Pub Date : 2023-08-01DOI: 10.1080/07366299.2023.2239882
D. Maertens, K. Binnemans, T. Cardinaels
ABSTRACT Annular centrifugal contactors (ACCs) have appealing properties as counter-current multistage solvent extraction (SX) equipment, allowing high throughput at short residence times, small liquid hold-up, and small footprint. The number of commercial suppliers of laboratory-scale ACCs is limited, and their designs have restricted flexibility. Commercial 25 mm diameter ACCs were customized with transparent PMMA surroundings of the mixing zones, allowing visual process monitoring and identification of operational malfunctions. The separation zone of several rotors was lengthened compared to the factory design, which allows longer average residence times in the modified contactors, while keeping the organic flow rate constant in the bank of interconnected contactors. The Couette gap could be increased or decreased without affecting the mixing performance. A 3D-printed stator allows for more efficient draining of the light and heavy phases, and reduces liquid hold-up and volumes required to efficiently achieve steady-state conditions in the process. The hydrodynamic performance of the modified equipment was demonstrated by a SX process of uranium with TBP. First a literature data set of distribution ratios for uranium in HNO3 and 30% TBP diluted in dodecane was utilized to create an empirical model in SX Process simulation software. A flowsheet was designed to validate the model, and it provides an example of the methodology to progress from batch to multistage process. Online density measurements were used to monitor and control the uranium concentrations, and to achieve the desired high metal loading steady-state conditions. It was demonstrated that ruthenium decontamination from uranium could be improved in modified ACCs with longer residence time in the mixing zones of the scrubbing section.
{"title":"Design of a Modular Annular Centrifugal Contactor for Lab-Scale Counter-Current Multistage Solvent Extraction","authors":"D. Maertens, K. Binnemans, T. Cardinaels","doi":"10.1080/07366299.2023.2239882","DOIUrl":"https://doi.org/10.1080/07366299.2023.2239882","url":null,"abstract":"ABSTRACT Annular centrifugal contactors (ACCs) have appealing properties as counter-current multistage solvent extraction (SX) equipment, allowing high throughput at short residence times, small liquid hold-up, and small footprint. The number of commercial suppliers of laboratory-scale ACCs is limited, and their designs have restricted flexibility. Commercial 25 mm diameter ACCs were customized with transparent PMMA surroundings of the mixing zones, allowing visual process monitoring and identification of operational malfunctions. The separation zone of several rotors was lengthened compared to the factory design, which allows longer average residence times in the modified contactors, while keeping the organic flow rate constant in the bank of interconnected contactors. The Couette gap could be increased or decreased without affecting the mixing performance. A 3D-printed stator allows for more efficient draining of the light and heavy phases, and reduces liquid hold-up and volumes required to efficiently achieve steady-state conditions in the process. The hydrodynamic performance of the modified equipment was demonstrated by a SX process of uranium with TBP. First a literature data set of distribution ratios for uranium in HNO3 and 30% TBP diluted in dodecane was utilized to create an empirical model in SX Process simulation software. A flowsheet was designed to validate the model, and it provides an example of the methodology to progress from batch to multistage process. Online density measurements were used to monitor and control the uranium concentrations, and to achieve the desired high metal loading steady-state conditions. It was demonstrated that ruthenium decontamination from uranium could be improved in modified ACCs with longer residence time in the mixing zones of the scrubbing section.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41555623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-29DOI: 10.1080/07366299.2023.2220765
C. Zarzana, J. McAlpine, A. Wilden, Michelle Hupert, Andrea Stärk, M. Iqbal, W. Verboom, B. Mincher, G. Groenewold, G. Modolo
ABSTRACT The radiolytic stabilities of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) were investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. The objective of Part I of this series of papers covers was to evaluate the contribution of the phenyl group to the radiolytic stability of these diglycolamides when irradiated in a) n-dodecane, and b) n-dodecane in the presence of a nitric acid-containing aqueous phase. The results indicate that the presence of the phenyl group decreases the overall radiolytic stability compared to unsubstituted TODGA. However, the results also indicate that the phenyl groups interact with nitric acid in a cooperative fashion that enhances the radiation stability of the phenylated diglycolamide (DGA) derivatives in the presence of a nitric acid-containing aqueous phase compared to irradiation in only n-dodecane. The results are consistent with the hypothesized formation of nitric acid-phenylated DGA complexes in the n-dodecane phase that are significantly more stable with respect to gamma irradiation, compared to the phenylated DGA molecules alone.
