Extraction Chromatographic Resin Research Articles

Evaluation of an Extraction Chromatographic Resin Based on the DOODA Extractant: Characterization, Comparison to DGA, and Potential Applications

ABSTRACT The extraction of selected metal ions by an extraction chromatographic (EXC) resin containing N,N,N’,N’-tetraoctyl-3,6-dioxaoctane diamide (DOODA) on a porous methacrylate support was measured from nitric acid and hydrochloric acid. Metal ion extraction with the DOODA resin was compared to structurally similar diglycolamide (DGA) resins containing the extractants N,N,N’,N’-tetraoctyl-diglycolamide (TODGA; DGA, Normal resin) and N,N,N’,N’-tetra(2-ethyl-1-hexyl)-diglycolamide (TEHDGA; DGA, Branched resin). The EXC resins were studied via batch uptake, column elution, extraction capacity, and column stability experiments focusing on potential applications in analytical radiochemistry and nuclear medicine isotope production and purification. The DOODA resin exhibited similar extraction trends to the DGA resins for many metal ions, however, the capacity factors (k’) were reduced, typically following the trend of DGA, normal > DGA, branched > DOODA. The selectivity of DOODA resin towards rare earth elements, trivalent actinides, and some transition metal ions, particularly Cd, Ca, and Ac, is quite different from the existing DGA resins, but follows trends previously identified in solvent extraction experiments. The capacity for extraction of Ca(II) and Eu(III) from nitric acid was higher for the DOODA resin than either DGA resin, while all resins exhibited little extractant loss to the mobile phase over >18,000 bed volumes of elution.

Adsorption of terbium (III) on DGA and LN resins: Thermodynamics, isotherms, and kinetics

Two commercially available extraction chromatography (EXC) resins containing N,N,N’,N’-tetra-n-octyldiglycolamide (DGA Resin, Normal, 50 – 100 μm) and Bis(2-ethylhexyl) phosphate (LN Resin, 100 – 150 μm) were used as adsorbents to study fundamental adsorption properties such as thermodynamic values, equilibrium isotherms, and kinetic uptake models for terbium(III) adsorption. Weight distribution ratios (Dw) for terbium on DGA and LN resins were measured using a [160Tb]Tb3+radiometric tracer in nitric acid as a function of acidity, temperature, initial analyte concentration, and equilibrium time. The Dw values showed increasing binding affinity for DGA resin at high nitric acid concentrations and decreasing binding affinity for LN resins. Thermodynamic studies for DGA and LN resins revealed that the Gibbs free energy (ΔG) increased consistently with temperature. To model equilibrium data, increasingly higher parameter equilibrium isotherm models (Henry (1) < Langmuir, Freundlich (2) < Redlich-Peterson (3) < Fritz-Schluender (4)) were compared on their root mean squared errors (RMSE) and adjusted determination coefficients to determine the most applicable model. In all cases, the empirical four-parameter Fritz-Schluender isotherm demonstrated a superior fit. Similar comparisons for reaction-based kinetic models (Pseudo-first-order < Pseudo-second-order < Pseudo-n-order) revealed that the higher-order PNO model yielded a superior fit of kinetic data for both resins. However, in some cases, adsorption isotherms and kinetic models could also be modeled by a lower-order model with minimal change in error parameters. Weber-Morris plots revealed that two linear sections are observed for each resin, where the first linear segment is attributed to fast (film diffusion) adsorption of terbium, followed by slower intraparticle diffusion of terbium through the pores as the rate-limiting step. Based on the Weber-Morris plot, both film and intraparticle diffusion are involved in controlling the kinetic rate of adsorption for DGA and LN resins.

