide processing anion-exchange resins in concentrated nitric acid

International Nuclear Information System (INIS)

Buscher, C. T.; Donohoe, R. J.; Mecklenburg, S. L.; Berg, J. M.; Tait, C. D.; Huchton, K. M.; Morris, D. E.

1999-01-01

Degradation of two types of anion exchange resins, Dowex 11 and Reillex HPQ, from the action of concentrated nitric acid (4 to 12 M) and radiolysis [from depleted uranium as UO 2 2+ nitrate species and 239 Pu as Pu(IV) nitrate species] was followed as a function of time with Raman vibrational spectroscopy. Elevated temperatures (∼50 degree sign C) were used in the absence of actinide metal loading to simulate longer exposures of the resin to a HNO 3 process stream and waste storage conditions. In the absence of actinide loading, only minor changes in the Dowex resin at acid concentrations ≤10 M were observed, while at 12 M acid concentration, the emergence of a Raman peak at 1345 cm-1 indicates the addition of nitro functional groups to the resin. Similar studies with the Reillex resin show it to be more resistant to nitric acid attack at all acid concentrations. Incorporation of weakly radioactive depleted uranium as the UO 2 2+ nitrate species to the ion-exchange sites of Dowex 11 under differing nitric acid concentrations (6 to 12 M) at room temperature showed no Raman evidence of resin degradation or nitration, even after several hundred days of contact. In contrast, Raman spectra for Dowex 11 in the presence of 239 Pu as Pu(IV) nitrate species reveal numerous changes indicating resin alterations, including a new mode at 1345 cm-1 consistent with a Pu(IV)-nitrate catalyzed addition of nitro groups to the resin backbone. (c) 2000 Society for Applied Spectroscopy

Features of molybdenum disulfide interaction with nitric acid

International Nuclear Information System (INIS)

Chursanov, Yu.V.; Potashnikov, Yu.M.; Rumyantsev, V.K.

1987-01-01

Experiments on studying composition of products of molybdenite concentrate (MoS 2 ) oxidation by HNO 3 solutions were conducted. Molybdenite oxidation was conducted in a glass temperature controlled vessel in absence of oxygen. It was shown that nitrogen (2) oxide represented the final product of molybdenite interaction with nitric acid. The process was accompanied as well by separation of NO 2 and HNO 2 under dynamic conditions, and nitrogen (4) oxide acted as catalyst of oxidation at that

Integrating nitric oxide into salicylic acid and jasmonic acid/ethylene plant defense pathways

DEFF Research Database (Denmark)

Mur, Luis A J; Prats, Elena; Pierre, Sandra

2013-01-01

to be tailored to particular biotic stresses. Nitric oxide (NO) has emerged as a major signal influencing resistance mediated by both signalling pathways but no attempt has been made to integrate NO into established SA/JA/ET interactions. NO has been shown to act as an inducer or suppressor of signalling along......Plant defence against pests and pathogens is known to be conferred by either salicylic acid (SA) or jasmonic acid (JA)/ethylene (ET) pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defence responses...

Double liquid membrane system for the removal of actinides and lanthanides from acidic nuclear wastes

International Nuclear Information System (INIS)

Chiarizia, R.; Danesi, P.R.

1985-01-01

Supported liquid membranes (SLM), consisting of an organic solution of n-octyl-(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl-phosphate (TBP) in decalin are able to perform selective separation and concentration of actinide and lanthanide ions from aqueous nitrate feed solutions and synthetic nuclear wastes. In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of nitric acid which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO 3 from the strip solution. In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HNO 3 concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion. 15 refs., 10 figs., 1 tab

Extraction of lanthanides and actinides (III) by DI-2 ethyl dithiophosphoric acid and DI-2 ethyl hexyl monothiophosphoric acid. Structure of the complexes in the organic phase

International Nuclear Information System (INIS)

Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

1986-09-01

To operate a trivalent actinide-lanthanide (III) group chemical separation from low pH nitric solutions we studied the extractive properties of the di-2 ethyl hexyl dithiophosphoric acid (HDEHDTP); this bidentate ligand which possesses a sulfur donor atom is a good extractant of soft acids. We so expect a better selectivity for the actinides (III) extraction. We also have investigated extractive properties of di-2 ethyl hexyl monothiophosphoric acid (HDEHTP) for trivalent actinides and lanthanides; HDEHDTP is a bidentate ligand with one oxygen donor atom and so is a better extractant for hard acids like actinides and lanthanides (III); but its selectivity is weak. The addition of TBP (tri-n butyl phosphate) to HDEHDTP deals to strong synergistic organic complexes with a great selectivity for Am(III). We explicited this phenomenon. When the metal is macroconcentrated the organic complexes aggregate and form inverted micelles

Separation of actinide elements by solvent extraction using centrifugal contactors in the NEXT process

International Nuclear Information System (INIS)

Nakahara, Masaumi; Sano, Yuichi; Koma, Yoshikazu; Kamiya, Masayoshi; Shibata, Atsuhiro; Koizumi, Tsutomu; Koyama, Tomozo

2007-01-01

Using the advanced aqueous reprocessing system named NEXT process, actinides recovery was attempted by both a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery and the SETFICS process for Am and Cm recovery from the raffinate. In U, Pu and Np co-recovery experiments a single cycle flow sheet was used under high nitric acid concentration in the feed solution or scrubbing solution. High nitric acid concentration in the feed solution aided Np oxidation not only in the feed solution, but also at the extraction section. This oxidation reaction accomplished Np extraction by TBP with U and Pu. Most of Np could be recovered into the product solution. In the SETFICS process, a TRUEX solvent of 0.2 mol/dm 3 CMPO and 1.4 mol/dm 3 TBP in n-dodecane was employed instead of 0.2 mol/dm 3 CMPO and 1.0 mol/dm 3 TBP in n-dodecane in order to increase the loading of metals. Instead of sodium nitrate, hydroxylamine nitrate was applied to this experimental flow sheet in accordance with a 'salt-free' concept. The counter current experiment succeeded with the Am and Cm product. On the high-loading flow sheet, compared with the previous flow sheet, the flow of the aqueous effluents and spent solvent were expected to decrease by about one half. Two solvent extraction experiments for actinides recovery demonstrated the utility of the flow sheet of these processes in the NEXT process. (author)

Nitric acid leaching of radium and other significant radionuclides from uranium ores and tailings

International Nuclear Information System (INIS)

Ryon, A.D.; Hurst, F.J.; Seeley, F.G.

1977-08-01

Nitric acid leaching of representative uranium ores and mill tailings from the western U.S. mining districts removes up to 98% of the 226 Ra and 230 Th, yielding a residue containing 17 to 60 pCi of radium per gram. At best, this is an order of magnitude greater than that in surrounding soils, but about the same level as a standard proposed for building materials in the United Kingdom. Data are also presented on the water penetration and leaching of tailings, the solubility of BaSO 4 , and radon emanation coefficients of ores, tailings, and nitric acid-leached residues

Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

Energy Technology Data Exchange (ETDEWEB)

Lines, Amanda M. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Adami, Susan R. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Casella, Amanda J. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Sinkov, Sergey I. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Lumetta, Gregg J. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Bryan, Samuel A. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352

2017-09-20

The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.

Solvent extraction of aurocyanide by extractant CTMAB and TBP

International Nuclear Information System (INIS)

Yan Wenfei; Zhang Tianxi; Wu Jinguang

2000-01-01

A novel extraction system using KAu(CN) 2 -CTMAB as aqueous phase and 30% TBP-dodecane as organic phase is studied by 198 Au radioactive tracer and FT-IR spectroscopy. The results show that the organic phase separates into two phases, when the gold concentration is bigger than 20 g/L. From the analysis of FT-IR it is seen that the most of gold is in the lower organic phase

Effect of nitrate on corrosion of austenitic stainless steel in boiling nitric acid solution containing chromium ions

International Nuclear Information System (INIS)

Hasegawa, Satoshi; Kim, Seong-Yun; Ebina, Tetsunari; Ito, Tatsuya; Nagano, Nobumichi; Hitomi, Keitaro; Ishii, Keizo; Tokuda, Haruaki

2016-01-01

The oxidation behavior of chromium and the corrosion behavior of austenitic stainless steel in boiling nitric acid solution containing highly concentrated nitrates were investigated using UV-visible spectroscopic measurements, Raman spectral measurements, immersion tests, and potentiodynamic polarization measurements. The oxidation rate measurement of chromium from Cr(III) to Cr(VI) was performed by 1 M boiling nitric acid solution containing each highly concentrated nitrates: Al(NO_3)_3, Nd(NO_3)_3, Ca(NO_3)_2, Mg(NO_3)_2, and NaNO_3 as a simulant of uranium nitrate in uranium concentrator in reprocessing plants. As a result, the rate of chromium oxidation was different depending on the added nitrates even at the same nitric acid concentration. In addition, the oxidation rate of chromium was increased with increasing the calculated partial pressure of nitric acid in consideration of the hydration of cation of nitrates. Furthermore, the corrosion rate of type 310 stainless steel was accelerated by the solution having a high chromium oxidation rate containing nitrates. These results indicated that the acceleration of the corrosion rate in the solutions depending on the oxidation rate of chromium, and the rate is affected by the salt-effect of nitrates. (author)

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

Energy Technology Data Exchange (ETDEWEB)

Cames, B

1997-12-31

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media ({<=} 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 {<=} E {<=} 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

Study of Cs recovery by extraction chromatography (2)

International Nuclear Information System (INIS)

Hoshi, Harutaka; Zhang, Anyun; Uchida, Hiromi; Kuraoka, Etsushu

2005-02-01

In order to apply CalixR14 extractant to extraction chromatography for Cs separation, basic characteristics of CalixR14 adsorbent were studied. CalixR14 impregnated resin and CalixR14 + TBP impregnated resin were prepared. CalixR14 extractant showed no adsorption for Cs by liquid-liquid extraction and CalixR14 impregnated resin also showed no adsorption for Cs. Therefore, it is concluded that CalixR14 itself has no affinity for Cs. On the other hand, Cs was adsorbed onto CalixR14-TBP impregnated resin from a concentrated nitric acid solution. The distribution coefficients of Cs were more than 10 cm 3 /g from 2 to 6 M nitric acid. While Rb showed week adsorption, Na, K, Sr and La showed no adsorption and separation factor was over 100. A slight amount of CalixR14 and TBP was leaked from impregnated resin into the aqueous phase. Separation from simulated liquid waste was carried out by using a column packed with CalixR14-TBP adsorbent. Na, K, Sr and La were not adsorbed onto the column, however, Cs and Rb were adsorbed onto the column. Cs and Rb were eluted from the column by water. Cs and Rb were quantitatively recovered. (author)

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Science.gov (United States)

R. Cisneros; A. Bytnerowicz; D. Schweizer; S. Zhong; S. Traina; D.H. Bennett

2010-01-01

Two-week average concentrations of ozone (O3), nitric acid vapor (HNO3) and ammonia (NH3) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were...

Passive Sampler for Measurements of Atmospheric Nitric Acid Vapor (HNO3 Concentrations

Directory of Open Access Journals (Sweden)

Andrzej Bytnerowicz

2001-01-01

Full Text Available Nitric acid (HNO3 vapor is an important nitrogenous air pollutant responsible for increasing saturation of forests with nitrogen and direct injury to plants. The USDA Forest Service and University of California researchers have developed a simple and inexpensive passive sampler for monitoring air concentrations of HNO3. Nitric acid is selectively absorbed on 47-mm Nylasorb nylon filters with no interference from particulate NO3-. Concentrations determined with the passive samplers closely corresponded with those measured with the co-located honeycomb annular denuder systems. The PVC protective caps of standardized dimensions protect nylon filters from rain and wind and allow for reliable measurements of ambient HNO3 concentrations. The described samplers have been successfully used in Sequoia National Park, the San Bernardino Mountains, and on Mammoth Mountain in California.

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides; Contribution a l'etude de l'extraction d'acides mineraux et de cations actinides aux degres d'oxydation (IV) et (VI) par des N,N-dialkylamides

Energy Technology Data Exchange (ETDEWEB)

Condamines, N

1990-03-15

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO{sub 3}, UO{sub 2}{sup 2+}, Pu{sup 4+}, Th{sup 4+} are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO{sub 3})L{sub 2}, (HNO{sub 3})L, (HNO{sub 3}){sub 2}L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing.