{"title":"Gamma Radiolysis of Phenyl-Substituted TODGAs: Part I","authors":"C. Zarzana, J. McAlpine, A. Wilden, Michelle Hupert, Andrea Stärk, M. Iqbal, W. Verboom, B. Mincher, G. Groenewold, G. Modolo","doi":"10.1080/07366299.2023.2220765","DOIUrl":"https://doi.org/10.1080/07366299.2023.2220765","url":null,"abstract":"ABSTRACT The radiolytic stabilities of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) were investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. The objective of Part I of this series of papers covers was to evaluate the contribution of the phenyl group to the radiolytic stability of these diglycolamides when irradiated in a) n-dodecane, and b) n-dodecane in the presence of a nitric acid-containing aqueous phase. The results indicate that the presence of the phenyl group decreases the overall radiolytic stability compared to unsubstituted TODGA. However, the results also indicate that the phenyl groups interact with nitric acid in a cooperative fashion that enhances the radiation stability of the phenylated diglycolamide (DGA) derivatives in the presence of a nitric acid-containing aqueous phase compared to irradiation in only n-dodecane. The results are consistent with the hypothesized formation of nitric acid-phenylated DGA complexes in the n-dodecane phase that are significantly more stable with respect to gamma irradiation, compared to the phenylated DGA molecules alone.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47632004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-28DOI: 10.1080/07366299.2023.2239866
Emma M. Archer, Shane S. Galley, J. Jackson, J. Shafer
ABSTRACT Separations relevant to trivalent actinides and lanthanides have been a focus of the f-element community in the past few decades. A central focus of this effort has been optimizing ligands for separations. From a fundamental perspective, one must investigate the metal–ligand interactions for optimal ligand design. A well-explored class of ligands, phenanthroline diamides, is reviewed to further elucidate the actinide or lanthanide–ligand interactions of primarily Am3+, Cm3+, and Eu3+. Mixed nitrogen and oxygen donors of this nature are of interest to explore due to their increased selectivity for the trivalent actinides over the trivalent lanthanides. Phenanthroline diamide ligands have shown to have promise in industrial-scale separations compared to bipyridine and pyridine diamide ligands with larger selectivity for the trivalent actinides. These interactions are studied through solvent extraction, spectroscopic, and thermodynamic techniques. Further analysis provided in this review includes an overview of the computational results provided and relevant comparisons to experimental data. The computational parameters considered are the calculated bond lengths, thermodynamic parameters, and values that provide insight to a discussion of covalent interactions between metal and ligand. The information provided is important to benchmark the state-of-the-art basic, applied, and computational chemistry of the phenanthroline diamide class of ligands. GRAPHICAL ABSTRACT
{"title":"Investigation of f-Element Interactions with Functionalized Diamides of Phenanthroline-Based Ligands","authors":"Emma M. Archer, Shane S. Galley, J. Jackson, J. Shafer","doi":"10.1080/07366299.2023.2239866","DOIUrl":"https://doi.org/10.1080/07366299.2023.2239866","url":null,"abstract":"ABSTRACT Separations relevant to trivalent actinides and lanthanides have been a focus of the f-element community in the past few decades. A central focus of this effort has been optimizing ligands for separations. From a fundamental perspective, one must investigate the metal–ligand interactions for optimal ligand design. A well-explored class of ligands, phenanthroline diamides, is reviewed to further elucidate the actinide or lanthanide–ligand interactions of primarily Am3+, Cm3+, and Eu3+. Mixed nitrogen and oxygen donors of this nature are of interest to explore due to their increased selectivity for the trivalent actinides over the trivalent lanthanides. Phenanthroline diamide ligands have shown to have promise in industrial-scale separations compared to bipyridine and pyridine diamide ligands with larger