Remarkable enhancement in radio-cesium uptake from acidic feeds into an extraction chromatography resin containing a calix[4]arene-mono-crown-6 ligand

An extraction chromatography resin, prepared by the impregnation of bis-octyloxy-calix[4]arene-mono-crown-6 (BOCMC)onto an acrylic ester based polymeric support material, gave excellent uptake data for the removal of radio-cesium (Cs-137) from nitric acid feed solutions. The weight distribution coefficient (Kd) value of >300 obtained during the present study at 3 M HNO3 was the highest reported so far while using a calix-crown-6 based extraction chromatographic resin material. Analogous resin reported previously has yielded a Kd value <100 at comparable feed conditions. The sorbed metal ions could be efficiently desorbed with de-ionized water. Kinetic modeling of the uptake data indicated that both the film and the intra-particle diffusion mechanism are simultaneously operating in the sorption of Cs+ion onto the BOCMC resin. The metal ion sorption data were fitted to the sorption isotherm models and did not conform to the chemisorptions of physisorption models and indicated a pi-pi interaction between the benzene rings of the calix-crown-6 ligand and the Cs+ ion. The reusability of the resins was quite satisfactory after 5 cycles and the radiation stability of the resin material was very good upto an absorbed dose of 500 kGy. The results of column studies were quite encouraging with 15 mL (9 bed volumes) as the breakthrough volume while the elution was complete in about 12 bed volumes of de-ionized water.

Novel dialkylphosphinic acid modified Merrifield resins: Synthesis, characterization, and their adsorption and separation behaviors for zirconium and hafnium

Deep separation of Zr and Hf has always been a great challenging due to their very similar physicochemical properties. In this study, we established a method to synthesize two novel extraction chromatographic resins which graft dialkylphosphinic acid groups through amide group. The dialkylphosphinic acid modified resins were characterized by FT-IR, EA, SEM-EDS, XPS, and BET. Their adsorption and separation behaviors for Zr and Hf were investigated, and the adsorption mechanism was studied. The Zr and Hf adsorption onto Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 both fit pseudo-second order model and Langmuir isotherm model. Mer-CON-POOH-HYY2 has stronger affinity to Zr and Hf than Mer-CON-POOH-272. Mer-CON-POOH-272 has a theoretical maximum loading capacity of 5.663 mg·g−1 Zr and 11.111 mg·g−1 Hf, while Mer-CON-POOH-HYY2 has a higher theoretical maximum loading capacity of 8.376 mg·g−1 Zr and 13.157 mg·g−1 Hf. Dialkylphosphinic acids are the functional groups of Mer-CON-POOH-272 and Mer-CON-POOH-HYY2 that interact with Zr and Hf during adsorption. They adsorb Zr and Hf through cation exchange mechanism, which can be expressed as M(SO4)32– + 2HL ⇌ M(SO4)L2 +.2H+ + 2SO42-. With increasing H2SO4 concentration, the Zr and Hf extraction percentages and their separation efficiency reduce. The DFT calculation reveals that the adsorption process is accompanied by charge transfer. Adsorption occurs mainly at P = O and P-O positions. The affinity of the two resins for Hf is higher than that of Zr, which is the reason why the resin preferentially adsorbs Hf.

Separation of gold from irradiated actinide material utilizing a 2- thenoyltrifluoroacetone extraction resin

Post-detonation nuclear forensics capabilities depend on the ability to rapidly isolate radionuclides to improve measurement quality. In this work an extraction chromatography resin was developed utilizing thenoyltrifluoroacetone and 1-octanol supported on Eichrom prefilter resin. The resin was tested in nitric and hydrochloric acid matrices. In nitric acid the resin was able to extract zirconium, while in hydrochloric acid matrices it was possible to extract iron and gallium. In all acid conditions tested, gold was retained but can be eluted from the column with 10 % thiourea.

