Improved Performance of the Alkaline-Side CSEX Process

60 Pages·2001·6.05 MB·English

ORNIJTM-1999/209
Improved Performance of the
Alkaline-Side CSEX
Process for Cesium Extraction
from Alkaline High-Level Waste
Obtained by Characterization of
the Effect of Surfactant Impurities
Laetitia H. Delmau
Gary J. Van Berkel
Peter V. Bonnesen
Bruce A. Moyer
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j : IMPROVEI)PERFORMANCEOFTHEALKALINE-SIPECSEXPROCESSFOR
c s /Irc,.".
CE~IUMEXTRACTIONFR~MALKALINEHIGH-LEVELWASTEOBTAINEDBY
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CHARACTERIZATIONOFTHEEFFECTOFSURFACTANTIMPURITIES
r* Laetitia H. Delmau, Gary J. Van Berkel, Peter V. Bonnesen, and Bruce A. Moyer
I. II
Chemical and Analytical SciencesD ivision
Oak Ridge National Laboratory
P.O. Box 2008, Oak Ridge, Tennessee,3 78316119 USA
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., The submitted manuscript has been authored by a
contractor of the U.S. Government under contract No.
DB-AC05960R22464. Accordingly, the U.S.
Government retains a nonexclusive, royalty-free license
to publish or reproduce’ the published form of this
contribution, or allow others to do so, for U.S.
m
Government purposes.
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This researchw as sponsoredb y the Efficient Separations and Processing Crosscutting Program,
Office of Science and Technology, Office of Environmental Management, U. S. Department of
Energy, under contract number DE-AC05-960R22464 with Oak Ridge National Laboratory,
managed by’lockheed Martin Energy ResearchC orp.
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ORN-UTM- 1999/209
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Chemical and Analytical SciencesD ivision
IMPIiOVED -PtiRFORklANCti Op. THE ALKALINE-SIDE CSEX PldoCESS FOR
p CESIUM EXTRACTION FROM ALKALINE HIGH-LEVEL WASTE OBTAINED
; BY C’HARACTERIZATION (SF THE EFFECT OF SURFACTANT IMPURITIES
Laetitia H. Delmau, Gary J. Van Berkel, Peter V. Bonnesen, and Bruce A. Moyer
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Date Published-October 1999
\ _\,? , .._,
Preparedf or the
U. S. Department of Energy, Office of Environmental Management,
Office of Sciencea nd Technology,
Efficient Separationsa nd ProcessingC ross-Cutting Program
Preparedb y the
OAK RIDGE NATIONAL LABORATORY
Oak Ridge, Tennessee3 783 l-61 19
managedb y
LOCKHEED MARTIN ENERGY RESEARCH CORP.
for the
U. S. DEPARTMENT OF ENERGY
under contractD E-AC05-960R2.2464
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L i . .. . ,,_ “ ..,.) / .. CONTENTS ..)
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i: LIST OF FIGURES . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . .. .. .. . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . .. . .. . . . . . . . .. .. .. . . . . . . .. . . . . . . . . . . . . v
LIST OF TABLES . . . . . . . . . . . . . . . . .. . . . . .. . . . ..“....‘~................................................................................“. vi
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ACKNOWLEDGMENTS . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . .. . . . . .. . . . .. . . . . . . . . . . . . . . . .. .. . . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . .. . . . . .v ii
s EXECUTIVE SUMMARY . . ..“........................~...............................~............................................i x
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1. PROJECT OBJECT& . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . .. . . . . .. . . . . . . .. . .. . .. . . . . . . . . . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . .. . 1
m 1.1 OVERALL PROGRAM OBJECTIVES . . . . . . . . .. . . .. . . . . . .. . . .. . . . . . . .. . . . . .. . .. . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 PROCESSING REQUIREMENTS .. . . . . . . . . . . . . . .. . . .. . .. . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . .. . . . ...*.2
1.3” SUMMARY-• F’TIIE PREVIOUS RESULTS . . .. . . . . . . !..::.:.:Z.:: . . .. .. . . . . .. . .. . . . .. . . . . . . . . 3
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.I 1.4 QUESTIONS NEEDING TO BE ANSWERED .. . . . . . .. . . . .. . . . . . .. . .. . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . 5
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iF INITIALTiSTS1 ^-. ‘. i _ : t, ._,, 2, , “_ ._ _ .. , ._... ,__. ‘. .~
L 1 2. . .. . . . . . . . .. . . . . . . . . . . . . . . .. . . . . .. . . . . . .. . . .. .. . . . . . . .. . . .. . . . . .. .. . .. . .. .. . . . . . . . . . . . . .. . . . . .. . . . . . . . . . . . . . . . . 6
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Ib7 j 2.1 INTRODUCTIO_ N ,/ _.. ,r ., .,_ . . . .. .” . . ., .‘ .. . . .. . . . . . . . .. . . . . . . . . . . . .- .: .>. .I . . . . .i. , . . .. . . .. . . . . . . .. . . . . .. . .. . . . . . . . . . . . . . . . . . . ._ . . . . . 6
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2.2 EXPERIMENTAL .................................................................................................. 6
2.2.1 Materials and Instrumentation ..................................................................... 6