Hydrolysis of TBF and TiAP in presence of zirconium

International Nuclear Information System (INIS)

Vladimirova, M.V.; Kulikov, I.A.; Kuprij, A.A.

1992-01-01

Acid hydrolysis of organic solutions of tributyl phosphate (TBP) and tri-iso-amylphosphate (TiAP) in n-paraffin diluent in the presence of zirconium (0.025-0.1 mole/l) at nitric acid concentration of 0.3-1 mole/l is studied. Hydrolysis of extractants in a two-phase system, modelling conditions of spent fuel reprocessing and consisting of 1.1 mole/l TAP, 3 mole/l nitric acid at zirconium concentration in water phase 0.05-0.11 mole/l, at water-organic phase ratio 10:1 and at 60 deg C is also studied. Constants of TAP hydrolysis in organic and water phases are determined. Mechanism of increasing the TAP hydrolysis rate in zirconium presence is discussed. 5 refs., 2 figs., 5 tabs

U.S. Department of Energy radioactive nitric acid shipping campaign

International Nuclear Information System (INIS)

Penn, H.R.

1996-01-01

This report is about the disposal of a large quantity of chemicals previously used in the Plutonium/Uranium Extraction Plant (PUREX). Several alternatives were considered for disposal of the over 700,000 liters of this radiologically contaminated nitric acid. These alternatives included sugar denitration, biodenitrification, calcination, chemical conversion to solid sodium nitrate or to ammonium nitrate, or decontamination and re-use. Another alternative was to solicit interest from others that might be able to utilize this material in its current condition. British Nuclear Fuels Inc., located in the United Kingdom, expressed interest in this alternative. DOE Headquarters requested Westinghouse Hanford Company (WHC) Transportation and Packaging group to investigate the feasibility of transferring the radiologically contaminated nitric acid to the United Kingdom. Shipments began in May 1995, and were monitored with DOE's satellite tracking system TRANSCOM. This shipping campaign was successfully completed, with no incidents, and savings realized for cleanup of the PUREX facility in excess of $37 million. This process will be duplicated at the Savannah River Site, with cooperation between SRS and Hanford personnel sharing lessons learned

The uranium separation from Ru using Tbp solvent by membrane emulsion method

International Nuclear Information System (INIS)

Bintarti, A. N.; Bambang, EHB. J.; Pramono, J.

1998-01-01

An extraction process for uranium (U) separation from ruthenium (Ru) by tributyl phosphate (Tbp) as a solvent with kerosene as a diluent and surfactant the Span-80 as emulator has been performed. A sodium carbonate solution having ph 10-11 was used as the internal phase. the feed contained U and Ru in HNO 3 solution, while butanol was used as the membrane sp liter. the membrane used for extraction had a composition of 5% vol surfactant, 10% vol Tbp, 35% vol kerosene and 50% vol Na 2 CO 3 solution. The mixing time and speed were varied in value, so were the acidity levels, ranging from 0.5 M, 0.75 M up to 1 M. The result of the experimental separation of a mixture containing 5000 ppm U and 325 ppm Ru showed that a molarity of 0.5 M HNO 3 in the feed, 15 minutes mixing time, and 800 rpm mixing speed were found to be the best conditions for the extraction. Such condition had resulted in achieving the value of stripping distribution coefficient K d for U= 0.5660 with 49.73% U recovery efficiency and a practically zero separation factor from Ru

Extraction of fission product rhodium from nitric acid solutions. 1

International Nuclear Information System (INIS)

Gorski, B.; Beer, M.; Russ, L.

1988-01-01

The extraction of noble metals from nitric acid solutions represents one problem of separating valueable substances from nuclear wastes in nuclear fuel reprocessing. Results of distribution experiments demonstrate the possibility of solvent extraction of rhodium using tertiary amines in presence of nitrite. Even short mixing times realize high distribution coefficients allowing quantitative separation from aqueous solutions. (author)

4.2. The kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit

International Nuclear Information System (INIS)

Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

2015-01-01

Present article is devoted to kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit. The dependence of nitric acid decomposition of calcined boric raw material for extraction of boron oxide on temperature (20-100 deg C) and process duration (15-60 minutes) was defined. It was defined that at temperature increasing the extraction rate of boron oxide increases from 20.8 to 78.6%.

Recovery of nitric acid from simulated acidic high level radioactive waste using pore-filled anion exchange membranes

International Nuclear Information System (INIS)

Chavan, Vivek; Agarwal, Chhavi; Pandey, A.K.; Goswami, A.

2014-01-01

Acidic waste is generated at different stages of nuclear fuel cycle. The waste contains minor amounts of actinides ( 241 Am, Pu, Np) along with large number of long-lived radionuclides such as 137 Cs, 90 Sr, 106 Ru etc. Before disposal or storage, the overall activity of the waste needs to be reduced. Along with this, the high amount of acid present in the waste needs to be removed. In this study, DD has been used to recover nitric acid from acidic solutions with compositions similar to radioactive waste using pore-filled anion exchange membranes

Fabrication of silica ceramic membrane via sol-gel dip-coating method at different nitric acid amount

Science.gov (United States)

Kahlib, N. A. Z.; Daud, F. D. M.; Mel, M.; Hairin, A. L. N.; Azhar, A. Z. A.; Hassan, N. A.

2018-01-01

Fabrication of silica ceramics via the sol-gel method has offered more advantages over other methods in the fabrication of ceramic membrane, such as simple operation, high purity homogeneous, well defined-structure and complex shapes of end products. This work presents the fabrication of silica ceramic membrane via sol-gel dip-coating methods by varying nitric acid amount. The nitric acid plays an important role as catalyst in fabrication reaction which involved hydrolysis and condensation process. The tubular ceramic support, used as the substrate, was dipped into the sol of Tetrethylorthosilicate (TEOS), distilled water and ethanol with the addition of nitric acid. The fabricated silica membrane was then characterized by (Field Emission Scanning Electron Microscope) FESEM and (Fourier transform infrared spectroscopy) FTIR to determine structural and chemical properties at different amount of acids. From the XRD analysis, the fabricated silica ceramic membrane showed the existence of silicate hydrate in the final product. FESEM images indicated that the silica ceramic membrane has been deposited on the tubular ceramic support as a substrate and penetrate into the pore walls. The intensity peak of FTIR decreased with increasing of amount of acids. Hence, the 8 ml of acid has demonstrated the appropriate amount of catalyst in fabricating good physical and chemical characteristic of silica ceramic membrane.

Inside versus Outside: Ion Redistribution in Nitric Acid Reacted Sea Spray Aerosol Particles as Determined by Single Particle Analysis (Invited)

Science.gov (United States)

Ault, A. P.; Guasco, T.; Ryder, O. S.; Baltrusaitis, J.; Cuadra-Rodriguez, L. A.; Collins, D. B.; Ruppel, M. J.; Bertram, T. H.; Prather, K. A.; Grassian, V. H.

2013-12-01

Sea spray aerosol (SSA) particles were generated under real-world conditions using natural seawater and a unique ocean-atmosphere facility equipped with actual breaking waves or a marine aerosol reference tank (MART) that replicates those conditions. The SSA particles were exposed to nitric acid in situ in a flow tube and the well-known chloride displacement and nitrate formation reaction was observed. However, as discussed here, little is known about how this anion displacement reaction affects the distribution of cations and other chemical constituents within and phase state of individual SSA particles. Single particle analysis of individual SSA particles shows that cations (Na+, K+, Mg2+ and Ca2+) within individual particles undergo a spatial redistribution after heterogeneous reaction with nitric acid, along with a more concentrated layer of organic matter at the surface of the particle. These data suggest that specific ion and aerosol pH effects play an important role in aerosol particle structure in ways that have not been previously recognized. The ordering of organic coatings can impact trace gas uptake, and subsequently impact trace gas budgets of O3 and NOx.

MLS/Aura L2 Nitric Acid (HNO3) Mixing Ratio V003

Data.gov (United States)

National Aeronautics and Space Administration — ML2HNO3 is the EOS Aura Microwave Limb Sounder (MLS) standard product for nitric acid derived from radiances measured by the 240 GHz radiometer at and below 10 hPa,...

MLS/Aura Level 2 Nitric Acid (HNO3) Mixing Ratio V004

Data.gov (United States)

National Aeronautics and Space Administration — ML2HNO3 is the EOS Aura Microwave Limb Sounder (MLS) standard product for nitric acid derived from radiances measured by the 240 GHz radiometer at and below 10 hPa,...

MLS/Aura L2 Nitric Acid (HNO3) Mixing Ratio V002

Data.gov (United States)

National Aeronautics and Space Administration — ML2HNO3 is the EOS Aura Microwave Limb Sounder (MLS) standard product for nitric acid derived from radiances measured by the 240 GHz radiometer at and below 10 hPa,...

Reducing NO(x) emissions from a nitric acid plant of domestic petrochemical complex: enhanced conversion in conventional radial-flow reactor of selective catalytic reduction process.

Science.gov (United States)

Abbasfard, Hamed; Hashemi, Seyed Hamid; Rahimpour, Mohammad Reza; Jokar, Seyyed Mohammad; Ghader, Sattar

2013-01-01

The nitric acid plant of a domestic petrochemical complex is designed to annually produce 56,400 metric tons (based on 100% nitric acid). In the present work, radial-flow spherical bed reactor (RFSBR) for selective catalytic reduction of nitric oxides (NO(x)) from the stack of this plant was modelled and compared with the conventional radial-flow reactor (CRFR). Moreover, the proficiency of a radial-flow (water or nitrogen) membrane reactor was also compared with the CRFR which was found to be inefficient at identical process conditions. In the RFSBR, the space between the two concentric spheres is filled by a catalyst. A mathematical model, including conservation of mass has been developed to investigate the performance of the configurations. The model was checked against the CRFR in a nitric acid plant located at the domestic petrochemical complex. A good agreement was observed between the modelling results and the plant data. The effects of some important parameters such as pressure and temperature on NO(x) conversion were analysed. Results show 14% decrease in NO(x) emission annually in RFSBR compared with the CRFR, which is beneficial for the prevention of NO(x) emission, global warming and acid rain.

Electrochemical mechanism of uranium mononitride dissolution in aqueous solutions of nitric acid

Energy Technology Data Exchange (ETDEWEB)

Ershov, Boris G. [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Inst. of Physical Chemistry and Electrochemistry

2017-09-01

It was shown that the dissolution of UN with metallic conduction follows an electrochemical mechanism when it proceeds in contact with an electrically conductive medium (HNO{sub 3} solution). According to this mechanism, the oxidation of UN (at the anode) passes an electron into the UN matrix, which is a conductor, and can then reduce nitric acid in a parallel reaction a short distance away at another exposed surface of the UN (at the cathode). As a result, the reduction of HNO{sub 3} affords NO and NO{sub 2}, while oxidation of uranium mononitride affords NH{sub 3}, N{sub 2}, and N{sub 2}O. The occurrence of these two separate processes accounts for the composition and yields of the products formed from UN and HNO{sub 3} as well as for the nitrogen isotope distribution between them when UN and HNO{sub 3} were labeled with {sup 14} N or {sup 15}N. A mathematical equation describing the dependence of N{sub 2} and N{sub 2}O yields on HNO{sub 3} concentration was derived. It was also shown that the calculated value of standard electromotive force of the galvanic pair formed on the UN surface during its dissolution in HNO{sub 3} is high enough to initiate and support the electrochemical mechanism of its dissolution in nitric acid.

Studies on Pu(IV)/(III)-oxalate precipitation from nitric acid containing high concentration of calcium and fluoride ions

International Nuclear Information System (INIS)

Kalsi, P.K.; Pawar, S.M.; Ghadse, D.R.; Joshi, A.R.; Ramakrishna, V.V.; Vaidya, V.N.; Venugopal, V.

