845. Separation factors in fractional crystallisation or precipitation of the lanthanons

Author(s):  
R. J. Callow
1985 ◽  
Vol 50 (3) ◽  
pp. 581-599 ◽  
Author(s):  
Petr Vaňura ◽  
Emanuel Makrlík

Extraction of microamounts of Sr2+ and Ba2+ (henceforth M2+) from the aqueous solutions of perchloric acid (0.0125-1.02 mol/l) by means of the nitrobenzene solutions of dicarbolide (0.004-0.05 mol/l of H+{Co(C2B9H11)2}-) was studied in the presence of monoglyme (only Ba2+), diglyme, triglyme, and tetraglyme (CH3O-(CH2-CH2O)nCH3, where n = 1, 2, 3, 4). The distribution of glyme betweeen the aqueous and organic phases, the extraction of the protonized glyme molecule HL+ together with the extraction of M2+ ion and of the glyme complex with the M2+ ion, i.e., ML2+ (where L is the molecule of glyme), were found to be the dominating reactions in the systems under study. In the systems with tri- and tetraglymes the extraction of H+ and M2+ ions solvated with two glyme molecules, i.e., the formation of HL2+ and ML22+ species, can probably play a minor role. The values of the respective equilibrium constants, of the stability constants of complexes formed in the organic phase, and the theoretical separation factors αBa/Sr were determined. The effect of the ligand structure on the values of extraction and stability constants in the organic phase is discussed.


1986 ◽  
Vol 51 (3) ◽  
pp. 498-515 ◽  
Author(s):  
Emanuel Makrlík ◽  
Petr Vaňura

Extraction of Eu3+ and Ce3+ microamounts from 0.1-0.4M perchloric acid by the nitrobenzene solution of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (Mr = 200, 300, 400) has been studied. The equilibrium data and the typical maxima on the dependence of the metal distribution ratio on the total analytical concentration of polyethylene glycol in the system can be explained assuming that the species ML3+org, ML3+2org, ML3+3org, MLH2+-1org, and HL+org (where M3+ = Eu3+, Ce3+; L = polyethylene glycol) are extracted into the organic phase. The values of extraction and equilibrium constants in the organic phase were determined and the effect of the polyethylene glycol molecular weight on the equilibrium constants and on the abundances of individual species in the organic phase is discussed. It has been found that the addition of polyethylene glycol to the acid - nitrobezene - dicarbolide system increases the values of the separation factors αCe/Eu.


1981 ◽  
Vol 46 (1) ◽  
pp. 194-200 ◽  
Author(s):  
Marta Vojtíšková ◽  
Věra Jedináková ◽  
Libor Kuča

Benzyldibutylamine is a suitable extractant for the separation of Am(III) and Ln(III) from the acidic nitrate solutions. The effect of lanthanides and yttrium on the extraction of Am(III) has been followed under the conditions modelling the content of these components in the spent nuclear fuel. The separation factors αAm/Ln were evaluated for the optimum conditions found for the separation of Am(III) from the lanthanides. The coextraction of nitric acid and water into the organic phase is discussed.


Materials ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 2024 ◽  
Author(s):  
Xiaofei Hao ◽  
Hongjie Hu ◽  
Zhen Li ◽  
Limei Wu ◽  
Xueqin Liu ◽  
...  

Coalbed methane (CBM) is a kind of unconventional gas. CBM often contains a great deal of air when it comes out of the well. So, it must be condensed and purified before it can be applied. In this paper, raw clinoptilolite (Cp) was treated with grinding, gravimetric concentration, and ion-exchange using different aqueous solutions of salts. Then, the modified Cp powder was prepared into particles as adsorbents. Then, the adsorbents were used for nitrogen/methane separation in pressure swing adsorption (PSA) at the same condition of 0.2 MPa and 298 K. Research results indicated that there were micropores and lots of mesopores in the Cp, and the pores were mainly slit holes formed by sheet stacking. The adsorbents of NH4-Cp, Cs-Cp, and Cu-Cp showed good equilibrium selectivity for CH4, and the equilibrium separation factors of CH4 and N2 were 2.56, 2.31, and 1.95, respectively. The adsorbents of Na-Cp and Ag-Cp showed good equilibrium selectivity for N2, and the equilibrium separation factors of N2 and CH4 were 7.25 and 6.53, respectively. Consequently, the adsorbent of Na-Cp was suitable for nitrogen/methane mixture separation, which could make the concentration of methane concentrated from 19.7% to 30.72%.


