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Title: Real-Time Automated pH Control within Batch Processes Relying on Raman pH Measurement

Journal Article · · ACS Omega

Nuclear fission is an energy source that can provide consistent power with very low associated carbon emissions. However, management of the used nuclear fuel is an important aspect of the application of nuclear power. Recycling of useful components from used fuel is an attractive option, but this involves chemical processing of the fuel. Possible chemical separation technologies that might be used in this regard are sensitive to solution pH. Raman spectroscopy is a promising technique for monitoring the pH of solutions in real time. Classical pH probes are too fragile to be used in the harsh environments encountered in nuclear fuel processing. Raman probes are robust and can withstand these harsh environments to track pH. Coupled with chemometric analysis, the demonstration of the use of Raman spectroscopy to track and predict the pH in carboxylate-buffered systems is made possible. Utilizing this spectroscopy in conjunction with Programmable Logic Controllers mimics industrial control systems used in many modern industrial settings. This showcases a pragmatic approach toward leveraging Raman spectroscopy and chemometric model outputs as inputs for a real-time control system. The model to predict pH created by chemometrics proved to be successful in tracking pH. The optimal pH for TALSPEAK extraction of lanthanides and actinides from aqueous solution is known to proceed in a narrow pH range of around pH = 2.8 ± 0.1. This study uses Raman optical monitoring and automated control to return and maintain solution pH within this range after acid or base perturbations move the solution pH well outside this region. Root-mean-square errors show that pH changes measured using Raman spectroscopy on the batch process solution are reliably measured and used to automatically correct and maintain solution pH. Measurement of solution pH tracks favorably with electrochemical pH probe comparison measurements. As a result, the ability to showcase Raman spectroscopy paired with chemometrics analysis acts as a durable, better alternative data source compared to traditional pH probes to optimize the separation efficiency in the used nuclear fuel processing.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2563629
Journal Information:
ACS Omega, Journal Name: ACS Omega Vol. 10; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (48)

Pre‐whitening of data by covariance‐weighted pre‐processing journal March 2003
Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems journal September 2017
The Thorp Approach to Safe Control book January 1987
Uranium(VI) speciation by spectroscopy journal October 1997
The Nuclear Fuel Cycle book January 1995
Spectrophotometric determination of Rare Earth Elements in aqueous nitric acid solutions for process control journal April 2015
Review of on-line and near real-time spectroscopic monitoring of processes relevant to nuclear material management journal April 2020
Symmetric cell for improving solid-contact pH electrodes journal January 2023
Measuring local pH in electrochemistry journal February 2021
Nuclear power, climate change and energy security: Exploring British public attitudes journal September 2011
On-line monitoring applications in nuclear power plants journal March 2011
The development of future options for aqueous recycling of spent nuclear fuels journal October 2023
Implementation of Americium Separation from a PUREX Raffinate journal January 2012
Monitoring of pollutant in waste water by infrared spectroscopy using chalcogenide glass optical fibers journal June 2004
Water O–H Stretching Raman Signature for Strong Acid Monitoring via Multivariate Analysis journal March 2013
Development of Online Spectroscopic pH Monitoring for Nuclear Fuel Reprocessing Plants: Weak Acid Schemes journal April 2015
Enabling Microscale Processing: Combined Raman and Absorbance Spectroscopy for Microfluidic On-Line Monitoring journal December 2020
Raman Spectroscopy Coupled with Chemometric Analysis for Speciation and Quantitative Analysis of Aqueous Phosphoric Acid Systems journal March 2021
Development of Online pH Monitoring for Lactic, Malonic, Citric, and Oxalic Acids Based on Raman Spectroscopy Using Hierarchical Chemometric Modeling journal December 2022
Multivariate Analysis for Quantification of Plutonium(IV) in Nitric Acid Based on Absorption Spectra journal August 2017
Reimagining pH Measurement: Utilizing Raman Spectroscopy for Enhanced Accuracy in Phosphoric Acid Systems journal March 2020
Exploring the Complex Chemistry of Uranium within Molten Chloride Salts journal September 2023
Online, Real-Time Analysis of Highly Complex Processing Streams: Quantification of Analytes in Hanford Tank Sample journal October 2019
Overcoming Oxidation State-Dependent Spectral Interferences: Online Monitoring of U(VI) Reduction to U(IV) via Raman and UV–vis Spectroscopy journal April 2020
Quantification of Uranium in Complex Acid Media: Understanding Speciation and Mitigating for Band Shifts journal October 2023
PCA and PLS Analysis of Lanthanides Using Absorbance and Single-Beam Visible Spectra journal July 2024
Sensor Fusion: Comprehensive Real-Time, On-Line Monitoring for Process Control via Visible, Near-Infrared, and Raman Spectroscopy journal July 2020
Challenges for Actinide Separations in Advanced Nuclear Fuel Cycles book January 2010
Potentiometric titrations using Gran plots: A textbook omission journal July 1965
Non-linear multivariate curve resolution applied to the spectrophotometric determination of cerium( iii ) in aqueous nitric acid solutions for process control journal January 2016
Development and testing of a novel micro-Raman probe and application of calibration method for the quantitative analysis of microfluidic nitric acid streams journal January 2018
Review Article: A Review of the Development and Operational Characteristics of the TALSPEAK Process journal October 2007
Recent Advances in the Development and Application of Annular Centrifugal Contactors in the Nuclear Industry journal December 2013
An Advanced TALSPEAK Concept Using 2-Ethylhexylphosphonic Acid Mono-2-Ethylhexyl Ester as the Extractant journal December 2014
A Review of Online Monitoring within Used Nuclear Fuel Recycling Processes journal July 2024
Review of multidimensional data processing approaches for Raman and infrared spectroscopy journal June 2015
Electrochemical Oxidation and Speciation of Lanthanides in Potassium Carbonate Solution journal April 2022
Measuring Nd(III) Solution Concentration in the Presence of Interfering Er(III) and Cu(II) Ions: A Partial Least Squares Analysis of Ultraviolet–Visible Spectra journal October 2021
Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States journal February 2022
Stimulated Raman generation in two-mode long-length fibers pumped by a mode-locked laser journal October 1982
Long fiber-optic remote Raman probe for detection and identification of weak scatterers journal December 1992
Ultrafast pH-jump two-dimensional infrared spectroscopy journal October 2019
Combination of optical spectroscopy and chemometric techniques—a possible way for on-line monitoring of spent nuclear fuel (SNF) reprocessing journal March 2012
Advanced separation techniques for nuclear fuel reprocessing and radioactive waste treatment book January 2011
Chemical engineering for advanced aqueous radioactive materials separations book January 2011
Standard and advanced separation: PUREX processes for nuclear fuel reprocessing book January 2011
On Line Spectrophotometric Measurement of Uranium and Nitrate in H Canyon report July 2002
Detection of Water pH Using Visible Near-Infrared Spectroscopy and One-Dimensional Convolutional Neural Network journal August 2022