selectivity for the trivalent actinides. These interactions are studied through solvent extraction, spectroscopic, and thermodynamic techniques. Further analysis provided in this review includes an overview of the computational results provided and relevant comparisons to experimental data. The computational parameters considered are the calculated bond lengths, thermodynamic parameters, and values that provide insight to a discussion of covalent interactions between metal and ligand. The information provided is important to benchmark the state-of-the-art basic, applied, and computational chemistry of the phenanthroline diamide class of ligands. GRAPHICAL ABSTRACT","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47555648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-25DOI: 10.1080/07366299.2023.2229888
D. Cao, Shuai Wang, Xin Ma, Jia Yang, Hong Zhong
ABSTRACT Herein, a novel C=O–NOH-contained compound was synthesized and used in the extraction and recovery of copper from sulfate solution. Dodecyl phenyl ethyl hydroxamic acid (DPEHA) exhibited high selectivity to Cu(II) over the competing ions, and the separation factors (β) obtained were β Cu/Zn = 227.370, β Cu/Co = 199.094, β Cu/Ni = 188.889, respectively. The separation effect was stronger than that of 2-hydroxy-5-nonyl acetophenone oxime. Meanwhile, extraction capacity of 0.10 g Cu(II) per gram DPEHA was reached, and the extracted Cu(II) can be stripped effectively. The investigation of extraction mechanism revealed that O atoms in C=O and O-H groups of DPEHA operate as active sites, which could powerfully chelate with Cu(II) by forming stable five-membered rings. The high copper extraction efficiency and selectivity associated with a simple synthesis of DPEHA make it to serve as the potential selective Cu(II) extractant, which also provide a novel insight for the research and development of economical Cu(II) extractants. Graphical Abstract
摘要本文合成了一种新型含C= o - noh化合物，并将其用于硫酸盐溶液中铜的提取和回收。十二烷基苯基乙基羟肟酸(DPEHA)对Cu(II)具有较高的选择性，得到的分离因子(β)分别为β Cu/Zn = 227.370， β Cu/Co = 199.094， β Cu/Ni = 188.889。分离效果优于2-羟基-5-壬基苯乙酮肟。同时，每g DPEHA萃取量为0.10 g Cu(II)，萃取后的Cu(II)可以有效剥离。萃取机理研究表明，DPEHA的C=O和O- h基团中的O原子作为活性位点，能与Cu(II)形成稳定的五元环进行强螯合。DPEHA具有较高的铜萃取效率和选择性，且合成简单，可作为铜(II)的选择性萃取剂，这也为经济型铜(II)萃取剂的研究和开发提供了新的思路。图形抽象
{"title":"Selective Extraction of Cu (II) Using Novel C=O–NOH-Contained Compound-Dodecyl Phenyl Ethyl Hydroxamic Acid and Its Extraction Mechanism","authors":"D. Cao, Shuai Wang, Xin Ma, Jia Yang, Hong Zhong","doi":"10.1080/07366299.2023.2229888","DOIUrl":"https://doi.org/10.1080/07366299.2023.2229888","url":null,"abstract":"ABSTRACT Herein, a novel C=O–NOH-contained compound was synthesized and used in the extraction and recovery of copper from sulfate solution. Dodecyl phenyl ethyl hydroxamic acid (DPEHA) exhibited high selectivity to Cu(II) over the competing ions, and the separation factors (β) obtained were β Cu/Zn = 227.370, β Cu/Co = 199.094, β Cu/Ni = 188.889, respectively. The separation effect was stronger than that of 2-hydroxy-5-nonyl acetophenone oxime. Meanwhile, extraction capacity of 0.10 g Cu(II) per gram DPEHA was reached, and the extracted Cu(II) can be stripped effectively. The investigation of extraction mechanism revealed that O atoms in C=O and O-H groups of DPEHA operate as active sites, which could powerfully chelate with Cu(II) by forming stable five-membered rings. The high copper extraction efficiency and selectivity associated with a simple synthesis of DPEHA make it to serve as the potential selective Cu(II) extractant, which also provide a novel insight for the research and development of economical Cu(II) extractants. Graphical Abstract","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48867932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-24DOI: 10.1080/07366299.2023.2221708
M. Gausmann, Diana Wall, A. Jupke