2003-01-01

Plutonium (IV)/(III) oxalate precipitation from nitric acid solution, containing large amount of calcium and fluoride ions was investigated. It was observed that direct precipitation of Pu (IV) oxalate from nitric acid containing large amount of calcium and fluoride ions did not give good decontamination of Pu from calcium and fluoride impurities. However, incorporation of hydroxide precipitation using ammonium hydroxide prior to Pu (IV) oxalate precipitation results into PuO 2 with much less calcium and fluoride impurities. Whereas, good decontamination from calcium and fluoride impurities could be obtained by employing Pu (III) oxalate precipitation directly from nitric acid containing large amount of calcium and fluoride ions. A method was also developed to recover Pu from the oxalate waste containing calcium and fluoride ions. (author)

Standard and applied material testing methods of austenitic CrNi stainless steels in different nitric acid media - procedures and results

International Nuclear Information System (INIS)

Leistikow, S.; Kraft, R.; Schanz, G.

1989-07-01

Extended ASTM Standard Huey Testing has been performed in at 120 0 C boiling 14.4 molar (65%) nitric acid during 15 periods (15x48 = 720 h duration) for quality control of numerous commercial nitric acid resistant austenitic CrNi steels. It was shown how sensitively the chosen testing conditions could differentiate between CrNi steels of the same nominal composition as specified for DIN W.Nr. 1.4306 (AISI Type 304 L), but with varying residual element contents. Within an attempt to differentiate within this group of steels by application of electrochemical methods, potentiostatic tests at 1250 mV in nitric acid of equal concentration and temperature were able to detect remarkable differences in corrosion behaviour already after one hour. Another approach, more typical for the electrochemical potentials during materials application in reprocessing plants of nuclear fuel, gave preference to long-term immersion tests, which were performed in nitric acid of lower concentration and temperature. Reference tests in pure 7 molar, 90 0 C nitric acid could only reveal by surface attack small differences in steel quality by exposures of 720 h duration. To shorten the test time by an increase of the redox potential chromium (VI) ions were added to the nitric acid. In a solution of 0,5 g Gr (VI)/l at 90 0 C remarkable differences in corrosion behavior of the steels - similar to the Huey test results - became measurable by means of gravimetry and metallography already during a short-term exposure of 24-71 h. (orig./MM) [de

Catalytic decomposition of nitrous oxide from nitric acid production tail gases. Investigation of inhibition effects. Executive summary

International Nuclear Information System (INIS)

Mul, G.; Perez-Ramirez, J.; Xu, Xiaoding; Oonk, H.; Yakovlev, A.

2001-06-01

Nitric acid production is an important source of nitrous oxide, one of the green-house gases. Catalytic decomposition of N2O in nitric acid tail-gases might be a possibility for emission reduction, but technology is not yet available. As a part of development of suitable catalytic systems, research was performed, aiming at: gaining an improved understanding of catalytic decomposition of N2O and the inhibiting effects of NO, NO2, H2O and O2; and preparing a 'go-no go' decision whether or not to proceed with subsequent re-search and development and if yes, to indicate what technology further development should aim for. Due to the presence of NOx and water in the nitric acid tail gases, catalytic decomposition proves not to be feasible at temperatures below 350C. At higher temperatures possibilities do exist and a number of promising catalysts are identified. These are active (80 - 100 % conversion) in the temperature range of 400 - 500C and under simulated tail gas conditions. Considering process conditions only (temperatures and composition of the tail-gases), the catalysts studied (pref. the Rh/Al2O3 types) could be in principle applied successfully in all Dutch nitric acid plants

Study on reduction and back extraction of Pu(IV) by urea derivatives in nitric acid conditions

International Nuclear Information System (INIS)

Ye, G.A.; Xiao, S.T.; Yan, T.H.; Lin, R.S.; Zhu, Z.W.

2013-01-01

The reduction kinetics of Pu(IV) by hydroxyl-semicarbazide (HSC), hydroxyurea (HU) and di-hydroxyurea (DHU) in nitric acid solutions were investigated separately with adequate kinetic equations. In addition, counter-current cascade experiments were conducted for Pu split from U in nitric acid media using three kinds of reductant, respectively. The results show that urea derivatives as a kind of novel salt-free reductant can reduce Pu(IV) to Pu(III) rapidly in the nitric acid solutions. The stripping experimental results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by the urea derivatives, and the separation factors of plutonium /uranium can reach more than 10 4 . This indicates that urea derivatives is a kind of promising salt-free agent for uranium/plutonium separation. In addition, the complexing effect of HSC with Np(IV) was revealed, and Np(IV) can be back-extracted by HSC with a separation factor of about 20

Study on reduction and back extraction of Pu(IV) by urea derivatives in nitric acid conditions

Energy Technology Data Exchange (ETDEWEB)

Ye, G.A.; Xiao, S.T.; Yan, T.H.; Lin, R.S.; Zhu, Z.W. [China Institute of Atomic Energy, P.O.Box 275(26), Beijing 102413 (China)

2013-07-01

The reduction kinetics of Pu(IV) by hydroxyl-semicarbazide (HSC), hydroxyurea (HU) and di-hydroxyurea (DHU) in nitric acid solutions were investigated separately with adequate kinetic equations. In addition, counter-current cascade experiments were conducted for Pu split from U in nitric acid media using three kinds of reductant, respectively. The results show that urea derivatives as a kind of novel salt-free reductant can reduce Pu(IV) to Pu(III) rapidly in the nitric acid solutions. The stripping experimental results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by the urea derivatives, and the separation factors of plutonium /uranium can reach more than 10{sup 4}. This indicates that urea derivatives is a kind of promising salt-free agent for uranium/plutonium separation. In addition, the complexing effect of HSC with Np(IV) was revealed, and Np(IV) can be back-extracted by HSC with a separation factor of about 20.

Radiolysis of concentrated nitric acid solutions

International Nuclear Information System (INIS)

Nagaishi, R.; Jiang, P.Y.; Katsumura, Y.; Domae, M.; Ishigure, K.

1995-01-01

A study on electron pulse- and 60 Co γ-radiolysis of concentrated nitric acid and nitrate solutions has been carried out to elucidate the radiation induced reactions taking place in the solutions. Dissociation into NO 2 - and O( 3 P) was proposed as a direct action of the radiation on nitrate and gave the G-values were dependent on the chemical forms of nitrate: g s2 (-NO 3 - )=1.6 and g s2 (-HNO 3 )=2.2 (molecules/100eV). Based on the experimental yields of HNO 2 and reduced Ce IV , the primary yields of radiolysis products of water, g w , were evaluated to clarify the effects of nitrate on spur reactions of water in various nitrate solutions. (author)

Distribution of zirconium in the nitric acid-water-TPB-diluent system

International Nuclear Information System (INIS)

Shu, J.; Floh de Araujo, B.

1984-10-01

This paper deals with the extraction behaviour of zirconium in TBP/diluent-HNO 3 -H 2 O systems. The main purpose is to increase the uranium decontamination factor by adjusting the extraction conditions so that zirconium extraction is kept at a mininum. Equilibrium diagram, TBP concentration, aqueous: organic phases ratio, salting-out effects and uranium loading in the organic phase were the main factors studied. All the experiments have been carried out with zirconium in the 10 -2 - 10 -3 M concentration range. The extractant degradation products influence upon ziconium behaviour was also verified. With the data obtained it was possible to introduce some modification in the standard Purex flow-sheet with the increase of the decontamination of uranium from zirconium. 5 refs., 9 figs

Synergistic extraction of Am(III) using HTTA and bi-functional (DHDECMP) and mono-functional (TBP) donors

International Nuclear Information System (INIS)

Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

1999-01-01

The equilibrium constant (log Ks) for the organic phase synergistic reaction for Am(III)-HTTA system with bi-functional neutral donor di-hexyl di-ethyl carbamoylmethyl phosphonate (DHDECMP) was found to be about two orders of magnitude higher than that of the mono-functional neutral donor (TBP) with comparable basicity values. This log Ks value along with a large positive entropy change with DHDECMP compared to that with TBP confirms that the neutral donors like DHDECMP behave as bi-functional, in sharp contrast to its mono-functional behaviour in Pu(VI). (author)

Inducible nitric oxide synthase (iNOS) in tumor biology: the two sides of the same coin

NARCIS (Netherlands)

Lechner, Matthias; Lirk, Philipp; Rieder, Josef

2005-01-01

Inducible nitric oxide synthase (iNOS) is one of three key enzymes generating nitric oxide (NO) from the amino acid l-arginine. iNOS-derived NO plays an important role in numerous physiological (e.g. blood pressure regulation, wound repair and host defence mechanisms) and pathophysiological

Response of marine and freshwater algae to nitric acid and elevated carbon dioxide levels simulating environmental effects of bolide impact

Science.gov (United States)

Boston, P. J.

1988-01-01

One of the intriguing facets of the Cretaceous-Tertiary extinction is the apparently selective pattern of mortality amongst taxa. Some groups of organisms were severely affected and some remained relatively unscathed as they went through the K/T boundary. While there is argument concerning the exact interpretation of the fossil record, one of the best documented extinctions at the Cretaceous-Tertiary boundary is that of the calcareous nannoplankton. These organisms include coccolithic algae and foraminiferans. Attempts to explain their decline at the K/T boundary center around chemistry which could affect their calcium carbonate shells while leaving their silica-shelled cousins less affected or unaffected. Two environmental consequences of an extraterrestrial body impact which were suggested are the production of large quantities of nitrogen oxides generated by the shock heating of the atmosphere and the possible rise in CO2 from the dissolution of CaCO3 shells. Both of these phenomena would acidify the upper layers of the oceans and bodies of freshwater not otherwise buffered. The effects of nitric acid, carbon dioxide, or both factors on the growth and reproduction of calcareous marine coccoliths and non-calcareous marine and freshwater species of algae were considered. These experiments demonstrate that nitric acid and carbon dioxide have significant effects on important aspects of the physiology and reproduction of modern algae representative of extinct taxa thought to have suffered significant declines at the Cretaceous-Tertiary boundary. Furthermore, calcareous species showed more marked effects than siliceous species and marine species tested were more sensitive than freshwater species.

Determination of tributyl phosphate (TBP) by precision densimetry in the TBP-Varsol-HNO3 system

International Nuclear Information System (INIS)

Matsuda, H.T.; Araujo, B.F. de; Araujo, J.A. de.

1981-05-01

A direct TBP determination by digital density measurements is presented. The method is based on the variation of the natural frequency of a hollow oscillator when filled with a solvent. For this purpose a digital densimeter DMA 02C, from PAAR was used. There is a simple relationship between the density of the sample and the frequency of the filled oscillator. (I.C.R.) [pt

Hydrogen generation in SRAT with nitric acid and late washing flowsheets

International Nuclear Information System (INIS)

Hsu, C.W.

1992-01-01

Melter feed preparation processes, incorporating a final wash of the precipitate slurry feed to Defense Waste Processing Facility (DWPF) and a partial substitution of the SRAT formic acid requirement with nitric acid, should not produce peak hydrogen generation rates during Cold Chemical Runs (CCR's) and radioactive operation greater than their current, respective hydrogen design bases of 0.024 lb/hr and 1.5 lb/hr. A single SRAT bench-scale process simulation for CCR-s produced a DWPF equivalent peak hydrogen generation rate of 0.004 lb/hr. During radioactive operation, the peak hydrogen generation rate will be dependent on the extent DWPF deviates from the nominal precipitate hydrolysis and melter feed preparation process operating parameters. Two actual radioactive sludges were treated according to the new flowsheets. The peak hydrogen evolution rates were equivalent to 0.038 and 0.20 lb/hr (DWPF scale) respectively. Compared to the formic acid -- HAN hydrolysis flowsheets, these peak rates were reduced by a factor of 2.5 and 3.4 for Tank 15 and Tank 11 sludges, respectively

Procedure of Destructive Chemical Recovery of Precious Metals in Nitric Acid Production

Directory of Open Access Journals (Sweden)

Ljubičić, M.

