Several diamide derivates were synthesized in our laboratory. The extraction of actinides and some fission products by these
compounds were studied. N,N,N’,N’-tetra-(2-ethylhexyl)-3-oxa pentanediamide [TEHOPDA) was proven to be a suitable extractant
for the removal of actinides from nitric acid solution. The actinides can be stripped from the loaded solvent by the dilute
nitric acid. TEHOPDA showed a high loading capacity to actinides and lanthanides with a mixture of n-octanol and kerosene
as the diluent. Considering the effective-extraction and easy-stripping of actinides, 0.25 mol/l TEHOPDA — 30% n-octanol +
70% kerosene was selected as the solvent. A cascade extraction experiment was carried out with the simulated dissolver solution
of spend fuel as feed. 99.99% U and 99.999% Am, Pu, and Np were extracted in a 4-stage test. Based on the experimental results,
a conceptual reprocessing process was proposed.
The extraction of Tc(VII) by the mixture of tri-n-butyl phosphate (TBP) and 2-nitrophenyl octyl ether (NPOE) has been studied. 0.2M NPOE-TBP can extract Tc(VII) effectively from 1M HNO3 and 1M NaOH solutions with distribution ratios of 57.1 and 12.3, respectively. The distribution ratio of Tc(VII) decreases with increasing (>0.5M) HNO3 concentration but increases with the increase of NaOH concentration. A pH 9 NaOH solution has proven to be suitable for Tc(VII) stripping. A simple extraction-stripping cycle can remove Tc(VII) from a sodium hydroxide solution. A more sophisticated extraction process is proposed to remove Tc(VII) from nitric acid solution because the co-extracted HNO3 prevents the direct stripping of Tc(VII) by NaOH solution of pH 9.
Valency control of neptunium is an important issue in the partitioning of high level liquid waste (HLLW) from power-reactor
spent fuel treatment. The redox behavior of neptunium in HLLW is quite different from that in nitric acid because of the effect
of the large amount of ions in HLLW. In order to remove neptunium from HLLW, we studied the reduction of neptunium in synthetic
HLLW (SHLLW) to maintain its valency at IV so that it can be extracted by TRPO extractant in the well developed Chinese TRPO
process. Five different reductants were tested and the reduction behavior was investigated. The influence of some active elements
in SHLLW was studied. The mechanism that the reductants react with neptunium through Fe element was supposed and proved by
experiments. The reduction rate of Np(V) was highly enhanced by Fe element. Finally, a hybrid reductant was suggested and
good reduction efficiency was obtained.
An overview of the work carried out on the development of the stripping of transuranium elements which are extracted by trialkyl
phosphine oxide in the actinides-partitioning TRPO process in recent years. Several representative stripping agents and corresponding
processes are introduced in three categories of the management of TRU elements: transmutation, alpha waste conditioning and
Purex-TRPO integrated process.
This study discusses the thermal behavior of the 6.5 Ah cylinder Ni/MH hydride battery with 0.5 wt% ytterbium oxide (Yb2O3) in nickel electrode and 1.0 wt% super absorbent polymer (SAP) in hydrogen-storage alloy (MH) electrode during charging to 150% of its rating capacity. Quantity of heat and heat generation rate of the battery during charging are studied by quartz frequency microcalorimeter. Heat generation curve is fitted into a function, and heat transport equation is solved. Using measured data, the internal temperature profiles at the terminal moment of charging at 1C, 3C, and 5C are simulated by FEM. Influence of Yb2O3 and SAP on the thermal behavior of Ni/MH battery is examined by the two-dimensional thermal model. Results show that addition of Yb2O3 and SAP can achieve substantial improvement for thermal behavior of Ni/MH battery at 1C,3C, and 5C charging.
The present work confirms the high separation ability of purified Cyanex 301 towards trivalent americium over europium in liquid-liquid extraction. Solvent 2-nitrophenyl octyl ether (NPOE) lowered the partitioning of Am3+ but remained the separation ability over europium. Solvent toluene and 3-octanone lowered the separation factor to 1000. It is feasible to separate Am3+ from Eu3+ by Cyanex 301 which was immobilized in the macro porous polymer (MPP). 3-Octanone is a suitable solvent for dissolving NH4OH-saponified Cyanex 301 and MPP is a suitable solid supported material for column operation. A five-step column experiment demonstrated the feasibility to separate Am3+ from Eu3+ in column which was packed with Cyanex 301-impregnated MPP.