ABSTRACT Reactive extraction of succinic acid by tertiary amines is an effective separation technique. Its potential application for the initial recovery of bio-based succinic acid from fermentation broth. However, the co-extraction of inorganic anions significantly impairs the extraction performance. In this study, we use a statistically backed design of experiments method (DoE) to screen and identify the factors with a significant effect and relevant impact on extraction yield and selectivity. Eight operational factors (Extractant, solvent, succinic acid concentration, amine concentration, initial pH, the type of anion, electrolyte concentration, and temperature) were screened by applying an orthogonal design plan for the experiments. The choice of the extractant and diluent as well as the type of anion had the most significant effect on the extraction yield. In contrast, the selectivity was mainly affected by the concentration ratios of succinic acid and electrolyte. The screening plan reduced the number of experiments from 1728 possible combinations to 72 experiments required to identify the factors while maintaining the significance of the identified effects. We suggest competing mass-action relationships between the pH-dependent protonation of amines and the complexation of succinic acid to explain the observed trends. Graphical abstract
{"title":"Reliable Identification of Relevant Factors for the Reactive Extraction of Succinic Acid from Electrolyte Containing Solutions","authors":"M. Gausmann, Diana Wall, A. Jupke","doi":"10.1080/07366299.2023.2221708","DOIUrl":"https://doi.org/10.1080/07366299.2023.2221708","url":null,"abstract":"ABSTRACT Reactive extraction of succinic acid by tertiary amines is an effective separation technique. Its potential application for the initial recovery of bio-based succinic acid from fermentation broth. However, the co-extraction of inorganic anions significantly impairs the extraction performance. In this study, we use a statistically backed design of experiments method (DoE) to screen and identify the factors with a significant effect and relevant impact on extraction yield and selectivity. Eight operational factors (Extractant, solvent, succinic acid concentration, amine concentration, initial pH, the type of anion, electrolyte concentration, and temperature) were screened by applying an orthogonal design plan for the experiments. The choice of the extractant and diluent as well as the type of anion had the most significant effect on the extraction yield. In contrast, the selectivity was mainly affected by the concentration ratios of succinic acid and electrolyte. The screening plan reduced the number of experiments from 1728 possible combinations to 72 experiments required to identify the factors while maintaining the significance of the identified effects. We suggest competing mass-action relationships between the pH-dependent protonation of amines and the complexation of succinic acid to explain the observed trends. Graphical abstract","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45129882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-06DOI: 10.1080/07366299.2023.2221290
C. Zarzana, J. McAlpine, A. Wilden, Michelle Hupert, Andrea Stärk, M. Iqbal, W. Verboom, B. Mincher, G. Groenewold, G. Modolo
ABSTRACT The radiolytic degradation chemistry of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) was investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. In Part II of this series of papers radiolytic degradation products were identified after separation with liquid chromatography by High Resolution, Accurate-Mass mass spectrometry and collision-induced dissociation. At least twenty-two radiolytic degradation products were identified for PhTODGA, twenty-nine for PhMeTODGA, and over three dozen for DHDPDGA. The suite of radiolytic degradation products of these three investigated ligands was significantly larger than has been reported for previously studied diglycolamides, owing to their asymmetric nature, and to the identification of several new degradation mechanisms, including addition of methyl, hydroxyl, and nitrogen oxide radicals, that have not been previously reported for diglycolamides. Degradation products that contained addition of a NO2 or NO3 group were particularly prevalent for DHDPDGA, likely due to the phenyl side-groups. Several of these newly observed mechanisms do not appear to depend on the presence of the phenyl groups, suggesting these novel mechanisms may apply to other diglycolamides