2012-07-01

Full Text Available The heart of the nitric acid production process is the chemical reactor containing a platinum-based catalyst pack and an associated catchment system, which allows the ammonia oxidation reaction to take place efficiently. Under the severe operating conditions imposed by the high-pressure ammonia oxidation process, the catalyst gauzes experience progressive deterioration, as shown by the restricted surface of the catalyst wires, the loss of catalytic activity and the loss of catalytic materials. The higher the pressure of gaseous ammonia oxidation, the greater the loss of platinum group metals from the surface of the applied selective heterogeneous catalysts. Total losses for one batch over the whole period of using selective heterogeneous catalysts may account in the range from 20 to 40 % of the total installed quantity of precious metals. An important part of the platinum removed from the platinum-rhodium alloy wires can be recovered at the outlet of the reactor by means of palladium catchment gauzes. However, this catchment process, which is based on the great ability of palladium to alloy with platinum, is not 100 % effective and a fraction of the platinum and practically all of the rhodium lost by the catalyst wires, evades the catchment package and is then deposited in other parts of the plant, especially heat exchangers. From the above mentioned operating equipment, the retained mass of precious metals can be recovered by the technical procedure of non-destructive and destructive chemical solid-liquid extraction.Shown is the technical procedure of destructive chemical recovery of preheater and boiler for preheating and production of steam by applying sulfuric acid (w = 20 % and subsequent procedure of raffination of derived sludge, to the final recovery of precious metals. The technical procedure of destructive chemical recovery of precious metals from preheater and boiler for preheating and production of steam in nitric acid production is

Corrosion-Resistant Ti- xNb- xZr Alloys for Nitric Acid Applications in Spent Nuclear Fuel Reprocessing Plants

Science.gov (United States)

Manivasagam, Geetha; Anbarasan, V.; Kamachi Mudali, U.; Raj, Baldev

2011-09-01

This article reports the development, microstructure, and corrosion behavior of two new alloys such as Ti-4Nb-4Zr and Ti-2Nb-2Zr in boiling nitric acid environment. The corrosion test was carried out in the liquid, vapor, and condensate phases of 11.5 M nitric acid, and the potentiodynamic anodic polarization studies were performed at room temperature for both alloys. The samples subjected to three-phase corrosion testing were characterized using scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDAX). As Ti-2Nb-2Zr alloy exhibited inferior corrosion behavior in comparison to Ti-4Nb-4Zr in all three phases, weldability and heat treatment studies were carried out only on Ti-4Nb-4Zr alloy. The weldability of the new alloy was evaluated using tungsten inert gas (TIG) welding processes, and the welded specimen was thereafter tested for its corrosion behavior in all three phases. The results of the present investigation revealed that the newly developed near alpha Ti-4Nb-4Zr alloy possessed superior corrosion resistance in all three phases and excellent weldability compared to conventional alloys used for nitric acid application in spent nuclear reprocessing plants. Further, the corrosion resistance of the beta heat-treated Ti-4Nb-4Zr alloy was superior when compared to the sample heat treated in the alpha + beta phase.

Adsorption of zirconium from nitric acid solutions on hydrated tin dioxide

Energy Technology Data Exchange (ETDEWEB)

Tret' yakov, S Ya; Sharygin, L M; Egorov, Yu V

1977-01-01

Adsorption of zirconium from nitric acid solutions has been studied with the use of the labeled atom method on hydrated tin dioxide depending on the sorbate concentration, pH and prehistory of the solution. It has been found that adsorption behavior of zirconium essentially depends on its state in the solution.

Argon Shrouded Plasma Spraying of Tantalum over Titanium for Corrosion Protection in Fluorinated Nitric Acid Media

Science.gov (United States)

Vetrivendan, E.; Jayaraj, J.; Ningshen, S.; Mallika, C.; Kamachi Mudali, U.

2018-02-01

Argon shrouded plasma spraying (ASPS) was used to deposit a Ta coating on commercially pure Ti (CP-Ti) under inert argon, for dissolver vessel application in the aqueous spent fuels reprocessing plant with high plutonium content. Oxidation during plasma spraying was minimized by shrouding argon system. Porosity and oxide content were controlled by optimizing the spraying parameters, to obtain a uniform and dense Ta coating. The Ta particle temperature and velocity were optimized by judiciously controlling the spray parameters, using a spray diagnostic charge-coupled device camera. The corrosion resistance of the Ta coatings developed by ASPS was investigated by electrochemical studies in 11.5 M HNO3 and 11.5 M HNO3 + 0.05 M NaF. Similarly, the durability of the ASPS Ta coating/substrate was evaluated as per ASTM A262 Practice-C test in boiling nitric acid and fluorinated nitric acid for 240 h. The ASPS Ta coating exhibited higher corrosion resistance than the CP-Ti substrate, as evident from electrochemical studies, and low corrosion rate with excellent coating stability in boiling nitric, and fluorinated nitric acid. The results of the present study revealed that tantalum coating by ASPS is a promising strategy for improving the corrosion resistance in the highly corrosive reprocessing environment.

Flotation-nitric acid leach procedure for increasing uranium recovery from a refractory ore

International Nuclear Information System (INIS)

Carnahan, T.G.; Lei, K.P.V.

1979-01-01

The Bureau of Mines investigated a flotation-nitric acid leach procedure as part of the goal to maximize minerals and metals recovered from primary and secondary domestic resources. Studies were conducted on an ore that contained carbon-bearing and sulfide mineralization that rendered a portion of the ore refractory (resistant) to conventional leaching technology. The procedure investigated for treating the ore consisted of the following: (1) separation by flotation of the carbonaceous and sulfidic components from the ore, (2) leaching the flotation concentrate with nitric acid at 100 0 to 110 0 C, (3) leaching the flotation tailings with sulfuric acid, and (4) processing the combined leached slurries in a conventional manner to recover yellow cake. In step 2, HNO 3 is converted to gaseous products from which it is regenerated by reacting these products with air and water for further leaching. An overall uranium extraction of 96% was achieved by this procedure

Redox chemistry of americium in nitric acid media

Energy Technology Data Exchange (ETDEWEB)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM

2004-07-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Redox chemistry of americium in nitric acid media

International Nuclear Information System (INIS)

Picart, S.; Jobelin, I.; Armengol, G.; Adnet, JM.

2004-01-01

The redox properties of the actinides are very important parameters for speciation studies and spent nuclear fuel reprocessing based on liquid-liquid extraction of actinides at different oxidation states (as in the Purex or Sesame process). They are also very useful for developing analytical tools including coulometry and redox titration. This study addressed the americium(IV)/americium(III) and americium(VI)/americium(V) redox couples, focusing on exhaustive acquisition of the thermodynamic and kinetic parameters of americium oxidation at an electrode in a complexing nitric acid medium. (authors)

Pseudomacrocyclic effect in extraction processes of metal salts by polyethers from nitric acid solutions

International Nuclear Information System (INIS)

Yakshin, V.V.; Vilkova, O.M.; Kotlyar, S.A.; Kamalov, G.L.

1997-01-01

Comparison of macrocyclic (ME) and pseudmacrocyclic effects (PME), originating by conduct of the metal salt extraction processes (Cs, Sr, In, Zr, Cd, etc) from nitric acid solutions through linear and cyclic polyethers, containing 5 or 6 atoms of ether oxygen and having close molecular masses (290-360), is carried out. It is shown that ordinary ethers practically do not extract the studied metals from nitric acid solutions. By transfer from linear polyethers to their macrocyclic analogs the ME impact is expressed clearly enough: the separation coefficient value grows by tens and hundred times. At the some time the PME role in the extraction processes of metal nitrates through crown-ethers with alkyl and groups is expressed less clearly

Dissolution of Used Nuclear Fuel Using a TBP/N-Paraffin Solvent

Energy Technology Data Exchange (ETDEWEB)

Rudisill, T. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Shehee, T. C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Jones, D. H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); DelCul, G. D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-10-02

The dissolution of unirradiated used nuclear fuel (UNF) pellets pretreated for tritium removal was demonstrated using a tributly phosphate (TBP) solvent. Dissolution of pretreated fuel in TBP could potentially combine dissolution with two cycle of solvent extraction required for separating the actinides and lanthanides from other fission products. Dissolutions were performed using UNF surrogates prepared from both uranyl nitrate and uranium trioxide produced from the pretreatment process by adding selected actinide and stable fission product elements. In laboratory-scale experiments, the U dissolution efficiency ranged from 80-99+% for both the nitrate and oxide surrogate fuels. On average, 80% of the Pu and 50% of the Np and Am in the nitrate surrogate dissolved; however, little of the transuranic elements dissolved in the oxide form. The majority of the 3+ lanthanide elements dissolved. Only small amounts of Sr (0-1.6%) and Mo (0.1-1.7%) and essentially no Cs, Ru, Zr, or Pd dissolved.

Kinetic and thermodynamic modelling of TBP synthesis processes

International Nuclear Information System (INIS)

Azzouz, A.; Attou, M.

1989-02-01

The present paper deals with kinetic and thermodynamic modellisation of tributylphosphate (TBP) synthesis processes. Its aim consists in a purely comparative study of two different synthesis ways i.e. direct and indirect estirification of butanol. The methodology involves two steps. The first step consists in approximating curves which describe the process evolution and their dependence on the main parameters. The results gave a kinetic model of the process rate yielding in TBP. Further, on the basis of thermodynamic data concerning the various involved compounds a theoretical model was achieved. The calculations were carried out in Basic language and an interpolation mathematical method was applied to approximate the kinetic curves. The thermodynamic calculations were achieved on the basis of GIBBS' free energy using a VAX type computer and a VT240 terminal. The calculations accuracy was reasonable and within the norms. For each process, the confrontation of both models leads to an appreciable accord. In the two processes, the thermodynamic models were similar although the kinetic equations present different reaction orders. Hence the reaction orders were determined by a mathematical method which conists in searching the minimal difference between an empiric relation and a kinetic model with fixed order. This corresponds in fact in testing the model proposed at various reaction order around the suspected value. The main idea which results from such a work is that this kind of processes is well fitting with the model without taking into account the side chain reactions. The process behaviour is like that of a single reaction having a quasi linear dependence of the rate yielding and the reaction time for both processes

Corrosion resistance of nickel alloys with chromium and silicon to the red fuming nitric acid

International Nuclear Information System (INIS)

Gurvich, L.Ya.; Zhirnov, A.D.

1994-01-01

Corrosion and electrochemical behaviour of binary Ni-Cr, Ni-Si nickel and ternary Ni-Cr-Si alloys in the red fuming nitric acid (RFNA) (8-% of HNO 3 +20% of N 2 O 4 ) is studied. It is shown that nickel alloying with chromium improves its corrosion resistance to the red fuming nitric acid. Nickel alloying with silicon in quantities of up to 5 % reduces, and up to 10%-increases abruptly the corrosion resistance with subsequent decrease of the latter after the further increase of concentration. Ni-15% of Cr alloy alloying with silicon increases monotonously the corrosion resistance. 10 refs., 7 figs., 3 tabs

Market Analysis DeN2O. Market potential for reduction of N2O emissions at nitric acid facilities

International Nuclear Information System (INIS)

Smit, A.W.; Gent, M.M.C.; Van den Brink, R.W.

2001-05-01

ECN has developed a technique for the removal of nitrous oxide (N2O) from the tail gases of a nitric acid plant. The aim of this project was to make an assessment of the market opportunities of this technique. To this end a study was made of the relevant international regulations and agreements on the field of climate policy. The formulation of an international greenhouse gas policy and concomitant flexible mechanisms is a prerequisite for the market introduction of any N2O abatement technique. The available techniques and techniques in development for N2O abatement in the nitric acid industry are described and the strengths and weaknesses are given. Furthermore, the costs per ton CO2 equivalents removed are estimated. Direct decomposition of N2O (either in the NH3 combustion reactor or downstream the absorber) are the most cost efficient techniques. Finally, the number and sizes of nitric acid plants in Europe and the developments in the fertiliser market are described. The current difficult fertiliser market makes the nitric acid producers reluctant to invest in N2O abatement technologies

The liquid membrane for extraction of Yttrium and Dysprosium from Acid Nitric

International Nuclear Information System (INIS)

Johny, W.S.; Raldi-Artono-Koestoer; Kris-Tri-Basuki; Sudibyo

1996-01-01

The determination of surfactant in liquid membrane has been done. The surfactant is span-80 (sorbitol-monooleate), the liquid membrane phase was the organic phase (O), the internal liquid phase (W) with ratio O/W = 1, and surfactant. The organic phase using D 2 EHPA in the kerosene and the internal liquid phase using aqua des or acid nitric. The determination of surfactant with variation of span-80 (0,25 - 2%) in the liquid membrane volume. The speed of stirrer was 3500 rpm in 20 minute. The ratio of liquid membrane phase form and external phase (aqua des or acid nitric) was 1, the speed of stirrer was 350 rpm in 10 minute (permeation process). The liquid phase and the liquid membrane phase was separated and then determinated the volume of liquid membrane, the result of percentage of span-80 was 0,25 % volume. The extraction of yttrium and dysprosium in 2 M HNO 3 was Kd y = 2.945 and Kd D y = 0.019

Evaluation of the Magnesium Hydroxide Treatment Process for Stabilizing PFP Plutonium/Nitric Acid Solutions

Energy Technology Data Exchange (ETDEWEB)

Gerber, Mark A.; Schmidt, Andrew J.; Delegard, Calvin H.; Silvers, Kurt L.; Baker, Aaron B.; Gano, Susan R.; Thornton, Brenda M.