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2.2.2 Contacting~~rocetfi;res... . : ..:. .....: ^... .:..... i.‘:;.. ...........: .::..:.:....:::,~.~..~...~... ...... .12
p 2.3 RESULTS AND DISCUSSION ............................................................................ 13
2.3.1 Cesium Extraction from Simulants Preparedf rom ANL Salts... ................ .13
2.3.2 Influence of Physical Methods . . . . . . . . . . . . . . . . . . . . . . .. . . . .. . . . . . . .. . . . . . . . .. . . . . . . .. . . . . . . .. . . . . . 14
ra
i 2.3.3 Influence of Multiple Extractions . .. . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .. . .. . . . . . . . . . . . . .. . .. . . . . . 15
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2.3.4 Influence of Simulant Pre-Wash. . . .. .. . .. . .. .. . . .. . .. . . .. . . . .. . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . 16
2.‘3.5 Influence of Trioctylamine Addition . . ..t..................................................... 17
-2.4 CONCLUSIONS . . . . . . . . . . . .. . . . .. . . . . .. . . . . . .. . . . . . . . . . . . . . . .. . . . . . .. . . . .. . . .. . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . 18
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3. ELECTROSPRAY EXPERIMENTS . . . . . . . . . . . .. . .. . . .. .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . ..~......~.1 9
3.1 INTRODUCTION ................................................................................................ 19 -
3.2 EXPERIMENTAL ................................................................................................ 19
3.2.1 Materials and Contacting Procedure. ......................................................... 19 -
3.2.2 Electrospray Analysis ................................................................................ 20
3.3 RESULTS AND DISCUSSION.. ......................................................................... .20
3.3.1 Overview of the Solvent at Different Stages. ............................................. 20
3.3.2 Peak Identifications .................................................................................. .23
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3.3.3 Comparison Between Simulants ............................................................... .28
3.3.4 Identification of the Impurity.. .................................................................. -28
3.4 CONCLUSIONS .................................................................................................. 33
QUANTIFICATION AND REMEDIATION . . . . .. . . . . .. . . . . .. . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . ..*........... 34
4.1 INTRODUCTION ............................................................................................... .34
4.2 EXPERIMENTAL ............................................................................................... .34
4.2.1 Materials and Preparation of Solutions ...................................................... 34
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4.2.2 Contacting Procedures... ........................................................................... .35
4.3 RESULTS AND DISCUSSION ............................................................................ 35
4.3.1 Effect of Dodecylsulfonate Anion on Cesium Extraction .......................... .35
4.3.2 Approximation of the Quantity of Sulfonate Present in ANL Simulant .... ..3 7
4.3.3 Remediation with Trioktylamine.. ......................................... . ................... .38
4.4 CONCLUSIONS AND FURTHER DEVELOPMENTS I...................................... 38 ’
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5. REFERENCES . . . . . . .. . . . . . . . . . . . . . .. . . .. . . . . . . .. . . . . .. . . . . .. .. . . . . . . .. .. . . . . . . . .. . . . . . . ..I.................................. 41
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: LIST OF FIGURES
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1.1 Structures of Cs-3 and BoBCalixC6 . . . .. . . . . .. .. . .. . . . . . . .. . . . . .. . . . . . . . . . . . . .. . . . . . . .. . . . . . . . . . . . . . . . . . . . . 4
3.1 Cation-Mode Electrospray Spectrum of the Pristine Solvent . . . . . . . . . . . . . . . . . . . . . . . . . ..I..... 21
3.2 Cation-Mode Electrospray Spectrum of the Solvent Contacted 10 times with the
_ .;. ANL, Simulant . . . . . . .. . . . . . . .. . .. .. . . .. . . . . . . .. .. . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
~ L..x”“.,a,.Il” ., .,
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3.3 Anion-Mode Electrospray Spectrum of the Solvent Contacted 10 times with the
ANL Simulant . .. . .. . . . . . . .. . . . . . . .. .. . . . . .. . . . . . . . .. .. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . 24
3.4 Anion-Mode Blectrospray Spectrum of the Scrubbed Solvent . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . 25
~ .-,.. _ <z..,. _.. ! +.cI: ‘ %t ,.‘ ;A.-“.:# ..I .%is, “ . .*, ,._i ._,. ^_ +I .,..l., .clI‘,~.._ .p. /. ;,.’