Efficient actinide sequestration with ionic liquid-based extraction chromatography resins containing Aza-crown ether functionalized diglycolamides

Two new extraction chromatographic resins (ECRs) were prepared by impregnating two exotic diglycolamide (DGA) ligands (having three or four DGA moieties tethered to aza-crown ether scaffolds) dissolved in an ionic liquid onto an inert solid support. A room temperature ionic liquid (RTIL) was used for enhancing the performance of the ECRs. The ECR containing triaza-9-crown-3 functionalized with three DGA moieties (TAM-3-DGA), and tetraaza-12-crown-4 tethered with four DGA arms (TAM-4-DGA) were evaluated for the separation of Am3+ and Pu4+from nitric acid solutions. The resin capacity for Eu3+ was 9.52 mg/g and 7.24 mg/g for TAM-3-DGA and TAM-4-DGA resins, respectively. Similarly, the resin capacity for Pu4+was 7.44 mg/g and 5.72 mg/g for TAM-3-DGA and TAM-4-DGA resins, respectively. These maximum loading values corresponded to the formation of a 1:1 metal/ligand complex for the Eu3+ ion and a 1:2 metal/ligand complex for the Pu4+ ion. The sorption of Eu3+and Pu4+on the resins followed a chemisorption phenomenon on both resins. The sorbed Eu3+and Pu4+ions from the resin phase could be efficiently desorbed with complexing ligands such as guanidine carbonate/HEDTA and oxalic acid, respectively.

Comparison of sorption characteristics of solid extractants based on tetraoctyldiglycolamide with respect to lutetium and ytterbium

The paper compares the sorption characteristics of solid extractants (extraction chromatographic resin (EXC)) based on tetraoctyldiglycolamide, DGA Resin (Triskem, France) and AXIONIT MND 40T (Russia), under static and dynamic conditions with respect to Lu and Yb. It was found that for AXIONIT MND 40T (EXC-TODGA), in contrast to DGA Resin (EXC-DGA), sorption equilibrium is attained much more slowly and signi cantly depends on the temperature and size of the extractant granules. The desorption of ytterbium and lutetium using various reagents was studied, and the solutions of DTPA and ammonium citrate were found to be the most e ective. The optimal conditions for concentration ytterbium and lutetium with the given solid extractants were determined and tested using real radioactive solutions.

An isotope generator of Po-210 based on SR resin

The work describes an isotope generator of polonium-210 based on an extraction chromatographic resin SR Resin. It was shown that a high selectivity of 4,4’(5’)-di-t-butylcyclohexano-18-crown-6, an active component of SR Resin, for lead allows a clear separation of Pb-210 from impurities, easy elution of Po-210 with 5–7 mL of 0.05 M nitric acid solution as well as good retention of Pb-210 in the generator. The content of alpha emitting impurities in the Po-210 eluate did not exceed 0.65%. The experience of 3-years exploitation of the generator is described. It was shown that the SR Resin was stable against irradiation and complete drying, and Pb-210 loss from the SR Resin column for 3 years (seven elutions) was near to loss due to its radioactive decay within the error limits (less than 7%).

O-17 - TRIGA Reactor Production and Synergistic Separation of 161Tb from Enriched 160Gd Targets Using Novel Extraction Chromatographic Resins

O-17 - TRIGA Reactor Production and Synergistic Separation of 161Tb from Enriched 160Gd Targets Using Novel Extraction Chromatographic Resins

Uptake behavior of arsenic and selenium with sulfur-based extraction chromatography resins in HCl and HNO3 media

Uptake behavior of arsenic and selenium with sulfur-based extraction chromatography resins in HCl and HNO3 media

Modified Diglycolamide Resin: Characterization and Potential Application for Rare Earth Element Recovery