研究了三种苯基化N,N,N '，N ' -四辛基二甘醇酰胺(TODGA)的辐射降解化学性质。2-(2-(二-正辛胺)-2-氧乙氧基)- n, n-二-正辛基-2-苯乙醯乙酰胺(PhTODGA)，它有一个苯基取代基与中心亚甲基结合，2-(二-正辛胺)-2-氧-1-苯乙氧基)- n, n-二-正辛基-2-苯乙醯丙酰胺(PhMeTODGA)，它也含有一个甲基取代基与醚部分另一侧的亚甲基结合，以及2-(2- n-正己基-n-苯基苯基)-2-正己基-n-苯基乙醯乙酰胺(DHDPDGA)。苯基取代基位于酰胺基上而不是中间的亚甲基上。在本系列论文的第二部分中，通过液相色谱、高分辨率、精确质谱和碰撞诱导解离分离，对辐射降解产物进行了鉴定。PhTODGA至少鉴定出22种放射性降解产物，PhMeTODGA鉴定出29种，DHDPDGA鉴定出超过36种。由于这三种配体的不对称性质，以及发现了几种新的降解机制，包括甲基自由基、羟基自由基和氮氧化物自由基的加入，这在以前的二糖酰胺研究中没有报道过，因此这三种配体的辐射降解产物明显大于先前报道的二糖酰胺。含有NO2或NO3基团的降解产物对DHDPDGA尤其普遍，可能是由于苯基侧基。这些新观察到的机制中的一些似乎并不依赖于苯基的存在，这表明这些新的机制可能适用于其他二醇酰胺
{"title":"Gamma Radiolysis of Phenyl-Substituted TODGAs: Part II","authors":"C. Zarzana, J. McAlpine, A. Wilden, Michelle Hupert, Andrea Stärk, M. Iqbal, W. Verboom, B. Mincher, G. Groenewold, G. Modolo","doi":"10.1080/07366299.2023.2221290","DOIUrl":"https://doi.org/10.1080/07366299.2023.2221290","url":null,"abstract":"ABSTRACT The radiolytic degradation chemistry of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) was investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. In Part II of this series of papers radiolytic degradation products were identified after separation with liquid chromatography by High Resolution, Accurate-Mass mass spectrometry and collision-induced dissociation. At least twenty-two radiolytic degradation products were identified for PhTODGA, twenty-nine for PhMeTODGA, and over three dozen for DHDPDGA. The suite of radiolytic degradation products of these three investigated ligands was significantly larger than has been reported for previously studied diglycolamides, owing to their asymmetric nature, and to the identification of several new degradation mechanisms, including addition of methyl, hydroxyl, and nitrogen oxide radicals, that have not been previously reported for diglycolamides. Degradation products that contained addition of a NO2 or NO3 group were particularly prevalent for DHDPDGA, likely due to the phenyl side-groups. Several of these newly observed mechanisms do not appear to depend on the presence of the phenyl groups, suggesting these novel mechanisms may apply to other diglycolamides","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44118557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-07-04DOI: 10.1080/07366299.2023.2231493
Yifu Hu, Wenfeng Hao, Wentao Wang, Ye Zhang, Qi Chen, Wenfu Yan, T. Yan
ABSTRACT Effectively separating Zr(IV) from strong acidic and radioactive solutions is crucial for spent fuel reprocessing plants, but it remains a challenging task. This study investigated the adsorption of Zr(IV) in HNO3 solutions using zeolites as adsorbents. The zeolites were characterized by X-ray diffraction (XRD)，scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The effects of adsorption time, HNO3 concentration, the initial concentration of Zr(IV), zeolites dosage, and temperature on the Zr(IV) adsorption behaviors were investigated. The results demonstrated that HY zeolite had a higher adsorption capacity for Zr(IV) than H-SSZ-13 zeolite. The adsorption capacity of HY zeolite was influenced by its Si/Al ratio, which determined the density of adsorption sites. The optimal HY zeolite (HY-25) exhibited a maximum adsorption capacity of 30.438 mg/g in 3 M HNO3 solution. Furthermore, the adsorption isotherms and kinetics of Zr(IV) adsorption were investigated. The adsorption of Zr(IV) on zeolites was endothermic and spontaneous, in accordance with the Freundlich’s isotherm model and pseudo-second-order kinetic model. In a simulated strong acidic solution of Zr(IV) and 10 co-existing cations (Ag+, Ba2+, Cs+, Ce3+, Eu3+, Fe3+, La3+, Nd3+, Sm3+, Sr2+), HY-25 exhibited good selective adsorption of Zr(IV), indicating its potential application in the treatment of high-level radioactive liquid waste.
摘要从强酸和强放射性溶液中有效分离Zr（IV）对乏燃料后处理厂至关重要，但这仍然是一项具有挑战性的任务。本研究以沸石为吸附剂，研究了Zr（IV）在HNO3溶液中的吸附。用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和X射线光电子能谱（XPS）对沸石进行了表征。研究了吸附时间、HNO3浓度、Zr（IV）的初始浓度、沸石用量和温度对Zr（Ⅳ）吸附行为的影响。结果表明，HY沸石对Zr（IV）的吸附能力高于H-SSZ-13沸石。HY沸石的吸附容量受其Si/Al比的影响，Si/Al比值决定了吸附位点的密度。最佳HY沸石（HY-25）的最大吸附量为30.438 mg/g，3 M HNO3溶液。此外，还研究了Zr（IV）的吸附等温线和吸附动力学。根据Freundlich等温线模型和拟二阶动力学模型，Zr（IV）在沸石上的吸附是吸热和自发的。在Zr（IV）和10种共存阳离子（Ag+、Ba2+、Cs+、Ce3+、Eu3+、Fe3+、La3+、Nd3+、Sm3+、Sr2+）的模拟强酸溶液中，HY-25对Zr（Ⅳ）表现出良好的选择性吸附，表明其在高放射性废液处理中具有潜在的应用前景。