Non-isothermal crystallization of isotactic poly(4-methyl-pentene-1) (P4MP1) is studied by differential scanning calorimeter (DSC), and kinetic parameters such as the Avrami exponent and the kinetic crystallization rate (Zc) are determined. From the cooling and melting curves of P4MP1 at different cooling rates, the crystalline enthalpy increases with the increasing cooling rate, but the degree of crystalline by DSC measurement shows not much variation. Degree of crystalline of P4MP1 calculated by wide angle X-ray diffraction pattern shows the same tendency with crystalline enthalpy, indicating that re-crystallization occurs when samples heated above the second glass transition temperature of P4MP1. By Jeziorny analysis, n1 value suggests that mainly spherulites’ growth at 2.5 K min−1 transforms into a mixture mode of three-dimensional and two-dimensional space extensions with further increasing cooling rate. In the secondary crystallization process, n2 values indicate that the secondary crystallization is mainly the two-dimensional extension of the lamellar crystals formed during the primary crystallization process. The rates of the crystallization, Zc and t1/2 both increase obviously with the increase of cooling rate, especially at the primary crystallization stage. By Mo's method, higher cooling rate should be required in order to obtain a higher degree of crystallinity at unit crystallization time.
This study builds the interdisciplinary knowledge network of China, which is used to catch the knowledge exchange structure of disciplines, and investigates the evolution process from 1981 to 2010. A network analysis was performed to examine the special structure and we compare state of the networks in different periods to determine how the network has got such properties. The dataset are get from the reference relationship in literature on important Chinese academic journals from 1980 to 2010. The analytical results reveal the hidden network structure of interdisciplinary knowledge flows in China and demonstrate that the network is highly connected and has a homogeneous link structure and heterogeneous weight distribution. Through comparing of the network in three periods, that is 1981–1990, 1991–2000 and 2001–2010, we find that the special evolution process, which is limited by the number of nodes, play an important influence on interdisciplinary knowledge flows.
Authors:Ping Zhang, Hairong Wang, Jianchen Wang, and Jing Chen
To simplify TRPO process, a novel ligand, N,N’-dimethyl-3-oxa-glutaramic acid (DMOGA), was synthesized and used for stripping
of An(III, IV) from 30% TRPO-kerosene. The distribution ratios for transuranium elements, including Np(IV), Pu(IV), Am(III),
and some fission products, including Eu(III), Fe and Zr between 30% TRPO-kerosene and various HNO3-DMOGA solutions were measured. An(III, IV) and Ln(III) extracted to TRPO from simulated high level liquid waste could be
recovered with an efficiency of 99.9% above in one stream with a 3-stage crosscurrent strip experiment with 0.2M DMOGA in
HNO3 solution. Using this new agent, the back extraction of TRU elements from loaded TRPO phase becomes more simple and practical.
Therefore, the original TRPO process could be simplified.
Authors:Meng Wei, Qian’ge He, Xiaogui Feng, and Jing Chen
The crystal structure, melting range, decomposition temperature, solubilities in aqueous and organic phase, and distribution
ratio in biphase system of N,N,N′,N′-tetramethyl diglycolamide (TMDGA) have been studied in the present work. Water-soluble TMDGA with very low solubility in
kerosene or 30 % trialkyl phosphine (TRPO)/kerosene meets the primary requirement to act as the stripping agent in TRPO process
which has been developed for actinides partitioning from high level waste. Slope analysis, electrospray ionization mass spectrometry
(ESI–MS) and spectrophotometric titration indicate that in weak and moderate acidic aqueous solution, up to three TMDGA molecules
form complexes with Zr4+, trivalent lanthanides (Ln3+), trivalent actinides (An3+) or tetravalent actinides (An4+). Their complex formation constants determined by liquid–liquid extraction method follow the order predicted by the electrostatic
model of 4f and 5f elements and the covalent model of 4d transition elements: Ln3+ ~ An3+ < An4+ ≪ Zr4+. Hydrolysis of actinide cations, especially An4+, in the media of low acidity, reduces the complexation stability. In addition, the effect of aqueous acidity and temperature
has been investigated. No obvious influence of temperature on Np4+ complexes has been found. However, the influence on Am3+ and Pu4+, especially on their 1:1 or 1:2 complex species with TMDGA, is relatively considerable. Strong affinity of TMDGA to An3+ and An4+ implies that TMDGA has potential to strip An3+ and An4+ from TRPO.