3.5 . Anion-Mode Electrospray Spectrum of the Stripped Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
,_f .3.6 Struct,u,.rY,e, . ,o ~f/ . C_: s,<-,3, .., C o-n ,d‘.e~.nIi,>.s ,a. t.i.o .>,n. .P ,. ,r.o,,‘d“ Au,c_t .( M‘. ole_c_ucla, r Weigh,.t 642 g/mol) . . . . . . . . . . . . ...27
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3.7 Anion-Mode Electrospray Spectrum of the Solvent Contacted Twice with the
6k1 i
ANL Simulant...: .. . .. . . . . . . . . . i . . . . .. . . .. . . . . . .. . . . .. . . . . .. . . . .. . .l .....; . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . 29
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3.8 Anion-Mode Electrospray Spectrum of the Solvent Contacted Twice with the
oRTciL Sim;ilnt . ._
.. .. ; . .. . . . . . . .. . . . . . . .. . . .. . .. .. .. .. . . . . .. . .. . . . . . . .. . . . . . . . . . .. . . . . . .. . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . 29
8 .I _^, ___.*‘._ .,
3.9 Anion-Mode Electrospray Spectrum Electrospray Spectrum of a lOO,OOO-fold
dilution of&y@Liquid’Gei . . . . . . .. . . . . .. . i..: . . . . . . . ., ; . .. . . . . I.;.... . . . . . . . . . . . . I......; . . . . . . . . . . . . . . . . . . . 31
4.1 Effect of Dodecylsulfonate Anion on Cesium Distribution Ratios Under
Stripping Conditions . . . . . . . . . . . . . .. . . .. . . .. . . .. .. . . . .. . .. . . . . . . .. . . . . . . . . . . .. . . . . . . . . . . .. .. . . . . . . . . . . . . . . . . . . . . . . 36
4.2 Effect of TOA on Cesium Extraction in the Presenceo f Dodecylsulfonate
Anion m&e Siripping”Phase. . . . . . . .. . .: .I...: .. . . . . . . . . .I ..... ~~..................................,........3 9
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LIST OF TABLES
1.1 Alkaline Tank Waste Simulant . . . . .. . . . . . . . . . . . . .. .. . . . . . . . . . . . . . .. . . . . . .. . . . . . . . . . . . . . . . . .. .. . . .. . . . .. .. . . . . .2
2.1 Formulation of ORNL Simulant . . . . . . . . . . . . . .. . . . .. . . . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .. .. . . . .. . . 7
2.2 Formulation of ORNL Simulant Using ANL Salts and ORNL Water (ASOW-A) . ..8
2.3 Formulation of ORNL Simulant Using ANL Salts and ANL Water (ASAW)..........
2.4 Formulation of Simulant Containing Only One of the ANL Salts Preparedw ith
ORNL Water (ASOW-B) ..r.........................~.................................,....................... 10
2.5 Formulation of Simulant Containing Only Four of the ANL Salts Preparedw ith
ORNL Water (ASOW-C) . . .. . . . . .. . .. . . . . . . . . . .. . . . . . . . . . . . . . . . .. . . . .. . . . . . . . . . . . . . . . . .. . . .. . . .. . . . . . . . . . . . .. . 11
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2.6 Comparison of Batch Results Obtained Using Different Simulants.. . . . . . . .. . . . . .. .. . . . .. .I4
2.7 Influence of Multiple Contacting. . . . . .. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . .. . . . . . . . . . .. . . . 16
2.8 Influence of Simulant Washesw ith Different Solvents and Diluents . . .. . . . . . . .. .. .. . . .. . 17
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4.1 Cesium Distribution Ratios in Batch Tests Involving ORNL Simulant Containing
Controlled Amounts of S.ulfonate. . . . . . . .. . . . .. . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . .. . . . . . . 37
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