Neptunium, transmutation

The new elements neptunium and plutonium have been produced in quantity by neutron bombardment of uranium. Subsequently many isotopes have been obtained by transmutation and synthetic isotopes of elements such as Ac and Pa are more easily obtained than the naturally occurring species. Synthetic species of lighter elements, e.g. Tc and Pm are also prepared. 

Each of the elements has a number of isotopes (2,4), all radioactive and some of which can be obtained in isotopicaHy pure form. More than 200 in number and mosdy synthetic in origin, they are produced by neutron or charged-particle induced transmutations (2,4). The known radioactive isotopes are distributed among the 15 elements approximately as follows actinium and thorium, 25 each protactinium, 20 uranium, neptunium, plutonium, americium, curium, californium, einsteinium, and fermium, 15 each herkelium, mendelevium, nobehum, and lawrencium, 10 each. There is frequently a need for values to be assigned for the atomic weights of the actinide elements. Any precise experimental work would require a value for the isotope or isotopic mixture being used, but where there is a purely formal demand for atomic weights, mass numbers that are chosen on the basis of half-life and availabiUty have customarily been used. A Hst of these is provided in Table 1. 

Kilogram amounts of neptunium ( Np) have been isolated as a by-product of the large-scale synthesis of plutonium in nuclear reactors that utilise 235u and 238u as fuel. The following transmutations occur ... 

Neptunium has been recovered during the reprocessing of defense-related fuels. The is recycled back to a reactor where it is transmuted to... 

All isotopes of plutonium are radioactive. The two isotopes that have found the most uses are Pu-238 and Pu-239. Pu-238 is produced by bombarding U-238 with deuterons in a cyclotron, creating neptunium-238 and two free neutrons. Np-238 has a half-life of about two days, and through beta decay it transmutates into plutonium-238. There are six allotropic metallic crystal forms of plutonium. They all have differing chemical and physical properties. The alpha (a) aUotrope is the only one that exists at normal room temperatures and pressures. The alpha allotrope of metallic plutonium is a silvery color that becomes yellowish as it oxidizes in air. AH the other allotropic forms exist at high temperatures. 

Although americiums main valence (oxidation state) is +3, it is tetravalent. It can form compounds with its ions of +4, +5, and +6, particularly when oxidized. Its most stable isotope is americium-243, with a half-life of 7,379 years, which, over time through alpha decay, transmutates into neptunium-239. 

After a few years of storage, the main radioactive heat emitters in HLW are 90Sr and 137Cs. In addition, extremely long-lived actinides—neptunium, plutonium, americium, and curium—should be collected for transmutation in the future. Therefore, different flowsheets can be proposed for waste processing. It is possible to extract each radionuclide in the special extraction (sorption) cycle, for example, uranium and plutonium in the PUREX process, and after that, minor actinides (MAs) by the TRUEX process,4 strontium by the SREX process,5,6 and cesium by sorption7 or extraction.8... 

Recently much attention has been given to the accelerator driven systems, burning in inert matrices, and the use of thorium to burn plutonium. The concept of a closed nuclear fuel cycle was traditionally considered as transmutation (burning) of only plutonium and recycled uranium, with minor actinides (neptunium, americium, curium) destined for final geological disposal. But as time goes on, a new understanding is emerging reduction of the quantity of actinides would ease requirements for final repositories and make them relatively less expensive. 

Neptunium (Np) 93 2.14xl0 y From activation/transmutation in Neutron detectors... 

From 1992, the role of Phenix as an irradiation facility has been emphasized, particularly in support of the CEA R D programme in the context of line 1 of the December 30th 1991 law on long-lived radioactive waste management. The first experiment, called SUPERFACT, led to the incineration of minor actinides (neptunium and americium). This programme was further strengthened in 1997, to compensate for the shutdown of Superphenix. It involves transmutation of Minor Actinides and Long-Lived Fission Products. 

