Search Results

You are looking at 1 - 10 of 23 items for

  • Author or Editor: Shekhar Kumar x
  • Refine by Access: All Content x
Clear All Modify Search

Abstract  

Study of runaway reaction between tri-n-butyl phosphate (TBP) and nitric acid resulting in red-oil formation (and related problems) in the process evaporators of reprocessing plants has been a major safety concern since last 50 years. Thermal decomposition of nitrated TBP results in rapid pressurization and in close-vent condition it may lead to failure of process vessel and containment. Thermal decomposition of nitrated TBP is reported in the literature but corresponding studies for alternate PUREX/UREX solvent tri-iso-amyl phosphate (TiAP) are not available. In this work, comparative study of the thermal decomposition of nitrated solvents (TBP as well as TiAP) under adiabatic conditions in a sealed autoclave is presented. Experimental results indicate much lesser pressurization in the case of TiAP as compared to TBP.

Restricted access

Abstract  

Thermophysical properties of alternate PUREX/UREX extractant tri-iso-amyl phosphate (TiAP) in different diluents are not available in literature. In this study, density, viscosity and refractive indices of 36% v/v TiAP solutions (~1.1 M) in C6–C16 n-alkanes, benzene, toluene, carbon tetrachloride and iso-octane at 298.15 K and 0.1 MPa have been measured experimentally. In the case of n-alkanes, these properties were correlated by empirical functions of carbon number of diluents. In addition, for 36% TiAP and 100% TiAP solutions, nitric acid extraction studies were also performed and acid uptakes as well as thermophysical properties of equilibrated phases were also measured. Compositions of solvates in equilibrated organic phases were also proposed.

Restricted access

Abstract  

Flash point of a chemical characterizes its operating safety envelope. Tri-isoamyl phosphate (TiAP) is being proposed as an alternate to conventional nuclear solvent tri-n-butyl phosphate but flash point of TiAP containing organic solutions are not available in literature. Flash points of C8–C16 n-alkanes and 36% TiAP/C8–C16 n-alkane solutions were experimentally measured and correlated by means of empirical correlations. This paper is probably the first reported work in the literature on flash points of TiAP containing solutions.

Restricted access

Abstract  

Conventionally composition of the actinide-extractant solvate is assumed to be the same in the unpartitioned organic phase and the formed third phase. For example, if a m:n solvate has formed during extraction, the solvate is expected to be in the same state even during the third phase condition. However contemporary analysis, based on the spectroscopy measurements and empirical observations, has indicated the presence of an extended solvate. In this article, the proposed speciation in nitric acid and U(VI) third phase formation in nn dialkyl amide/dodecane-nitric acid systems has been modeled with empirical correlations.

Restricted access

Abstract  

Tri-n-butyl phosphate (TBP) is the workhorse of solvent extraction operations in nuclear fuel cycle as well as an important industrial chemical. Its PVT properties are not available in literature. In this study, PVT properties of TBP, estimated using group contribution method, are reported. Wagner constants were also reported in the range of 273.15 K to critical temperature.

Restricted access

Abstract  

Miniature annular centrifugal contactors are nearly perfect for shielded hot-cell applications during flowsheet evaluation but these contactors require complex maintenance of electrical drive-motors during radioactive experiments. To reduce the number of electrical drives in the shielded cell, an indigenous design of miniature Taylor Couette (TC) mixing based countercurrent differential extraction column has been developed. In this paper, results of mass transfer experiments for an indigenously developed TC column with 30% TBP/aqueous nitric acid solutions are reported. The developed device worked perfectly in counter–current differential mode and demonstrated equivalence to multiple-extraction stages while working with a single electrical drive. The developed TC unit demonstrated operation with a reduced efficiency without flooding even in absence of rotor rotation. This observation is a vital step towards designing of robust contactors, which do not flood during temporary power failure or failure of drive mechanism.

Restricted access

Abstract  

Acetohydroxamic acid (AHA) is an important complexant/reductant for Pu(IV) in the UREX process. It decomposes in the presence of nitric acid. In literature, its decomposition kinetics in nitric acid is traditionally reported as pseudo-first order reaction. In this study, new experimental data were reported for kinetics experiments under wide consecration conditions. It was found that the decomposition reaction was first order with respect to both the components hence overall second order.

Restricted access

Abstract  

Urea-adduct process is commercially used to selectively separate n-alkanes from industrial hydrocarbon mixtures. Authors have explored application of this method for recovery of n-alkane based diluents from spent PUREX/UREX solvent. Traditionally this separation is performed by vacuum distillation, an energy-intensive process. The proposed method is simple and does not involve either exotic chemicals or complex processing steps. Application of urea-adduct process for recovery of diluent from spent solvent is reported here possibly first time in literature. Physical properties such as densities, viscosities and vapour pressure for irradiated organic solutions were also measured and reported.

Restricted access

Abstract  

N,N,N′,N′-Tetraoctyl-3-oxapentanediamide (TODGA) is a versatile extractant for partitioning of fission products from highly active raffinate wastes. Its PVT properties are not available in literature. In this work, PVT properties of TODGA, estimated using group contribution method, are reported. A corresponding-states based equation as well as Wagner constants were also reported in the range of 273.15 K to critical temperature.

Restricted access

Abstract  

Hydroxyurea and its derivatives are important nonsalt forming reductants in partitioning of uranium and plutonium in the nuclear fuel reprocessing operations. There is no experimental data available in open literature describing pressurization due to the thermal decomposition of aqueous and nitric solutions of hydroxyurea at elevated temperatures. Authors studied thermal decomposition of hydroxyurea-nitric acid system and resultant pressurization at various concentrations of nitric acid in an adiabatic calorimeter in closed-vent conditions. During these experiments, pressurization was observed. In this paper, results of these experiments have been discussed.

Restricted access