Thermal Decomposition of Nitrated Tributyl Phosphate

Abstract

This report was prepared by Westinghouse Savannah River Company (WSRC) for the United States Department of Energy under Contract No. DE-ACO9-89SR18035 and is an account of work performed under that contract. Reference herein to any specific commercial product, process, or service by trademark, name, manufacturer or otherwise does not necessarily constitute or imply endorsement, recommendation, or favoring of Same by WSRC or by the United States Government or any agency thereof. The views and opinions of the authors fexpressed herein do not necessarily state or reflect those of the United States

Red Oil Excursions: A Review

“…Paddleford et al (28) and Hou et al (29) studied the decomposition of nitrated TBP by subjecting TBP, nitric acid, and water mixtures to thermal decomposition. The gaseous and liquid decomposition product yields were observed to be highly path dependent.…”

Synthesis of N,N,N′,N′-Tetraoctyl-3-oxapentane-1,5-diamide (TODGA) and Its Steam Thermolysis-Nitrolysis as a Nuclear Waste Solvent Minimization Method

“…22−24 Thermal decomposition of red oil in closed evaporators results in rapid pressurization due to the formation of N 2 , O 2 , H 2 , CO, CO 2 , N 2 O, NOx, and hydrocarbon gases (C 1 −C 4 ) and ultimately ends in explosive runaway reactions, which is often mentioned as a big source of worry. 25 Recently, different groups of amides have been extensively studied as alternative extractants to the phosphate based solvents. 26−29 The completely incinerable N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) has shown high distribution ratio (D) for actinide (Ac) ions between HNO 3 and n-dodecane.…”

“…However, the eliminated waste TBP and its analogues cannot be decomposed, and an enormous amount of phosphate bearing solid waste has to be managed at the end of its life cycle. − In addition, TBP has some drawbacks such as thermal and radiochemical instability under the operating conditions, the troublesome nature of its decomposition products, and its severe toxicity. − During the process of evaporation, to concentrate the aqueous waste or product nitric acid solutions, the dissolved or entrained TBP and its hydrolysis products, butanol is nitrated easily by HNO 3 and produces red oil (i.e., mixture of organic nitrates, nitrites, phosphates, alcohols, etc.) at above 130 °C. − Thermal decomposition of red oil in closed evaporators results in rapid pressurization due to the formation of N 2 , O 2 , H 2 , CO, CO 2 , N 2 O, NOx, and hydrocarbon gases (C 1 –C 4 ) and ultimately ends in explosive runaway reactions, which is often mentioned as a big source of worry …”