Nuclear transmutations have been used to produce the elements with atomic number above 92, collectively known as the transuranium elements because they follow uranium in the periodic table. Elements 93 (neptunium, Np) and 94 (plutonium, Pu) were produced in 1940 by bombarding uranium-238 with neutrons ... 

The investigation of safety and more particularly of severe accident conditions is important for accelerator driven systems (ADS). Subcritical ADS could be of particular interest for the actinide transmutation from the safety point of view, because fast reactors with Neptunium, Americium and Curium have a much smaller fraction of delayed neutron emitters (compared to the common fuels and U), a small Doppler effect and possibly a positive coolant void coefficient. This poses a particular problem of control since the fraction of delayed neutrons is essential for the operation of a nuclear reactor in the critical state. In addition, the IRC presented in the past a review of accelerator-driven sub-critical systems with emphasis on safety related power transients followed by a survey of thorium specific problems of chemistry, metallurgy, fuel fabrication and proliferation resistance. 

The aim of the present improvement work on the PUREX process is to make the separations more selective and to create effluent streams of high purity. Thus, modifications are performed to make neptunium end up in a fraction for later transmutation in a reactor or accelerator-driven system. This can be achieved by a better control of redox conditions in the process. Today neptunium is partially co-exlracted with plutonium and uranium. There are also suggestions to withdraw product streams with Tc and respectively, i.e., long-lived nuclides that might be of interest for transmutation. 

The P/T process will be coupled after an improved PUREX process that puts all technetimn, iodine, and neptunium into the waste fraction or into special fractions. Thus, the waste will contain fission products and minor actinides (americium and curium). The process will probably be a solvent extraction process although molten salt systems are also studied as an alternative. The main issue will be to obtain pure Am and Cm fractions for subsequent destruction, i.e., fractions that do not contain any lanthanides. Some of the lanthanides, which are chemically very similar to trivalent actinides, have very high neutron cross sections. Therefore, they must be removed to make actinide burning possible. In some cases, it may also be desirable to transmute some long-lived fission products, e.g., Tc and l, to more shortlived nuclides. 

For the purpose of transmutation, the minor actinides of concern in spent fuel are neptunium, americium, and curium although small amounts of the higher actinides, berkeUum, californium, einsteinium, and fermium can be made under the right conditions. The reaction pathways leading to the production of the transuranium elements are given in Fig. 61.4. 

The transmutation of curium in reactors poses yet another set of problems compared with neptunium and americium because the curium isotopes have both shorter half-lives and higher spontaneous fission branches. In spent fuel, (Tm = 163 d) is by mass about 100 times... 

Over the past 10 years, modifications to the PUREX process have made it possible to more effectively separate neptunium. To effect the efficient separation of Np within the conventional PUREX process, Np is oxidized to VI state by nitrous add and is extracted in the first cycle along with U and Pu into the organic phase. The extracted Np( VI) follows the uranium stream and is later separated during the second purification cycle of uranium. In the RFC, the neptunium is sent to vitrification and disposed of as HLW but in an AFC option, the neptunium can be blended with MOX fuel or fabricated into special targets for later transmutation. The other minor actinides, ameridum and curium cannot be separated by reasonable modifications to the PUREX process. These elements will require the addition of special processing steps to separate them from the PUREX high-level waste stream. 

Each of these elements may be used for production of nuclear fuel or other purposes. The recovery efficiency for uranium is reported as 99.87% and for plutonium 99.36%-99.51% (NEA 2012). The extended PUREX includes separation of neptunium and technetium as well as recovery of americium and curium that are also separated from each other by additional extraction stages as given in detail in the flowsheet (NEA 2012). The advanced UREX-i-3 process generates six streams after separation uranium for re-enrichment Pu-U-Np for mixed oxide fuel c for managed disposal Am-Cm to be used as burnable poisons and for transmutation high-heat-generating products (Cs and Sr) and a composite vitrified waste with all other fission products. Some fuel types may require preliminary steps like grinding to enable their dissolution. 

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