2021 ◽  
Author(s):  
◽  
Matthew Thomas Stevens

<p>The Coromandel Volcanic Zone (CVZ) was the longest-lived area of volcanism in New Zealand hosting the commencement of large explosive rhyolitic and ignimbrite forming eruptions. The NW trending Coromandel Peninsula is the subaerial remnant of the Miocene-Pliocene CVZ, which is regarded as a tectonic precursor to the Taupo Volcanic Zone (TVZ), currently the most dynamic and voluminous rhyolitic volcanic centre on Earth. This study presents new single glass shard major and trace element geochemical analyses for 72 high-silica volcanic tephra layers recovered from well-dated deep-sea sediments of the SW Pacific Ocean by the Ocean Drilling Program (ODP) Leg 181. ODP Site 1124, ~720 km south and east from the CVZ, penetrated sediments of the Rekohu Drift yielding an unprecedented record of major explosive volcanic eruptions owing to the favourable location and preservation characteristics at this site. This record extends onshore eruptive sequences of CVZ explosive volcanism that are obscured by poor exposure, alteration, and erosion and burial by younger volcanic deposits. Tephra layers recovered from Site 1124 are well-dated through a combination of biostratigraphic and palaeomagnetic methods allowing the temporal geochemical evolution of the CVZ to be reconstructed in relation to changes in the petrogenesis of CVZ arc magmas from ~ 10 to 2 Ma. This thesis establishes major and trace element geochemical "fingerprints" for all Site 1124-C tephras using well-established (wavelength dispersive electron probe microanalysis) and new (laser ablation inductively coupled plasma mass spectrometry) in situ single glass shard microanalytical techniques. Trace element analysis of Site 1124-C glass shards (as small as 20 um) demonstrate that trace element signatures offer a more specific, unequivocal characterisation for distinguishing (and potentially correlating) between tephras with nearly identical major element compositions. The Site 1124-C core contains 72 unaltered Miocene-Pliocene volcanic glass-shard-bearing laminae > 1 cm thick that correspond to 83 or 84 geochemical eruptive units. Revised eruptive frequencies based on the number of geochemical eruptive units identified represent at least one eruption every 99 kyr for the late Miocene and one per 74 kyr for the Pliocene. The frequency of tephra deposition throughout the history of the CVZ has not been constant, rather reflecting pulses of major explosive eruptions resulting in closely clustered groups of tephra separated by periods of reduced activity, relative volcanic quiescence or non-tephra deposition. As more regular activity became prevalent in the Pliocene, it was accompanied by more silicic magma compositions. Rhyolitic volcanic glass shards are characterised by predominantly calc-alkaline and minor high-K enriched major element compositions. Major element compositional variability of the tephras deposited between 10 Ma and 2 Ma reveals magma batches with pre-eruptive compositional gradients implying a broad control by fractional crystallisation. Trace element characterisation of glass shards reveals the role of magmatic processes that are not readily apparent in the relatively homogeneous major element compositions. Multi-element diagrams show prominent negative Sr and Ti anomalies against primitive mantle likely caused by various degrees of plagioclase and titanomagnetite fractional crystallisation in shallow magma chambers. Relative Nb depletion, characteristic of arc volcanism, is moderate in CVZ tephras. HFSEs (e.g. Nb, Zr, Ti) and HREEs (e.g. Yb, Lu) remain immobile during slab fluid flux suggesting they are derived from the mantle wedge. LILE (e.g. Rb, Cs, Ba, Sr) and LREE (e.g. La, Ce) enrichments are consistent with slab fluid contribution. B/La and Li/Y ratios can be used as a proxy for the flux of subducting material to the mantle wedge, they suggest there is a strong influence from this component in the generation of CVZ arc magmas, potentially inducing melting. CVZ tephra show long-term coherent variability in trace element geochemistry. Post ~ 4 Ma tephras display a more consistent, less variable, chemical fingerprint that persists up to and across the CVZ/TVZ transition at ~ 2 Ma. Initiation of TVZ volcanism may have occurred earlier than is presently considered, or CVZ to TVZ volcanism may have occurred without significant changes in magma generation processes.</p>


Author(s):  
B. Z. Egan ◽  
D. E. Fain ◽  
G. E. Roettger ◽  
D. E. White

Synthesis gas produced in coal gasification processes contains hydrogen, along with carbon monoxide, carbon dioxide, hydrogen sulfide, water, nitrogen, and other gases, depending on the particular gasification process. Development of membrane technology to separate the hydrogen from the raw gas at the high operating temperatures and pressures near exit gas conditions would improve the efficiency of the process. Tubular porous alumina membranes with mean pore radii ranging from about 9 to 22 A have been fabricated and characterized. Based on the results of hydrostatic tests, the burst strength of the membranes ranged from 800 to 1600 psig, with a mean value of about 1300 psig. These membranes were evaluated for separating hydrogen and other gases. Tests of membrane permeabilities were made with helium, nitrogen, and carbon dioxide. Measurements were made at room temperature in the pressure range of 15 to 589 psi. In general, the relative gas permeabilities correlated qualitatively with a Knudsen flow mechanism; however, other gas transport mechanisms such as surface adsorption may also be involved. Efforts are under way to fabricate membranes having still smaller pores. At smaller pore sizes, higher separation factors are expected from molecular sieving effects.


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