2000-09-28

This document summarizes an evaluation of the magnesium hydroxide [Mg(OH)2] process to be used at the Hanford Plutonium Finishing Plant (PFP) for stabilizing plutonium/nitric acid solutions to meet the goal of stabilizing the plutonium in an oxide form suitable for storage under DOE-STD-3013-99. During the treatment process, nitric acid solutions bearing plutonium nitrate are neutralized with Mg(OH)2 in an air sparge reactor. The resulting slurry, containing plutonium hydroxide, is filtered and calcined. The process evaluation included a literature review and extensive laboratory- and bench-scale testing. The testing was conducted using cerium as a surrogate for plutonium to identify and quantify the effects of key processing variables on processing time (primarily neutralization and filtration time) and calcined product properties.

Extraction of rare earth elements from a contaminated cropland soil using nitric acid, citric acid, and EDTA.

Science.gov (United States)

Tang, Hailong; Shuai, Weitao; Wang, Xiaojing; Liu, Yangsheng

2017-08-01

Rare earth elements (REEs) contamination to the surrounding soil has increased the concerns of health risk to the local residents. Soil washing was first attempted in our study to remediate REEs-contaminated cropland soil using nitric acid, citric acid, and ethylene diamine tetraacetic acid (EDTA) for soil decontamination and possible recovery of REEs. The extraction time, washing agent concentration, and pH value of the washing solution were optimized. The sequential extraction analysis proposed by Tessier was adopted to study the speciation changes of the REEs before and after soil washing. The extract containing citric acid was dried to obtain solid for the X-ray fluorescence (XRF) analysis. The results revealed that the optimal extraction time was 72 h, and the REEs extraction efficiency increased as the agent concentration increased from 0.01 to 0.1 mol/L. EDTA was efficient to extract REEs over a wide range of pH values, while citric acid was around pH 6.0. Under optimized conditions, the average extraction efficiencies of the major REEs in the contaminated soil were 70.96%, 64.38%, and 62.12% by EDTA, nitric acid, and citric acid, respectively. The sequential extraction analyses revealed that most soil-bounded REEs were mobilized or extracted except for those in the residual fraction. Under a comprehensive consideration of the extraction efficiency and the environmental impact, citric acid was recommended as the most suitable agent for extraction of the REEs from the contaminated cropland soils. The XRF analysis revealed that Mn, Al, Si, Pb, Fe, and REEs were the major elements in the extract indicating a possibile recovery of the REEs.

Studies of molybdenite interaction with nitric acid

International Nuclear Information System (INIS)

Potashnikov, Yu.M.; Lutsik, V.I.; Chursanov, Yu.V.

1984-01-01

Product composition and their effect on the reaction rate of molybdenite with nitric acid are specified. It is shown that alongside with NO NO 2 is included in the composition of the products of MoS 2 and HNO 3 interaction and it produces catalytic effect on the process considered. Under the conditions studied MoS 2 dissolution proceeds in the mixed regime, conditioned by similar values of molybdenite oxidation rate and reaction product diffusion into solution volume (Esub(act.=28.9 kJ/mol, K 298 =6.3x10 -7 , cmxs -1 ), at that due to catalytic effect of NO 2 the dependence V approximately αsup(-g.37) is observed

Sludge batch 9 simulant runs using the nitric-glycolic acid flowsheet

Energy Technology Data Exchange (ETDEWEB)

Lambert, D. P. [Savannah River Site (SRS), Aiken, SC (United States); Williams, M. S. [Savannah River Site (SRS), Aiken, SC (United States); Brandenburg, C. H. [Savannah River Site (SRS), Aiken, SC (United States); Luther, M. C. [Savannah River Site (SRS), Aiken, SC (United States); Newell, J. D. [Savannah River Site (SRS), Aiken, SC (United States); Woodham, W. H. [Savannah River Site (SRS), Aiken, SC (United States)

2016-11-01

Testing was completed to develop a Sludge Batch 9 (SB9) nitric-glycolic acid chemical process flowsheet for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). CPC simulations were completed using SB9 sludge simulant, Strip Effluent Feed Tank (SEFT) simulant and Precipitate Reactor Feed Tank (PRFT) simulant. Ten sludge-only Sludge Receipt and Adjustment Tank (SRAT) cycles and four SRAT/Slurry Mix Evaporator (SME) cycles, and one actual SB9 sludge (SRAT/SME cycle) were completed. As has been demonstrated in over 100 simulations, the replacement of formic acid with glycolic acid virtually eliminates the CPC’s largest flammability hazards, hydrogen and ammonia. Recommended processing conditions are summarized in section 3.5.1. Testing demonstrated that the interim chemistry and Reduction/Oxidation (REDOX) equations are sufficient to predict the composition of DWPF SRAT product and SME product. Additional reports will finalize the chemistry and REDOX equations. Additional testing developed an antifoam strategy to minimize the hexamethyldisiloxane (HMDSO) peak at boiling, while controlling foam based on testing with simulant and actual waste. Implementation of the nitric-glycolic acid flowsheet in DWPF is recommended. This flowsheet not only eliminates the hydrogen and ammonia hazards but will lead to shorter processing times, higher elemental mercury recovery, and more concentrated SRAT and SME products. The steady pH profile is expected to provide flexibility in processing the high volume of strip effluent expected once the Salt Waste Processing Facility starts up.

Nitric Acid and Water Extraction by T2EHDGA in n -Dodecane

Energy Technology Data Exchange (ETDEWEB)

Campbell, Emily L. [Pacific Northwest National Laboratory, Richland, Washington, USA; Chemistry Department, Washington State University, Pullman, Washington, USA; Holfeltz, Vanessa E. [Pacific Northwest National Laboratory, Richland, Washington, USA; School of Nuclear Science and Engineering, Oregon State University, Corvallis, OR; Hall, Gabriel B. [Pacific Northwest National Laboratory, Richland, Washington, USA; Nash, Kenneth L. [Chemistry Department, Washington State University, Pullman, Washington, USA; Lumetta, Gregg J. [Pacific Northwest National Laboratory, Richland, Washington, USA; Levitskaia, Tatiana G. [Pacific Northwest National Laboratory, Richland, Washington, USA

2017-11-10

Liquid-liquid distribution behavior of nitric acid (HNO3) and water by a diglycolamide ligand, N,N,N',N'-tetra-2-ethylhexyldiglycolamide (T2EHDGA) into n-dodecane diluent was investigated. Spectroscopic FTIR and NMR characterization of the organic extraction solutions indicate T2EHDGA carbonyl coordinates HNO3 and progressively aggregates at high acid conditions. Water extraction increases in the presence of HNO3. The experimentally observed distribution of HNO3 was modeled using the computer program, SXLSQI. The results indicated that the formation of two organic phase species—HNO3·T2EHDGA and (HNO3)2·T2EHDGA—satisfactory describes the acid transport behavior. Temperature dependent solvent extraction studies allowed for determination of thermodynamic extraction constants and ΔH and ΔS parameters for the corresponding extractive processes.

The reaction of hydrazine nitrate with nitric acid

International Nuclear Information System (INIS)

Kida, Takashi; Sugikawa, Susumu

2004-03-01

It is known that hydrazine nitrate used in nuclear fuel reprocessing plants is an unstable substance thermochemically like hydroxylamine nitrate. In order to take the basic data regarding the reaction of hydrazine nitrate with nitric acid, initiation temperatures and heats of this reaction, effect of impurity on initiation temperature and self-accelerating reaction when it holds at constant temperature for a long time were measured by the pressure vessel type reaction calorimeter etc. In this paper, the experimental data and evaluation of the safe handling of hydrazine nitrate in nuclear fuel reprocessing plants are described. (author)

Polarographic behaviour of uranium (VI) in tributyl phosphate organic solutions

International Nuclear Information System (INIS)

Degueldre, C.A.; Meklati, M.

1984-01-01

U(VI) determination by D.C. and differential pulse polarography was studied in the organic solutions derived from tributyl phosphate - diluent extracts (after separation from nitric acid media) along with a selected aprotic solvent (i.e.: propylene carbonate and N,N-dimethylacetamide). Miscibility of the TBP-diluent (e.g. cyclohexane, n-hexane, kerosene, n-dodecane) phase with nitric acid as supporting electrolyte, either by addition or already present in the extract was larger in DMA than in PC. In the DMA organic mixture, U(VI) exhibited a DPP peak due to a one electron step, with Esub(p)=-0.4 V (position connected with H 2 O and HNO 3 concentrations). This peak which was proportionnel to the U(VI) concentration from 5x10 -6 to 10 -3 M can be used to determinate directly hexavalent uranium in the industrial organic extraction phases TBP-diluent. (orig.)

Simultaneous determination of nitric acid and uranium concentrations in aqueous solution from measurements of electrical conductivity, density, and temperature

International Nuclear Information System (INIS)

Spencer, B.B.

1991-01-01

Nuclear fuel reprocessing plants handle aqueous solutions of nitric acid and uranium in large quantities. Automatic control of process operations requires reliable measurements of these solutes concentration, but this is difficult to directly measure. Physical properties such as solution density and electrical conductivity vary with solute concentration and temperature. Conductivity, density and temperature can be measured accurately with relatively simple and inexpensive devices. These properties can be used to determine solute concentrations will good correlations. This paper provides the appropriate correlations for solutions containing 2 to 6 Molar (M) nitric acid and 0 to 300 g/L uranium metal at temperatures from 25--90 degrees C. The equations are most accurate below 5 M nitric acid, due to a broad maximum in the conductivity curve at 6 M. 12 refs., 9 figs., 6 tabs

Singlet Ground State Magnetism: III Magnetic Excitons in Antiferromagnetic TbP

DEFF Research Database (Denmark)

Knorr, K.; Loidl, A.; Kjems, Jørgen

1981-01-01

The dispersion of the lowest magnetic excitations of the singlet ground state system TbP has been studied in the antiferromagnetic phase by inelastic neutron scattering. The magnetic exchange interaction and the magnetic and the rhombohedral molecular fields have been determined.......The dispersion of the lowest magnetic excitations of the singlet ground state system TbP has been studied in the antiferromagnetic phase by inelastic neutron scattering. The magnetic exchange interaction and the magnetic and the rhombohedral molecular fields have been determined....

Corrosion behaviour of alloy Ti-35 in boiling nitric acid solution

International Nuclear Information System (INIS)

Lan Cui; Qiu Shaoyu

2005-01-01

This report states the corrosion behaviors of alloy Ti-35 in boiling nitric acid solution. The results show that its general corrosion rate is by far superior to high-purity austenitic stainless steel with super-low carbon content, the stress corrosion and crevice corrosion have been not discovered in its samples, and oxide film can be quickly reproduced in scratch. The microstructural analysis on samples shows that there is a thin compact TiO 2 film on the sample surface of alloy Ti-35, and most of the film possess the crystal structure of rutile type, the other has the crystal structure of anatase type. This oxide layer plays a role in hindering corrosion development, so the corrosion resistance of alloy Ti-35 is raised. In contrast with it, the oxide film on the sample surface of austenitic stainless steel is not found. It is evident that alloy Ti-35 can become the prime candidate structural material for dissolver of reprocessing facility of spent fuel and be substituted for high-purity austenitic stainless steel with super-low carbon content which is used now. (authors)

Determination of americium and curium using ion-exchange in the nitric-acid-methanol medium for environmental analysis

International Nuclear Information System (INIS)

Holm, E.; Fukai, R.