Rare earth elements (REEs) are crucial for green energy applications due to their unique properties, but their extraction poses sustainability challenges because the global supply of REEs is concentrated in a few countries, particularly China, which produces 70% of the world’s REEs. To address this, the study investigated TK221, a modified extraction chromatographic resin featuring diglycolamide (DGA) and carbamoyl methyl phosphine oxide (CMPO), as a promising adsorbent for REE recovery. The elemental composition and functional groups of DGA and CMPO on the polystyrene-divinylbenzene (PS-DVB) support of TK221 were confirmed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The adsorption kinetics of neodymium (Nd), yttrium (Y), cerium (Ce), and erbium (Er) followed the pseudo-second-order kinetic model and Langmuir isotherm, indicating monolayer chemisorption. Furthermore, iron (Fe) adsorption reached apparent equilibrium after 360 min, with consistent Fe adsorption observed at both 360 min and 1440 min. The inclusion of Fe in the study is due to its common presence as an impurity in most REE leachate solutions. The Fe adsorption isotherm results are better fitted with the Langmuir isotherm, implying chemisorption. Maximum adsorption capacities (qmax) of the resin were determined as follows: Nd (45.3 mg/g), Ce (43.1 mg/g), Er (35.1 mg/g), Y (15.6 mg/g), and Fe (12.3 mg/g). ATR-FTIR analysis after adsorption suggested that both C=O and P=O bands shifted from 1679 cm−1 to 1618 cm−1 and 1107 cm−1 to 1142 cm−1 for Y, and from 1679 cm−1 to 1607 cm−1 and 1107 cm−1 to 1135 cm−1 for Ce, implying possible coordination with REEs. These results suggest that TK221 has a huge potential as an alternative adsorbent for REE recovery, thus contributing to sustainable REE supply diversification.

Highly Promising Method for the Decontamination of Europium from Americium Using an Extraction Chromatography Resin Containing a Tripodal Diglycolamide and SO3Ph-BTP as Eluent

Highly Promising Method for the Decontamination of Europium from Americium Using an Extraction Chromatography Resin Containing a Tripodal Diglycolamide and SO₃Ph-BTP as Eluent

DTPA(DOTA)-Nimotuzumab Radiolabeling with Generator-produced Thorium for Radioimmunotherapy of EGFR-overexpressing Carcinomas.

The feasibility of preparing the "in-house" generators and the Th- DTPA(DOTA)-Nimotuzumab radioimmunoconjugate was evaluated. 226Th is perspective for TAT, however, due to short half-life it is preferable to apply this radionuclide for readily available epithelial malignancies. Nimotuzumab being specific for EGFR expressing cells as a targeting moiety is considered to be suitable for thorium delivery. TEVA extraction chromatographic resin and anion exchange resin AG 1x8 were used as sorbents for 226Th generator. In order to determine features of labeling by Th4+ we applied 234Th as a longer-lived analog of short-lived 226Th and the immunoconjugates DTPA(DOTA)-Nimotuzumab were used for radiolabeling. The generator on the base of TEVA resin has shown higher volume activity of the product compared to the AG 1x8. The 226Th volume concentration was up to 80%/mL. The radiolabeling of BFCA by thorium radioisotopes reached 95% at the MR(Th:p-SCN-Bn-DTPA) = 1:100 and 86% for MR(Th:p-SCN-Bn-DOTA) = 1:5000 at 90°C. The procedure of Nimotuzumab labeling with Th4+ for radiotherapy of EGFR-overexpressing carcinomas was established. The overall labeling yield in both radioimmunoconjugates - DTPA and DOTA functionalized - was in the range of 45-50%. The immunoconjugate Nimotuzumab-p-SCN-Bn-DTPA was obtained with a molar ratio 1:25 (Nimotuzumab: BFCA), within 1 hour of conjugation at 25°C and labelled via postconjugation approach. Whereas Nimotuzumab-p-SCN-Bn-DOTA was obtained at the same conditions, but radiolabeled by the method of pre-conjugation. Thorium-234 incorporation into both radioimmunoconjugates reached 45-50%. It has been shown that Th-DTPA-Nimotuzumab radioimmunoconjugate specifically bound with EGFR overexpressing epidermoid carcinoma A431 cells.