{"title":"Selective Separation of Zr(IV) from Simulated High-Level Liquid Wastes by Zeolites","authors":"Yifu Hu, Wenfeng Hao, Wentao Wang, Ye Zhang, Qi Chen, Wenfu Yan, T. Yan","doi":"10.1080/07366299.2023.2231493","DOIUrl":"https://doi.org/10.1080/07366299.2023.2231493","url":null,"abstract":"ABSTRACT Effectively separating Zr(IV) from strong acidic and radioactive solutions is crucial for spent fuel reprocessing plants, but it remains a challenging task. This study investigated the adsorption of Zr(IV) in HNO3 solutions using zeolites as adsorbents. The zeolites were characterized by X-ray diffraction (XRD)，scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The effects of adsorption time, HNO3 concentration, the initial concentration of Zr(IV), zeolites dosage, and temperature on the Zr(IV) adsorption behaviors were investigated. The results demonstrated that HY zeolite had a higher adsorption capacity for Zr(IV) than H-SSZ-13 zeolite. The adsorption capacity of HY zeolite was influenced by its Si/Al ratio, which determined the density of adsorption sites. The optimal HY zeolite (HY-25) exhibited a maximum adsorption capacity of 30.438 mg/g in 3 M HNO3 solution. Furthermore, the adsorption isotherms and kinetics of Zr(IV) adsorption were investigated. The adsorption of Zr(IV) on zeolites was endothermic and spontaneous, in accordance with the Freundlich’s isotherm model and pseudo-second-order kinetic model. In a simulated strong acidic solution of Zr(IV) and 10 co-existing cations (Ag+, Ba2+, Cs+, Ce3+, Eu3+, Fe3+, La3+, Nd3+, Sm3+, Sr2+), HY-25 exhibited good selective adsorption of Zr(IV), indicating its potential application in the treatment of high-level radioactive liquid waste.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42618838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-06-21DOI: 10.1080/07366299.2023.2225067
A. Heidari, S. Shahini, Davoud Haghshenas Fatmehsari, E. Keshavarz Alamdari
ABSTRACT The study investigated the behavior of two amines, Trioctylamine (TOA) and Tris(2-Ethylhexyl) amine (TEHA), in the sulfuric acid extraction system, with varying concentrations of extractants and modifiers, as well as the temperature of the sulfuric acid extraction. The study found that TOA had a higher ability in the extraction of sulfuric acid and was less dependent on temperature. However, an increase in the initial sulfuric acid concentration resulted in a drop in acid extraction percentage when TOA was employed, while such a drop was not observed in the case of TEHA. The study also illustrated the necessity of using Octanol as a modifier, with different minimum levels required for TOA and TEHA. Additionally, Octanol showed a positive effect on the extraction level of sulfuric acid in the TEHA – H2SO4 extraction system, which can be considered an advantage in the facile stripping of the loaded organic phase. The slope analysis method revealed that more than 1 mol of TOA is necessary to extract 1 mol of sulfuric acid, while 1 mol of TEHA can absorb 2 mol of sulfuric acid. FTIR spectra analysis confirmed TOA's participation in the extraction of sulfuric acid and provided insights into the chemical bonds formed. Overall, the study provides a comprehensive understanding of the solvent extraction of sulfuric acid and can be useful in optimizing the extraction process for industrial applications.
{"title":"A Comparison Between Trioctylamine (TOA) and Tris(2-Ethylhexyl) Amine (TEHA) in Solvent Extraction of Sulfuric Acid*","authors":"A. Heidari, S. Shahini, Davoud Haghshenas Fatmehsari, E. Keshavarz Alamdari","doi":"10.1080/07366299.2023.2225067","DOIUrl":"https://doi.org/10.1080/07366299.2023.2225067","url":null,"abstract":"ABSTRACT The study investigated the behavior of two amines, Trioctylamine (TOA) and Tris(2-Ethylhexyl) amine (TEHA), in the sulfuric acid extraction system, with varying concentrations of extractants and modifiers, as well as the temperature of the sulfuric acid extraction. The study found that TOA had a higher ability in the extraction of sulfuric acid and was less dependent on temperature. However, an increase in the initial sulfuric acid concentration resulted in a drop in acid extraction percentage when TOA was employed, while such a drop was not observed in the case of TEHA. The study