1976-01-01

While transplutonic elements are only slightly sorbed to anion exchangers from hydrochloric or nitric acid media, the presence of alcohol enhances the anionic exchange of these elements, especially in nitric and sulfuric solutions. In the present work a method has been developed for determining americium and curium in environmental samples, on the basis of the difference between the sorption characteristics to anion exchangers in the acid-methanol system of these transplutonic elements and those of plutonium, polonium and thorium. The method also permits us to perform sequential determination of plutonium, when necessary

Modelling of nitric acid production in the Advanced Cold Process Canister due to irradiation of moist air

International Nuclear Information System (INIS)

Henshaw, J.

1994-01-01

This report summarises the work performed for SKB of Sweden on the modelling of nitric acid production in the gaseous environment of the Advanced Cold Process Canister (ACPC). The model solves the simultaneous chemical rate equations describing the radiation chemistry of He/Ar/N 2 /O 2 /H 2 O gas mixture, involving over 200 chemical reactions. The amount of nitric acid produced as a function of time for typical ACPC conditions has been calculated using the model and the results reported. 11 refs, 11 figs, 1 tab

Co-precipitation of plutonium(IV) and americium(III) from nitric acid-oxalic acid solutions with bismuth oxalate

International Nuclear Information System (INIS)

Pius, I.C.; Noronha, D.M.; Chaudhury, Satyajeet

2017-01-01

Co-precipitation of plutonium and americium from nitric acid-oxalic acid solutions with bismuth oxalate has been investigated for the removal of these long lived α-active nuclides from waste solutions. Effect of concentration of bismuth and oxalic acid on the co-precipitation of Pu(IV) from 3 M HNO_3 has been investigated. Similar experiments were also carried out from 3.75 M HNO_3 on co-precipitation of Am(III) to optimize the conditions of precipitation. Strong co-precipitation of Pu(IV) and Am(III) with bismuth oxalate indicate feasibility of treatment of plutonium and americium bearing waste solutions. (author)

Serum uric acid levels and leukocyte nitric oxide production in multiple sclerosis patients outside relapses

NARCIS (Netherlands)

Mostert, JP; Ramsaransing, GSM; Heerserna, DJ; Heerings, M; Wilczak, N; De Keyser, J

2005-01-01

Background: A number of studies found that patients with multiple sclerosis (MS) have low serum levels of uric acid. It is unclear whether this represents a primary deficit or secondary effect. Uric acid is a scavenger of peroxynitrite, which is the product of nitric oxide (NO) and superoxide.

Application of Primary Abatement Technology for Reduction of N2O Emmision in Petrokemija Nitric Acid Production

Directory of Open Access Journals (Sweden)

Ćosić, L.

2013-01-01

Full Text Available Industrial nitric acid production by oxidation of gaseous ammonia with Ostwald procedure produces an unwanted by-product – colorless nitrous oxide, N2O. As emission of N2O represents a very serious problem due of its huge contribution to global warming, certain measures focused on its maximum reduction should be undertaken. Minimization of N2O emission in nitric acid production can be achieved in different parts of the process flow, depending on the applied available technologies. For the abatement of N2O emissions in Petrokemija's nitric acid production processes from the list of the best available technologies chosen were primary and secondary abatement technologies. The mentioned ensures reduction of N2O by use of improved selective heterogeneous catalysts in the step of gaseous ammonia oxidation. Precious metals in the shape of gauzes are used as selective heterogeneous catalyst in primary technology, while in the case of secondary technology the Fe2 O3 catalyst on Al2O3 support in the shape of spherical pellets is chosen. Shown is the application of primary technology for the abatement of N2O in both nitric acid production facilities and their comparison with classical heterogeneous catalyst and preparation for the installation of secondary selective catalyst. N2O emissions with the application of primary technology in both production facilities were reduced from 12 kg of N2O to 7 kg of N2O per ton of pure HNO3. With the primary reduction in N2O emissions the foundation was established for further reduction with the secondary technology to the final value of 0.7 kg of N2O per ton of pure HNO3, which represents mass concentration in the tail gas below 200 mg m-3 (at n. c.. With the applied technologies for the abatement of N2O emissions in Petrokemija's nitric acid production the future prescribed emission limit value will be satisfied.

The effect of crystal textures on the anodic oxidization of zirconium in a boiling nitric acid solution

International Nuclear Information System (INIS)

Kato, Chiaki; Ishijima, Yasuhiro; Ueno, Fumiyoshi; Yamamoto, Masahiro

2016-01-01

The effects of crystal textures and the potentials in the anodic oxidation of zirconium in a boiling nitric acid solution were investigated to study the stress corrosion cracking of zirconium in nitric acid solutions. The test specimen was machined such that the specimen surface was parallel to the rolling surface, arranged with a (0002) crystal texture. The potentials applied for the anodic oxidation of zirconium were set at 1.2, 1.4, and 1.5 V against a saturated KCl–Ag/AgCl electrode (SSE) in boiling 6 M HNO_3. The growth of the zirconium oxide film dramatically changed depending on the applied potential at a closed depassivation potential (1.47 V vs. SSE in this study). At 1.5 V, the zirconium oxide film rapidly grows, and its growth exhibits cyclic oxidation kinetics in accordance with a nearly cubic rate law. The zirconium oxide film grows according to the quantity of electric charge and the growth rate does not depend on the crystal texture in the pretransition region before the cyclic oxidation kinetics. However, the growth and cracking under the thick oxide film depend on the crystal texture in the transition region. On the normal direction side, the oxide film thickness decreases on average since some areas of the thick oxide film are separated from the specimen surface owing to the cracks in the thick oxide. On the rolling direction (RD) side, no cracks in the thick oxide film are observed, but cracks are found under the thick oxide film, which deeply propagate in metal matrix along the RD without an external stress. The cracks under the thick oxide film propagate to the center of the oxide layer. The crystal orientation relationship between the oxide layer and the zirconium matrix is (0002)_Z_r//(111)_Z_r_O_2, and the cracks in the oxide layer propagate in the (0002)_Z_r plane in the zirconium matrix. The oxide layer consists of string-like zirconium oxide and zirconium hydride. The string-like zirconium oxide contains orthorhombic ZrO_2 in addition

Evaluation of nitric and acetic acid resistance of cement mortars containing high-volume black rice husk ash.

Science.gov (United States)

Chatveera, B; Lertwattanaruk, P

2014-01-15

This paper presents the performance of cement mortar containing black rice husk ash (BRHA) under nitric and acetic acid attacks. The BRHA, collected from an electrical generating power plant that uses rice husk as fuel, was ground using a grinding machine. The compressive strength loss, weight loss, and expansion of mortars under nitric and acetic acid attack were investigated. The test results of BRHA properties in accordance with the ASTM C 618 standard found that the optimal grinding time was 4 h as this achieved a Blaine fineness of 5370 cm(2)/g. For parametric study, BRHA were used as a Portland cement Type 1 replacement at the levels of 0%, 10%, 20%, 30%, 40%, and 50% by weight of binder. The water-to-binder ratios were 0.55, 0.60, and 0.65. From test results, when the percentage replacements of BRHA in cement increased, it was observed that the strength loss and weight loss of mortars containing BRHA under acetic acid attack were higher than those of the mortars against nitric acid attack. It was found that, of the various BHRA mortars, the strength loss and weight loss due to nitric and acetic acid attacks were the lowest in the mortar with 10% BRHA replacement. For 10%, 20% and 30% BRHA replacements, the rate of expansion of the BRHA mortar decreased when compared with the control mortar. For the mortars with other percentage replacements of BRHA, the rate of expansion increased. Furthermore, the effective water-to-binder ratios of control and BRHA mortars were the primary factor for determining the durability of mortar mixed with BRHA. Copyright © 2013 Elsevier Ltd. All rights reserved.

Steel corrosion in tributyl phosphate in the presence of water and ethyl mercaptan

International Nuclear Information System (INIS)

Pischik, L.M.; Tsinman, A.I.

1979-01-01

Studied is the corrosion of steels St3, 15Kh5M, 08Kh13, 10Kh14G14N4T, 08Kh18G8N2T, 10Kh17N13M2T in TBP, in mixtures of TBP with ethyl mercaptan (EM) and two-phase systems TBP-water and TBP-water-EM at 50-150 deg. In pure TBP St3 corrosion rate is low even at 150 deg. In the presence of water St 3 strongly corrodes at above 50 deg temperature in organic and water layers and also in gas phase. The steel-08Kh18G8N2T at 90 deg in acid TBP is passive and its corrosion rate is lower than 0.01 mm/year. In identical conditions the resistance of stainless steels increases together with chromium content but in TBP with acid number 100 and above at 150 deg all tested steels including steel-10Kh17N13M2T are slightly resistant. Thus, even in absence of corrosion active additions of EM the mixture of TBP-water at higher temperature is agressive in relation not only to carbon steel but also to stainless steels

Application of CWC analytical procedures for safeguards; Analysis of phosphorus-containing organic chemical signatures from environmental samples; Final report on task FIN A844 on the Finnish support programme to IAEA safeguards

Energy Technology Data Exchange (ETDEWEB)

Rautio, M; Bjoerk, H; Haekkinen, V; Kostiainen, O; Kuitunen, M L; Lehtonen, P; Mesilaakso, M; Soederstroem, M [Finnish Inst. for Verification of the Chemical Weapons Convention, Helsinki (Finland)

1995-03-01

Solvent extraction can be used for the recovery of U and Pu from irradiated fuel. The most potential organic chemical signatures are extractants and solvents used in reprocessing plants. The PUREX process is widely used in reprocessing. It uses tri-n-butyl phosphate (TBP) as extractant in an organic solvent for U and Pu from irradiated fuel and U from its ores. TBP is a strong extractant for tetra and hexavalent actinides from nitric acid media. Stable complexes are formed between actinide nitrate and TBP which are soluble in the organic phase. Sample containing TBP and some radiolysis products can indicate that TBP is used for reprocessing nuclear fuel. The TBP will decompose in the PUREX process to mono-and dibutyl phosphates (MBP and DBP). TBP, DBP and MBP have been analysed from air, water, soil, and sediment samples according to slightly modified procedures presented in Recommended Operating Procedures for Sampling and Analysis in the Verification of Chemical Disarmament. The limits of detection for the phosphates have been determined for air, water and soil samples. (orig.) (12 refs., 8 figs., 4 tabs.).

Changes in oxidative potential of soil and fly ash after reaction with gaseous nitric acid

Science.gov (United States)

Zhan, Ying; Ginder-Vogel, Matthew; Shafer, Martin M.; Rudich, Yinon; Pardo, Michal; Katra, Itzhak; Katoshevski, David; Schauer, James J.

2018-01-01

The goal of this study was to examine the impact of simulated atmospheric aging on the oxidative potential of inorganic aerosols comprised primarily of crustal materials. Four soil samples and one coal fly ash sample were artificially aged in the laboratory through exposure to the vapor from 15.8 M nitric acid solution for 24 h at room temperature. Native and acid-aged samples were analyzed with a cellular macrophage and acellular dithionthreitol assays to determine oxidative potential. Additionally, the samples were analyzed to determine the concentration of 50 elements, both total and the water-soluble fraction of these elements by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICMS) and crystalline mineral composition using X-ray Diffraction (XRD). The results show that reactions with gaseous nitric acid increase the water-soluble fraction of many elements, including calcium, iron, magnesium, zinc, and lead. The mineral composition analysis documented that calcium-rich minerals present in the soils (e.g., calcite) are converted into different chemical forms, such as calcium nitrate (Ca(NO3)2). The nitric acid aging process, which can occur in the atmosphere, leads to a 200-600% increase in oxidative potential, as measured by cellular and acellular assays. This laboratory study demonstrates that the toxic effects of aged versus freshly emitted atmospheric dust may be quite different. In addition, the results suggest that mineralogical analysis of atmospheric dust may be useful in understanding its degree of aging.