Highly efficient separation of Am(III) and Pu(IV) from lean feeds and soil using an extraction chromatographic resin containing a diglycolamide in an ionic liquid

A TODGA based extraction chromatographic resin containing an ionic liquid was used for the separation of actinide ions such as Am3+ and Pu4+ from samples such as lean effluents emanating from laboratory waste, environmental water as well as soil samples adjacent to a nuclear plant site. The methodology involved feed adjustment to 3 M HNO3 followed by conditioning of the column, loading, washing (3 M HNO3), and elution of the actinide ions. The elution of Am3+ was done using EDTA in a buffered medium (1 M guanidine carbonate) while that of Pu4+ was carried out using a mixture of 0.5 M oxalic acid and 0.5 M HNO3. The elution peaks were sharp with almost no tailing suggesting the efficiency of the separation method. The results obtained were compared with the literature results which suggested the high efficiency of the present method.

Stagnant pore-blocked supports for improved extraction chromatography

Prior work has demonstrated that the complex pore structure of the polymeric supports employed for the preparation of commercial extraction chromatographic resins is a major contributor to their poor column efficiency and susceptibility to pronounced peak tailing. Particularly problematic is the presence of a number of small, relatively inaccessible (“stagnant”) pores. By blocking these pores with an appropriate inert filler, the extractant can be confined to the more readily accessible intermediate and large pores. The result is improved column efficiency (i.e., up to a 40% increase in N), reduced peak tailing and asymmetry (i.e., up to a 34% reduction in As), and in some instances, higher metal ion uptake capacity (up to a 64% increase) versus a commercial resin. The utility of the improved chromatographic performance arising from this “stagnant pore blocking” is illustrated in the separation of selected trivalent lanthanide ions, specifically Nd(III) and Eu(III), whose resolution has been reported to be unsatisfactory using conventional extraction chromatographic materials.

Proof-of-concept studies of novel protocols for producing highly pure 48V from a 48Cr/48V generator

The quest to improve the quality of nuclear data, such as half-lives, transition yields, and reaction cross-sections, is a shared endeavor among various areas of nuclear science. 48V is a vanadium isotope for which experimental data on neutron reaction cross-sections is needed. However, traditional isotope production techniques cannot produce 48V with high enough isotopic purity for some of these measurements. “Isotope harvesting” at the Facility for Rare Isotope Beams (FRIB) is a new isotope production technique that could potentially yield 48V with the necessary purity for such studies. In this case, 48Cr would be collected and allowed to generate 48V that can be separated from undecayed 48Cr to yield highly pure 48V. Thus, any protocol for producing pure 48V via isotope harvesting would involve utilizing a separation technique that can effectively separate 48Cr and 48V. In this study, the radiotracers 51Cr and 48V were used to develop possible radiochemical separation methodologies, which can be translated to obtain high purity 48V via this novel isotope production method. The developed protocols utilize either ion exchange or extraction chromatographic resins. Separations of 51Cr and 48V with AG 1-X8 anion exchange resin respectively resulted in recoveries of 95.6(26)% and 96.2(12)% with radionuclidic purities of 92(2)% and 99(1)%. An even more effective Cr and V separation was obtained with an extraction chromatographic resin (TRU resin) and 10 M HNO3 loading solution. Here, 51Cr and 48V respectively had recoveries of 94.1(28)% and 96.2(13)% with high radionuclidic purities (100(2)% and 100(1)%) in small volumes (8.81(8) mL and 5.39(16) mL). This study suggests that, to maximize the yield and isotopic purity of 48V, the best production protocol would involve utilizing two separations with TRU resin and 10 M HNO3 to isolate 48Cr and purify the generated 48V.

Characterization of a Set of Improved, CMPO-Based, Extraction Chromatographic Resins: Applications to the Separation of Elements Important for Geochemical and Environmental Studies