also illustrated the necessity of using Octanol as a modifier, with different minimum levels required for TOA and TEHA. Additionally, Octanol showed a positive effect on the extraction level of sulfuric acid in the TEHA – H2SO4 extraction system, which can be considered an advantage in the facile stripping of the loaded organic phase. The slope analysis method revealed that more than 1 mol of TOA is necessary to extract 1 mol of sulfuric acid, while 1 mol of TEHA can absorb 2 mol of sulfuric acid. FTIR spectra analysis confirmed TOA's participation in the extraction of sulfuric acid and provided insights into the chemical bonds formed. Overall, the study provides a comprehensive understanding of the solvent extraction of sulfuric acid and can be useful in optimizing the extraction process for industrial applications.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44244607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-05-31DOI: 10.1080/07366299.2023.2218918
Yan Du, Qing Zhou, Jiankun Zhao, Hexi Wu, Xiaoyan Li, Yibao Liu, Z. Le
ABSTRACT Nanoscale ferrous hydroxide complex-zero nickel composites (FHC/Ni0) were fabricated by ball milling method for Se(IV) adsorption from aqueous solution. The effects of pH, solid-liquid ratio, time, temperature, initial concentration of Se(IV) on the adsorption of Se(IV) by FHC/Ni0 were investigated. FHC/Ni0 was characterized by SEM, XPS, XRD, FT-IR, BET and Zeta potential, and the mechanism of removing Se(IV) was analyzed. The results showed that FHC/Ni0 had a good removal effect on Se(IV). When pH was 5.0, the solid-liquid ratio was 0.15 g L−1, the reaction time was 40 min, the maximum adsorption capacity of Se(IV) by FHC/Ni0 could reach 216 mg g−1. The pseudo-second-order kinetic model and Langmuir had a good fit for the Se(IV) adsorption process of FHC/Ni0, indicating that the monolayer and chemical adsorption played a leading role in the adsorption process. XPS analysis further confirmed that the adsorption of Se on FHC/Ni0 was mainly due to the formation of stable complexes with a large number of functional groups containing Fe, Ni and S, meanwhile, the removal of Se(IV) by the material is achieved through a combination of chemical adsorption and reduction reactions. The research results can demonstrate the feasibility of FHC/Ni0 in Se(IV) removal and provide a theoretical basis for the treatment of wastewater containing Se(IV).
采用球磨法制备了纳米级氢氧化铁-零镍复合材料(FHC/Ni0)，并对Se(IV)进行了吸附。考察了pH、料液比、时间、温度、初始浓度对FHC/Ni0吸附Se(IV)的影响。采用SEM、XPS、XRD、FT-IR、BET和Zeta电位对FHC/Ni0进行了表征，并对其去除Se(IV)的机理进行了分析。结果表明，FHC/Ni0对Se(IV)有较好的去除效果。当pH = 5.0，料液比为0.15 g L−1，反应时间为40 min时，FHC/Ni0对Se(IV)的最大吸附量可达216 mg g−1。拟二级动力学模型和Langmuir对FHC/Ni0的Se(IV)吸附过程拟合较好，说明在吸附过程中，单层吸附和化学吸附起主导作用。XPS分析进一步证实了Se在FHC/Ni0上的吸附主要是由于与大量含Fe、Ni和S的官能团形成稳定的配合物，同时材料对Se(IV)的去除是通过化学吸附和还原反应相结合的方式实现的。研究结果验证了FHC/Ni0去除Se(IV)的可行性，为含Se废水的处理提供了理论依据。
{"title":"Adsorptive Removal of Selenium(IV) from Aqueous Solution by Ferrous Hydroxide Complex-Zero Nickel Composites","authors":"Yan Du, Qing Zhou, Jiankun Zhao, Hexi Wu, Xiaoyan Li, Yibao Liu, Z. Le","doi":"10.1080/07366299.2023.2218918","DOIUrl":"https://doi.org/10.1080/07366299.2023.2218918","url":null,"abstract":"ABSTRACT Nanoscale ferrous hydroxide complex-zero nickel composites (FHC/Ni0) were fabricated by ball milling method for Se(IV) adsorption from aqueous solution. The effects of pH, solid-liquid ratio, time, temperature, initial concentration of Se(IV) on the adsorption of Se(IV) by FHC/Ni0 were investigated. FHC/Ni0 was characterized by SEM, XPS, XRD, FT-IR, BET and Zeta potential, and the mechanism of removing Se(IV) was analyzed. The results showed that FHC/Ni0 had a good removal effect on Se(IV). When pH was 5.0, the solid-liquid ratio was 0.15 g L−1, the reaction time was 40 min, the maximum adsorption capacity of Se(IV) by FHC/Ni0 could reach 216 mg g−1. The pseudo-second-order kinetic model and Langmuir had a good fit for the Se(IV) adsorption process of FHC/Ni0, indicating that the monolayer and chemical adsorption played a leading role in the adsorption process. XPS analysis further confirmed that the adsorption of Se on FHC/Ni0 was mainly due to the formation of stable complexes with a large number of functional groups containing Fe, Ni and S, meanwhile, the removal of Se(IV) by the material is achieved through a combination of chemical adsorption and reduction reactions. The research results can demonstrate the feasibility of FHC/Ni0 in Se(IV) removal and provide a theoretical basis for the treatment of wastewater containing Se(IV).","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48671565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-05-26DOI: 10.1080/07366299.2023.2215833