Fast and Simultaneous Determination of Pu(Ⅳ) and Nitric Acid in Spent Nuclear Fuel Reprocessing Sample by Near Infrared Spectroscopy

Institute of Scientific and Technical Information of China (English)

LI; Ding-ming; ZHANG; Li-hua; WANG; Ling; GONG; Yan-ping; FAN; De-jun; YI; Bao-shan; CHEN; Qiang; JI; Yong-chao; WU; Ji-zong

2013-01-01

Determination of Pu(Ⅳ)and nitric acid plays significant role in nuclear fuel reprocessing plant to control process accurately and timely.Coupling C-T fixed-type grating with InGaAs detector,a new novel analytical system for simultaneous measurement of nitric acid and Pu(Ⅳ)was developed by our working group.After obtaining near infrared absorptive spectra by the spectroscopic instrument,the spectra data

Studies on extraction behavior of U(VI) and Th(IV) from nitric acid medium using tri-iso-amyl phosphate (TiAP)/ n-dodecane as extractant

International Nuclear Information System (INIS)

Jadhav, S.T.; Tripathi, S.C.; Singh, S.K.; Gandhi, P.M.; Janardan, P.

2012-01-01

Tri-iso-amyl phosphate is a higher homologue of TBP, retaining many advantages of TBP while eliminating or mitigating its disadvantages. Its longer, branched alkyl chain, resists third phase formation during overloading of actinides. The TiAP is being considered as an alternative of TBP for the reprocessing of Fast Breeder Reactor fuels due to its various advantages over TBP

Solvent Extraction of Uranium Towards Good Practice in Design, Operation and Management

International Nuclear Information System (INIS)

Ring, Bob; Freeman, Paul

2014-01-01

Historical Origins: •Originated from nuclear industry uranium concentrates –Based on TBP extractant from nitric acid solutions; –Extractant screening by Oak Ridge National laboratories; • Pilot investigations with acid leach slurries; • Development through commercial application: – Organic phosphoric acids; Dapex e.g. Shiprock –Secondary amine; e.g. Mexican Hat; – Tertiary amine; Amex, e.g. Grants; • Equipment design evolved with each installation

Process and device for liquid organic waste processing by sulfuric mineralization

International Nuclear Information System (INIS)

Aspart, A.; Gillet, B.; Lours, S.; Guillaume, B.

1990-01-01

In a chemical reactor containing sulfuric acid are introduced the liquid waste and nitric acid at a controlled flow rate for carbonization of the waste and oxidation of carbon on sulfur dioxide, formed during carbonization, regenerating simultaneously sulfuric acid. Optical density of the liquid is monitored to stop liquid waste feeding above a set-point. The liquid waste can be an organic solvent such as TBP [fr

Vapor pressures of nitric acid and water in the systems HNO3-H2O and HNO3-Th(NO3)4-H2O at 50oC

International Nuclear Information System (INIS)

Lemire, R.J.; Brown, C.P.; Campbell, A.B.

1985-01-01

The equilibrium compositions of the vapor above nitric acid-water, thorium nitrate-water, and nitric acid-thorium nitrate-water mixtures at 50 o C have been studied as a function of solution concentration by using a transpiration technique. Nitric acid concentrations were varied from 0 to 20 m and thorium nitrate concentrations from 0 to 2.5 m. Our data for the nitric acid-water system have been combined with literature data to obtain parameters for Scatchard's ion-component model, and these parameters provide a satisfactory description of the system at 50 o C over a wide concentration range. The enhancement, at 50 o C, of the nitric acid vapor pressure by added thorium nitrate was found to be less than that previously determined at 25 o C. The data for the nitric acid-thorium nitrate-water system at 50 o C were fitted to a single multiparameter function. (author)

The disproportionation of Pu4+ in nitric acid solutions

International Nuclear Information System (INIS)

Toth, L.M.; Bell, J.T.; Friedman, H.A.

1990-01-01

The Pu 4+ disproportionation equilibrium in nitric acid has been examined at ≤25deg C to extend our understanding and predictive ability with regard to species distribution under these conditions. Vis/UV absorption spectrophotometry has been used in a conventional manner to determine the concentrations of the various plutonium species. Values for the overall equilibrium quotient at 5, 15, and 25deg C were determined to be 0.098, 3.46, and 58.8, respectively, at zero ionic strength. From these values, the enthalpy of the reaction was found to be +52.7 kcal (220 kJ)/mol. The excellent reproducibility of the equilibrium quotients, even while parameters such as acid, nitrate ion and plutonium concentrations were changed, lend confidence to future predictive calculations regarding this reaction. (orig.)

Bronchoconstriction induced by citric acid inhalation in guinea pigs: role of tachykinins, bradykinin, and nitric oxide

NARCIS (Netherlands)

Ricciardolo, F. L.; Rado, V.; Fabbri, L. M.; Sterk, P. J.; Di Maria, G. U.; Geppetti, P.

1999-01-01

Gastroesophageal acid reflux into the airways can trigger asthma attacks. Indeed, citric acid inhalation causes bronchoconstriction in guinea pigs, but the mechanism of this effect has not been fully clarified. We investigated the role of tachykinins, bradykinin, and nitric oxide (NO) on the citric

Study of ion exchange behaviour of some elements at phosphonic-acid cationite in diluted solutions of nitric acid

International Nuclear Information System (INIS)

Razbash, A.A.; Sevast'yanov, Yu.G.

1985-01-01

Ce(3, 4), Eu(3), Gd(3), Sm(3), Sc(3) distribution coefficients are determined in the macroporic phosphonic acid cationite KRF-20T-60 in nitric acid solutions in 0.1-2.0 M concentration interval using statistical method. A simple method of cerium-139 radionuclide extraction from the industrial lanthanum target is developed. The product yield made up more than 99%, specific activity - 2.37x10 9 Bq/mg, radiochemical purity - no less than 99.9%

Synthesis and evaluation of N,N-di-alkyl-2-methoxyacetamides for the separation of U(VI) and Pu(IV) from nitric acid medium

Energy Technology Data Exchange (ETDEWEB)

Kumaresan, R.; Prathibha, T.; Selvan, B. Robert; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

2017-07-01

The homologs of N,N-di-alkyl-2-methoxyacetamides (DAMeOA) having three different alkyl chains varying from hexyl to decyl (C{sub 6}, C{sub 8} and C{sub 10}) were synthesized and characterized by NMR and IR spectral analyses. Extraction behavior of U(VI) and Pu(IV) from nitric acid medium in a solution of 0.5 M of DAMeOA in n-dodecane (n-DD) was studied and the results were compared with those obtained using N,N-di-hexyloctanamide (DHOA) in n-dodecane. The effect of various parameters on the distribution ratio of U(VI) and Pu(IV) in DAMeOA was studied. The extraction of nitric acid increased with decrease in chain length of alkyl group attached to amidic nitrogen atom of DAMeOA and the conditional nitric acid extraction constant was determined. The extraction of nitric acid in DAMeOA/n-DD resulted in the formation of third phase in organic phase and the third phase occurred early with DAMeOA having smaller alkyl chain length. In contrast to this, the distribution ratio (D) of U(VI) and Pu(IV) in DAMeOA/n-DD increased with increase in the concentration of nitric acid and with increase in the chain length of alkyl group attached to amidic nitrogen atom of DAMeOA. The stoichiometry of the metal - solvate was determined from the slope of extraction data. Quantitative recovery of uranium and plutonium from the loaded organic phase was achieved using dilute nitric acid.

Effect of diluent wash over the removal of aqueous dissolved TBP and DBP in reprocessing

International Nuclear Information System (INIS)

Manjula, R.; Dasi, Mahesh; Mohandas, Jaya; Vijaya Kumar, N.; Kumar, T.

2015-01-01

In reprocessing of nuclear spent fuels by PUREX process Tri-n-Butyl phosphate diluted with n-Dodecane (nDD) is used as solvent. This solvent undergoes degradation due to radiation yielding degradation products, mainly Di-n-butyl phosphate (HDBP). During extraction steps some amount of these organic gets dissolved in aqueous phase owing to its mutual solubility. Removal of dissolved organic from aqueous streams before evaporation is essential to prevent red oil related disasters. Diluent wash technique employing nDD as diluent is one of the commonly used method for the same. During the continuous operation of this process, the diluent will get loaded with dissolved organic and subsequently the performance of diluent will not remain same as pure diluent. While some reports are available in literature for the efficiency of removal of TBP by nDD, so far no work has been reported for the removal of DBP. The scope of the present work is to ascertain the efficiency of diluent wash technique on the removal of dissolved TBP as well as DBP. The results obtained indicate that the removal of dissolved TBP by nDD decreases with increase in percentage of TBP in nDD. In the case of DBP it is just reverse and the removal becomes more effective when the TBP percentage in the diluent increases. A/O ratio of 6:1 is found to be more suitable. As the DBP is getting extracted very effectively into nDD containing TBP, diluent wash solution should be treated as spent organic and managed accordingly for further utilization

Easy synthesis of graphene sheets from alfalfa plants by treatment of nitric acid

International Nuclear Information System (INIS)

Qu, Jiao; Luo, Chunqiu; Zhang, Qian; Cong, Qiao; Yuan, Xing

2013-01-01

Highlights: ► An easy method for synthesis of graphene sheets using alfalfa plants was introduced. ► An novelty formation mechanism of graphene sheets using alfalfa plants was proposed. ► This method exploits a new carbon source and provides a novel idea to synthesize graphene sheets. -- Abstract: This letter focuses on synthesis of graphene sheets from alfalfa plants by treatment of nitric acid. The transmission electron microscopy image (TEM) demonstrates that the graphene sheets are agglomerated and overlapped, the energy dispersive spectrum (EDS) indicates that the products are pure, and the Raman spectrum shows the graphene sheets are well graphitized. In addition, the formation mechanism of the graphene sheets from alfalfa plants by treatment nitric acid is discussed. These findings inspire the search for a new strategy for synthesis of graphene sheets from renewable natural products, and the lower cost of this new process and carbon source may facilitate industrial production

Easy synthesis of graphene sheets from alfalfa plants by treatment of nitric acid

Energy Technology Data Exchange (ETDEWEB)

Qu, Jiao, E-mail: qujiao@bhu.edu.cn [School of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013 (China); School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China); Luo, Chunqiu, E-mail: fplj_lcq@163.com [School of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013 (China); Zhang, Qian; Cong, Qiao [School of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013 (China); Yuan, Xing [School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China)

2013-04-01

Highlights: ► An easy method for synthesis of graphene sheets using alfalfa plants was introduced. ► An novelty formation mechanism of graphene sheets using alfalfa plants was proposed. ► This method exploits a new carbon source and provides a novel idea to synthesize graphene sheets. -- Abstract: This letter focuses on synthesis of graphene sheets from alfalfa plants by treatment of nitric acid. The transmission electron microscopy image (TEM) demonstrates that the graphene sheets are agglomerated and overlapped, the energy dispersive spectrum (EDS) indicates that the products are pure, and the Raman spectrum shows the graphene sheets are well graphitized. In addition, the formation mechanism of the graphene sheets from alfalfa plants by treatment nitric acid is discussed. These findings inspire the search for a new strategy for synthesis of graphene sheets from renewable natural products, and the lower cost of this new process and carbon source may facilitate industrial production.

Enrichment of 15N and 18O by chemical exchange reactions between nitrogen oxides (NO, NO2) and aqueous nitric acid

International Nuclear Information System (INIS)

Abrudean, M.; Axente, D.; Baldea, A.

1981-01-01

The enrichment of 15 N and 18 O by chemical exchange in the NO, NO 2 -H 2 O, HNO 3 system is described. A laboratory experimental plant and a cascade for producing the two isotopes has been used. The production plant consists of two exchange columns for 15 N separation and two 18 O separation columns feeded with nitrogen oxides, depleted of 15 N, from the top of the first 15 N separation column. The by-products nitric acid and sulphuric acid, both depleted of 15 N and 18 O, are of commercial interest. (author)

Extraction of Trivalent La, Nd and Eu from Nitric Acid Solution by Ion quest-801 Loaded on Lewatit CA 9221

International Nuclear Information System (INIS)

Nowier, H.G; Metwally, S.S; Abd El-Rehim, S.S; Aly, H.F.