ABSTRACT This article describes several extraction chromatographic materials aiming to offer improved potential for isolating trace elements with high charge/ionic radius ratio from accompanying matrix elements in natural samples. Starting with commercially available, field-proven, TRU- and RE-Spec materials (Eichrom Technologies), three resins containing less TBP in the CMPO-TBP mixtures, or even neat CMPO only, have been prepared and characterized through measurement of the distribution ratios of some fifty elements in HNO3 and HCl media of variable strength. These resins were further evaluated for analytical applications on geochemical samples. The results highlight a strong enhancement of weight distribution ratios of many elements of interest in geochemistry, cosmochemistry, and environmental sciences (Lanthanides, naturally occurring Actinides, High Field Strength Elements). Combined with good chromatographic characteristics, these high Dw’s make it possible to achieve excellent group separations by using very small columns operated at relatively high, gravity-driven flow rate. Moreover, in an attempt to further improve the selectivity against Fe(III) and Ti(IV), preliminary investigations were made on an additional pair of resin prototypes impregnated with a CMPO-substituted calixarene. Although promising distribution ratio data were obtained, these prototypes did not permit to prepare columns with satisfactory chromatographic characteristics, and this approach still waits for a better impregnation methodof the porous inert support.

Behavior of selenium and arsenic in HCl and HNO3 on TRU, TEVA, DGA, and Pb extraction chromatography resins

Behavior of selenium and arsenic in HCl and HNO3 on TRU, TEVA, DGA, and Pb extraction chromatography resins

Mechanism of astatine and bismuth sorption on extraction chromatography resins from nitric acid media

Systematic study of astatine (At) sorption on extraction chromatography resins from nitric acid media has been performed at Texas A&M University. This work covers commercially available resins such as LN, TK400, SR, TRU, and UTEVA. Acquiring an understanding of At behavior in up to 4 M HNO3 solutions is a key step to develop a rapid and reliable system for At separation and purification. The determined distribution coefficients are greater than 20 for all the resins studied, reaching 400 for TRU and UTEVA resins. The sorption uptake decreases in the order: TRU ≳ UTEVA > TK400 ≳ SR > LN. For each resin a thermodynamic model has been developed to suggest a possible mechanism of At sorption and corresponding sorption constants have been estimated. Literature data along with new results on bismuth (Bi) sorption by studied resins in nitric acid media have been reviewed and a mathematical model to describe its behavior has been suggested. A ratio of corresponding fit functions of At and Bi assigned to the same resin and acidity has been used to estimate separation factors of these elements. Only the TRU resin is not suitable for efficient At isolation from Bi, while the other four resins demonstrate promising results.

Study on Separation of Rhenium, a Surrogate Element of Fissiogenic Technetium, from Aqueous Matrices Using Ion-Selective Extraction Chromatographic Resins

Long-lived fissiogenic technetium, 99Tc (half-life, 2.11 × 105 yrs), is a byproduct of the 235U and 239Pu fission in nuclear reactors and is a major component in nuclear waste. Hence, the monitoring of 99Tc activity in the environmental samples is essential. Techniques used to measure 99Tc in environmental samples include radiometric and non-radiometric approaches. Inductively coupled plasma mass spectrometry (ICP-MS) has some advantages among the methods due to its high sample throughput, better selectivity, and commercial availability. Rhenium (Re) is often used as the non-isotopic tracer during 99Tc measurement by ICP-MS. From this perspective, studying the separation behavior of Re from the aqueous matrix can provide helpful insight regarding the ecological monitoring of 99Tc. In the current work, three extraction chromatographic resins (ECRs), MetaSEP AnaLig Tc-01, MetaSEP AnaLig Tc-02, and Eichrom TRU, have been used to separate Re from the aqueous matrix. Operating variables, such as solution pH, choice of eluent and eluent concentration, matrix cation effect, and retention capacity, have been studied to optimize the separation protocol. The extraction and recovery behavior of Re was used to interpret the selectivity behavior of the ECRs. The Re separation factor at optimized operating conditions comparing with Mo and Ru (interfering elements during the measurement by ICP-MS) for Meta SEP AnaLig Tc-01, Meta SEP AnaLig Tc-02, and Eichrom TRU resin, respectively, are SFRe/Mo~32, 16.51, and ∞ (metal not retained at all), while SFRe/Ru~∞, 3.25, 5437. In terms of selectivity and retention capacity, MetaSEP AnaLig Tc-01 is the better choice for selective separation of Re, and, assumably so, also Tc, from the aqueous matrices.