G. Hall, N. Bessen, P. Zalupski, Emily L. Campbell, T. Grimes, D. Peterman, G. Lumetta
ABSTRACT Increased focus on carbon neutral energy has generated a resurgence of interest in nuclear power, and in particular advanced reactors which are likely to utilize high assay low enriched uranium (HALEU). This in turn could increase the economic attractiveness of recovering still partially enriched uranium from used nuclear fuel. Concomitant to development of advanced reactors, advanced reprocessing schemes should be developed which address the disadvantages to well established reprocessing schemes. The present study focuses on using di-(2-ethylhexyl)-iso-butyramide (DEHiBA) under high metal loading conditions for the reprocessing of used nuclear fuel. The elements examined in the study include the dominant transuranic actinides (Np, Pu, Am) as well as the often-problematic Tc and Zr. By increasing the concentration of the extractant from the more commonly reported 1.0 M – 1.5 M, the extraction of hexavalent actinides is substantially increased, while maintaining effective rejection of tri, tetra, and pentavalent actinides, particularly in the presence of high loadings of uranium. The extraction of Zr by 1.5 M DEHiBA is noted to be negligible by comparison to tributyl phosphate (TBP), however the coextraction of Tc with U is observed to be nominally twice the quantity that is extracted by TBP indicating a need for effective Tc management.
对碳中和能源的日益关注已经引起了人们对核能，特别是可能使用高含量低浓缩铀(HALEU)的先进反应堆的兴趣的复苏。这反过来又会增加从乏燃料中回收仍然部分浓缩的铀的经济吸引力。在发展先进反应堆的同时，应开发先进的后处理方案，以解决现有后处理方案的缺点。研究了在高金属负荷条件下使用二-(2-乙基己基)-异丁酰胺(DEHiBA)进行乏燃料后处理的方法。研究中检查的元素包括主要的超铀锕系元素(Np, Pu, Am)以及经常出现问题的Tc和Zr。通过增加萃取剂的浓度，从更常见的1.0 M - 1.5 M，六价锕系元素的萃取量大大增加，同时保持有效的拒绝三，四，和五价锕系元素，特别是在存在高铀负荷的情况下。与磷酸三丁酯(TBP)相比，1.5 M DEHiBA对Zr的萃取可以忽略不计，然而，与U的共萃取在名义上是TBP萃取量的两倍，这表明需要有效的Tc管理。
{"title":"Extraction of Neptunium, Plutonium, Americium, Zirconium, and Technetium by Di-(2-Ethylhexyl)-Iso-Butyramide (DEHiBA) at High Metal Loadings","authors":"G. Hall, N. Bessen, P. Zalupski, Emily L. Campbell, T. Grimes, D. Peterman, G. Lumetta","doi":"10.1080/07366299.2023.2215833","DOIUrl":"https://doi.org/10.1080/07366299.2023.2215833","url":null,"abstract":"ABSTRACT Increased focus on carbon neutral energy has generated a resurgence of interest in nuclear power, and in particular advanced reactors which are likely to utilize high assay low enriched uranium (HALEU). This in turn could increase the economic attractiveness of recovering still partially enriched uranium from used nuclear fuel. Concomitant to development of advanced reactors, advanced reprocessing schemes should be developed which address the disadvantages to well established reprocessing schemes. The present study focuses on using di-(2-ethylhexyl)-iso-butyramide (DEHiBA) under high metal loading conditions for the reprocessing of used nuclear fuel. The elements examined in the study include the dominant transuranic actinides (Np, Pu, Am) as well as the often-problematic Tc and Zr. By increasing the concentration of the extractant from the more commonly reported 1.0 M – 1.5 M, the extraction of hexavalent actinides is substantially increased, while maintaining effective rejection of tri, tetra, and pentavalent actinides, particularly in the presence of high loadings of uranium. The extraction of Zr by 1.5 M DEHiBA is noted to be negligible by comparison to tributyl phosphate (TBP), however the coextraction of Tc with U is observed to be nominally twice the quantity that is extracted by TBP indicating a need for effective Tc management.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2023-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46619905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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