Butyraldehyde Oxime Anti-Nitrous Agent in Plutonium Reductive Back-Extraction

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Solution Overview

Problem

The reductive stripping of plutonium from an organic phase to an aqueous phase in nuclear fuel reprocessing is hindered by the inability of existing anti-nitrous agents like hydrazine to prevent reoxidation of plutonium(III) to plutonium(IV), leading to significant reagent consumption and operational constraints due to the agent's inextractability in the solvent phase.

Innovation Solution

The use of butyraldehyde oxime as an anti-nitrous agent, which is extractable in the solvent phase and effectively blocks the reoxidation of plutonium(III) to plutonium(IV), reducing the need for uranium nitrate and hydrazine and simplifying the reductive plutonium stripping operation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If hydrazine is used as an anti-nitrous agent in the aqueous phase, then nitrous acid destruction is achieved, but significant reagent consumption occurs and reoxidation of plutonium(III) to plutonium(IV) cannot be prevented in the solvent phase

Engineering Contradiction:
Improveprevention of plutonium reoxidationVSAvoiduranium nitrate and hydrazine consumption
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

Butyraldehyde oxime acts as an intermediary substance that transfers from the aqueous phase to the solvent phase, where it directly prevents plutonium(III) reoxidation. This mediator approach eliminates the need for large excesses of uranium nitrate and hydrazine, reducing reagent consumption while maintaining reliable prevention of reoxidation.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the chemical parameter of the anti-nitrous agent from hydrazine (water-soluble) to butyraldehyde oxime (organic-soluble). This parameter change allows the anti-nitrous agent to be present in the solvent phase where plutonium reoxidation occurs, fundamentally improving prevention reliability while reducing overall reagent consumption.

Inventive Principle:
Principle #35Parameter changes

2Object-generated harmful factors

If hydrazine is used as anti-nitrous agent, then nitrous acid is destroyed in aqueous phase, but additional operational constraints are imposed due to azohydric acid formation and explosiveness risks

Engineering Contradiction:
Improveazohydric acid formationVSAvoidoperational constraints and safety requirements
Core Design Contradiction:
Object-generated harmful factorsVSEase of operation

Solution Approach 1:

Butyraldehyde oxime serves as an intermediary that prevents the formation pathway of azohydric acid by blocking plutonium reoxidation in the solvent phase. This eliminates the harmful azohydric acid generation step, thereby removing the associated operational constraints and safety concerns regarding explosiveness.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention converts the harmful effect of nitrous acid (which leads to azohydric acid formation) into a beneficial outcome by using butyraldehyde oxime to prevent the intermediate reoxidation step. This eliminates the harmful azohydric acid pathway entirely, transforming a potentially dangerous process into a safer operation.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Object-generated harmful factors

If hydrazine is used as anti-nitrous agent, then nitrous acid destruction is achieved, but additional sodium supply is required for neutralization which conflicts with glass vitrification specifications

Engineering Contradiction:
Improveazohydric acid requiring neutralizationVSAvoidsodium content in waste stream
Core Design Contradiction:
Object-generated harmful factorsVSQuantity of substance

Solution Approach 1:

Butyraldehyde oxime acts as an intermediary that prevents azohydric acid formation by blocking plutonium reoxidation. This eliminates the need for sodium neutralization, thereby preventing additional sodium from entering the waste stream and avoiding conflicts with glass vitrification specifications.

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

Butyraldehyde oxime significantly reduces reagent consumption, eliminates operational constraints, and increases the plutonium concentration factor, simplifying equipment design and operation by preventing reoxidation in the solvent phase.

Implementation Method 1

The presence of plutonium(III) in the solvent phase, even in small quantities, catalyzes the oxidation of uranous nitrate through the first two reactions and thereby generates nitrous acid. Butyraldehyde oxime blocks this reoxidation process.

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Implementation Method 2

The reduction of plutonium(IV) to plutonium(III) is induced by a reducing agent which is added to the aqueous phase. The reducing agent used to extract the plutonium during the partitioning of the U/Pu flows is the uranous nitrate or U(IV).

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 3

The reaction of destruction of nitrous acid by hydrazine only takes place in the aqueous phase. The azohydric acid formed by the reaction of destruction of nitrous acid by hydrazine reacts in turn with nitrous acid.

Methodology Applied
Scientific EffectChemical reactions: Chemical Bonding

Implementation Method 4

passing this element from an organic phase (or solvent phase), in which it is at the oxidation state (IV), into an aqueous phase

Methodology Applied
Scientific EffectLiquid-liquid extraction: Liquid-Liquid Extraction

Data Source

PatentEP2162888B1Use of butyraldehyde oxime as Anti-nitrous agent in an operation for the reductive back-extraction of plutonium
Publication Date: 2014.04.16 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP2162888B1 patent drawingFigure 1~2
  • EP2162888B1 patent drawingFigure 3~4

AI summary

The invention relates to the use of butyraldehyde oxime as anti-nitrous agent in an operation for back-extracting plutonium based on a reduction of this element, from oxidation state (IV) to oxidation state (III). Applications: any method of reprocessing spent nuclear fuel in which the use of a compound having the two properties of being extractable in organic phase and capable of destroying the nitrous acid therein may be useful, and in particular to all those methods that comprise one or more operations for the reducing back-extraction of plutonium.