2005-01-01

The extraction of La 3+ , Nd 3+ and Eu 3+ from nitric acid medium by Lewatit CA 9221, Containing 2-ethylhexyl mono -2- ethylhexyl phosphonic acid ester, Ion quest-801, was studied. Batch experiments were carried out to investigate the effect of contact time, V/M ratio, extractant concentration, nitric acid molarity, lanthanide concentration and temperature. The data obtained are discussed in terms of extraction equilibrium and separation factors between the lanthanides as well as certain sorption models. Possible use of column chromatography containing the developed extractant material was assessed

Microsystems for anion exchange separation of radionuclides in nitric acid media

Energy Technology Data Exchange (ETDEWEB)

Losno, M.; Brennetot, R.; Mariet, C. [DEN/Service d' Etudes Analytiques et de Reactivite des Surfaces - SEARS, CEA, Centre de Saclay, Universite Paris-Saclay, F-91191, Gif sur Yvette (France); Ferrante, I.; Descroix, S. [MMBM Group, Institut Curie Research Center, CNRS UMR 168, Paris (France)

2016-07-01

An efficient and reproducible photo-polymerized poly(ethylene glycol methacrylate methacrylate-co- allyl methacrylate) monolith was synthesized and a photo-grafting process based on the ene-thiol click-chemistry has been performed to give anion exchange properties to the monolith. Since their introduction in the early 1990's polymethacrylate monoliths have emerged as a powerful alternative for microscale separations or sample treatment. Their relatively simple implementation in columns with small internal diameters makes them particularly attractive for the new chromatographic challenges of complex matrices analysis and on-chip separations. Despite their relatively poor ion-exchange capacity due to their highly porous structure, their use as anion exchangers is of large interest for nuclear analysis as numerous separations are based on this process. This paper presents a systematic study of the synthesis of the polymeric porous monolith and the versatile and robust functionalization method developed for the specific strong acidic media used in radiochemical procedures. The robustness of the stationary phase was tested in concentrated nitric acid. It appears that the C-S bond formed via thiol-ene chemistry is strong enough to be used to graft function of interest for separation in strong nitric acid medium. The photo-grafted anion exchanger, a quaternary ammonium, presents sufficient resistance to be used for radionuclide separation in [HNO{sub 3}]=5 mol.L{sup -1}so the next step is its integration in the cyclo olefin copolymer (COC) micro-system.

Adsorption of NI (II on activated Carbon of Coconut shell Chemicaly Modifieded with Acid Nitric Solutions

Directory of Open Access Journals (Sweden)

Mónica Hernández-Rodríguez

2017-01-01

Full Text Available In the research the effect of modification of coconut shell activated carbon with diluted solutions of nitric acid, in its chemical characteristics and removal capacity of the nickel (II ions present in modeling solutions of sulfates with similar characteristics to the acid liquor waste of the nickel industry, was studied. The characterization of the adsorbent material evidenced that the modification process increases the superficial acids groups according with the increase of acid nitric concentration employee in the treatment. The adsorption equilibrium tests, carried out with metallic species solutions at concentrations between 0,5 and 3,5 g/L evidenced that the process is described by Freundlich model. The effect of chemical modification of the adsorbent material in adsorption capacity of nickel (II ions was evaluated using a traditional experimental design at pH of 1,2 and 6,9 units, obtaining that the increase of acid groups in the carbon surface causes an increase of adsorption capacity and removal percentages of nickel (II, due to specific interactions of these groups with the metal cations.

Role of 4-tert-Butylpyridine as a Hole Transport Layer Morphological Controller in Perovskite Solar Cells.

Science.gov (United States)

Wang, Shen; Sina, Mahsa; Parikh, Pritesh; Uekert, Taylor; Shahbazian, Brian; Devaraj, Arun; Meng, Ying Shirley

2016-09-14

Hybrid organic-inorganic materials for high-efficiency, low-cost photovoltaic devices have seen rapid progress since the introduction of lead based perovskites and solid-state hole transport layers. Although majority of the materials used for perovskite solar cells (PSC) are introduced from dye-sensitized solar cells (DSSCs), the presence of a perovskite capping layer as opposed to a single dye molecule (in DSSCs) changes the interactions between the various layers in perovskite solar cells. 4-tert-Butylpyridine (tBP), commonly used in PSCs, is assumed to function as a charge recombination inhibitor, similar to DSSCs. However, the presence of a perovskite capping layer calls for a re-evaluation of its function in PSCs. Using TEM (transmission electron microscopy), we first confirm the role of tBP as a HTL morphology controller in PSCs. Our observations suggest that tBP significantly improves the uniformity of the HTL and avoids accumulation of Li salt. We also study degradation pathways by using FTIR (Fourier transform infrared spectroscopy) and APT (atom probe tomography) to investigate and visualize in 3-dimensions the moisture content associated with the Li salt. Long-term effects, over 1000 h, due to evaporation of tBP have also been studied. Based on our findings, a PSC failure mechanism associated with the morphological change of the HTL is proposed. tBP, the morphology controller in HTL, plays a key role in this process, and thus this study highlights the need for additive materials with higher boiling points for consistent long-term performance of PSCs.

Separation of An(III) from PUREX raffinate as an innovative SANEX process based on a mixture of TODGA/TBP

International Nuclear Information System (INIS)

Sypula, Michal; Wilden, Andreas; Schreinemachers, Christian; Modolo, Giuseppe

2010-01-01

Within the ACSEPT project, an innovative SANEX process based on TODGA/TBP for selective An(III) separation from PUREX raffinate was studied. Oxalic acid usually used for Zr complexation is considered a weak point. An investigation to substitute oxalic acid with a different masking agent was carried out. A new masking agent already studied in FZJ was applied and showed good complexation properties towards Zr and Pd. Re-investigation of the formula of the actinide stripping solution was also performed. Good separation of Ln over Am was obtained by means of DTPA and malic acid. Glycine appeared to be the strongest within the tested buffers. (authors)

Lessons learned from on-site safety assessments performed by DOE in response to the Tomsk accident

International Nuclear Information System (INIS)

Witmer, F.E.

1995-01-01

In response to the accident, in April 1993, at the nuclear fuel reprocessing plant of the Siberian chemical Combine, Tomsk, Russia, the U.S. Department of Energy (DOE) initiated concurrent efforts to understand the causes for the accident and to review potential vulnerabilities for similar occurrences across the DOE radiochemical complex. Because the accident occurred in the feed adjustment stage of a Purex type process, US facilities which contained significant inventories of TBP, organic diluent and nitric acid were evaluated by expert teams. From accident conditions, prior experience, modeling and experimental programs and confirmatory dialogue with the Russians, enhanced understanding was achieved and vulnerabilities (e.g., lack of safety analysis, organic layering, inadvertent acid addition, use of aromatic diluents, uncertain venting capability, no mitigative/emergency procedures, etc.) were identified and corrected

Development of ion-exchange properties of bamboo charcoal modified with concentrated nitric acid

Science.gov (United States)

Khandaker, S.; Kuba, T.; Toyohara, Y.; Kamida, S.; Uchikawa, Y.

2017-08-01

The surface chemistry and the structural properties of activated carbon can be altered by the acidic modification. The objective of this study is to investigate the changes occurring in bamboo charcoal (BC) during activation with concentrated nitric acid. Low temperature (500°C) carbonized BC has been prepared and oxidized with 70% concentrated boiling nitric acid (BC-AC). The porous properties of the BC are analyzed with nitrogen adsorption isotherm at 77 K. The surface structure is observed by Field emission scanning electronic microscope (FESEM) and the surface functional groups are examined by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and the pH of the point of zero charge (pHPZC). The results reveal that severe oxidation with HNO3 considerably decreases the surface area of BC with enhanced pore widening and FESEM observation demonstrates the erosive effect of oxidation. The FTIR analysis detects that some absorption bands are assigned for carboxyl, aldehyde and ketone groups on BC-AC. The XPS analysis also clearly shows that the ratio of oxygen and acidic functional groups has been enriched significantly on the BC-AC. The low pHPZC value of BC-AC confirms that the surface is highly acidic for the fixation of acidic functional groups on surface. In general, the existence of the abundant amount of acidic functional groups on adsorbents enhances the sorption of heavy metals ions in aqueous solution. Therefore, it is strongly expected that the modified BC, activated under the proposed conditions would be a promising ion exchanger in aqueous solution and can be applied for the adsorption of different heavy metal ions and radioactive materials from effluent.

Direct extraction of uranium and plutonium from oxide fuel using TBP-HNO3 complex for super-DIREX process

International Nuclear Information System (INIS)

Miura, S.; Kamiya, M.; Nomura, K.; Koyama, T.; Ogum, S.; Shimada, T.; Mori, Y.; Enokida, Y.

2004-01-01

Super-DIREX is a new reprocessing method which has high economical efficiency. Experimental study of this process was started on the direct extraction of U and Pu from irradiated MOX fuel by the supercritical carbon dioxide (SFCO 2 ) containing TBP-HNO 3 complex. This report describes direct extraction of U and Pu with TBP-HNO 3 complex at atmospheric pressure, as the first test for irradiated fuel, in order to investigate the applicability of SFCO 2 containing TBP-HNO 3 complex. In this test, dependency on dissolution temperature, Pu content, fuel/ TBP-HNO 3 complex ratio and effect of voloxidation were investigated. From these results, TBP-HNO 3 complex was found to be effective in the respect of the recovery of U and Pu. The number of the process step in dissolution and co-extraction is small, and amount of waste can be reduced. It is applicable to the direct extraction in Super-DIREX. (authors)

Evidence for a link between atmospheric thermonuclear detonations and nitric acid

International Nuclear Information System (INIS)

Holdsworth, G.

1986-01-01

Data are presented for an ice core, which show that during the era of intense atmospheric thermonuclear weapons testing, a significant part of the nitrate content in the snow was modulated by the intensity of the nuclear detonations. The fixation of nitrogen by nuclear fireballs leads to NOsub(x) gases in the atmosphere and ultimately to nitric acid in precipitation. At certain concentrations, these gases and the associated aerosols may perturb the climate. (author)

Extraction behavior of radionuclides in the first separation cycle in reprocessing

International Nuclear Information System (INIS)

Uchiyama, Gunzo; Asakura, Toshihide; Hotoku, Shinobu; Watanabe, Makio; Fujine, Sachio; Nemoto, Hideyuki.

1997-01-01

The chemical flowsheet experiment by using three mixer-settlers was conducted to study the extraction behavior of radionuclides such as technetium, neptunium, iodine, zirconium and ruthenium in the uranium-TBP-nitric acid solution system in the simulated first separation cycle in current reprocessing plants. The following results were obtained: More than 99.999% of the total uranium fed to the co-decontamination step in the simulated dissolver solution was extracted by TBP solvent. About 90% of the total uranium was recovered in the uranium back-extraction step. About 30% of the total neptunium fed to the co-decontamination step was in the raffinate solution in the co-decontamination step, 12% of the total neptunium was in the Tc solution in the Tc separation step and about 58% of the total neptunium was in the Pu solution in the U/Pu partitioning step. As for technetium, about 99% of the total technetium was extracted by TBP in the co-decontamination step, 86% of the total technetium was scrubbed with high acid nitric acid solution in the Tc separation step and 13% of the total technetium was in the Pu solution in the U/Pu partitioning step. As for the other radionuclides, 99% of the total ruthenium and 93% of the total zirconium were distributed into the raffinate in the co-decontamination step. In the Tc separation step, ruthenium was scrubbed more effectively than ruthenium with high acid solution. About 45% of the total iodine fed to the co-decontamination step was vaporized during the experiment. Iodine in aqueous solutions in the flowsheet was mainly in volatile I 2 form. Iodine was rarely distributed into the aqueous solution and was distributed with TBP solvent in the flowsheet. Significant amounts of iodine was contained in the washed solvent. (author)

Solar fuels and chemicals system design study (ammonia/nitric acid production process). Volume 2. Conceptual design. Final report

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