Nuclear reprocessing
Nuclear reprocessing is the chemical separation of fission products and actinides from spent nuclear fuel. Originally, reprocessing was used solely to extract plutonium for producing nuclear weapons. With commercialization of nuclear power, the reprocessed plutonium was recycled back into MOX nuclear fuel for thermal reactors. The reprocessed uranium, also known as the spent fuel material, can in principle also be re-used as fuel, but that is only economical when uranium supply is low and prices are high. Nuclear reprocessing may extend beyond fuel and include the reprocessing of other nuclear reactor material, such as Zircaloy cladding.
The high radioactivity of spent nuclear material means that reprocessing must be highly controlled and carefully executed in advanced facilities by specialized personnel. Numerous processes exist, with the chemical based PUREX process dominating. Alternatives include heating to drive off volatile elements, burning via oxidation, and fluoride volatility. Each process results in some form of refined nuclear product, with radioactive waste as a byproduct. Because this could allow for weapons grade nuclear material, nuclear reprocessing is a concern for nuclear proliferation and is thus tightly regulated.
Relatively high cost is associated with spent fuel reprocessing compared to the once-through fuel cycle, but fuel use can be increased and waste volumes decreased. Nuclear fuel reprocessing is performed routinely in Europe, Russia, and Japan. In the United States, the Obama administration stepped back from President Bush's plans for commercial-scale reprocessing and reverted to a program focused on reprocessing-related scientific research. Not all nuclear fuel requires reprocessing; a breeder reactor is not restricted to using recycled plutonium and uranium. It can employ all the actinides, closing the nuclear fuel cycle and potentially multiplying the energy extracted from natural uranium by about 60 times.
Separated components and disposition
The potentially useful components dealt with in nuclear reprocessing comprise specific actinides. The lighter elements components include fission products, activation products, and cladding.| material | disposition |
| plutonium, minor actinides, reprocessed uranium | fission in fast, fusion fission hybrid, or subcritical reactor or use as MOX fuel |
| reprocessed uranium, filters | less stringent storage as intermediate-level waste |
| long-lived fission and activation products | nuclear transmutation or geological repository |
| medium-lived fission products 137Cs and 90Sr | medium-term storage as high-level waste; decay heat could be used to drive a Stirling engine |
| useful radionuclides, rare earths, and noble metals | industrial and medical uses |
| cladding, fission product zirconium | re-use for zircalloy cladding or storage as intermediate level waste |
History
The first large-scale nuclear reactors were built during World War II. These reactors were designed for the production of plutonium for use in nuclear weapons. The only reprocessing required, therefore, was the extraction of the plutonium from the spent natural uranium fuel. In 1943, several methods were proposed for separating the relatively small quantity of plutonium from the uranium and fission products. The first method selected, a precipitation process called the bismuth phosphate process, was developed and tested at the Oak Ridge National Laboratory between 1943 and 1945 to produce quantities of plutonium for evaluation and use in the US weapons programs. ORNL produced the first macroscopic quantities of separated plutonium with these processes.The bismuth phosphate process was first operated on a large scale at the Hanford Site, in the later part of 1944. It was successful for plutonium separation in the emergency situation existing then, but it had a significant weakness: the inability to recover uranium.
The first successful solvent extraction process for the recovery of pure uranium and plutonium was developed at ORNL in 1949. The PUREX process is the current method of extraction. Separation plants were also constructed at Savannah River Site and a smaller plant at West Valley Reprocessing Plant which closed by 1972 because of its inability to meet new regulatory requirements.
Reprocessing of civilian fuel has long been employed at the COGEMA La Hague site in France, the Sellafield site in the United Kingdom, the Mayak Chemical Combine in Russia, and at sites such as the Tokai plant in Japan, the Tarapur plant in India, and briefly at the West Valley Reprocessing Plant in the United States.
In October 1976, concern of nuclear weapons proliferation led President Gerald Ford to issue a Presidential directive to indefinitely suspend the commercial reprocessing and recycling of plutonium in the U.S. On 7 April 1977, President Jimmy Carter banned the reprocessing of commercial reactor spent nuclear fuel. The key issue driving this policy was the risk of nuclear weapons proliferation by diversion of plutonium from the civilian fuel cycle, and to encourage other nations to follow the US lead. After that, only countries that already had large investments in reprocessing infrastructure continued to reprocess spent nuclear fuel. President Reagan lifted the ban in 1981, but did not provide the substantial subsidy that would have been necessary to start up commercial reprocessing.
In March 1999, the U.S. Department of Energy reversed its policy and signed a contract with a consortium of Duke Energy, COGEMA, and Stone & Webster to design and operate a mixed oxide fuel fabrication facility. Site preparation at the Savannah River Site began in October 2005. In 2011 the New York Times reported "...11 years after the government awarded a construction contract, the cost of the project has soared to nearly $5 billion. The vast concrete and steel structure is a half-finished hulk, and the government has yet to find a single customer, despite offers of lucrative subsidies." TVA said in April 2011 that it would delay a decision until it could see how MOX fuel performed in the nuclear accident at Fukushima Daiichi.
Separation technologies
Water and organic solvents
PUREX
PUREX, the current standard method, is an acronym standing for Plutonium and Uranium Recovery by EXtraction. The PUREX process is a liquid-liquid extraction method used to reprocess spent nuclear fuel, to extract uranium and plutonium, independent of each other, from the fission products. This is the most developed and widely used process in the industry at present.When used on fuel from commercial power reactors the plutonium extracted typically contains too much Pu-240 to be considered "weapons-grade" plutonium, ideal for use in a nuclear weapon. Nevertheless, highly reliable nuclear weapons can be built at all levels of technical sophistication using reactor-grade plutonium. Moreover, reactors that are capable of refueling frequently can be used to produce weapon-grade plutonium, which can later be recovered using PUREX. Because of this, PUREX chemicals are monitored.
Modifications of PUREX
Many of these concepts, particularly those that separate the minor actinides once U and Pu have been extracted, are summarised in the advanced reprocessing of spent nuclear fuel.UREX
The PUREX process can be modified to make a UREX process which could be used to save space inside high level nuclear waste disposal sites, such as the Yucca Mountain nuclear waste repository, by removing the uranium which makes up the vast majority of the mass and volume of used fuel and recycling it as reprocessed uranium.The UREX process is a PUREX process which has been modified to prevent the plutonium from being extracted. This can be done by adding a plutonium reductant before the first metal extraction step. In the UREX process, ~99.9% of the uranium and >95% of technetium are separated from each other and the other fission products and actinides. The key is the addition of acetohydroxamic acid to the extraction and scrub sections of the process. The addition of AHA greatly diminishes the extractability of plutonium and neptunium, providing somewhat greater proliferation resistance than with the plutonium extraction stage of the PUREX process.
TRUEX
Adding a second extraction agent, octyl-N, N-dibutyl carbamoylmethyl phosphine oxide in combination with tributylphosphate,, the PUREX process can be turned into the TRUEX process. TRUEX was invented in the US by Argonne National Laboratory and is designed to remove the transuranic metals from waste. The idea is that by lowering the alpha activity of the waste, the majority of the waste can then be disposed of with greater ease. In common with PUREX this process operates by a solvation mechanism.DIAMEX
As an alternative to TRUEX, an extraction process using a malondiamide has been devised. The DIAMEX process has the advantage of avoiding the formation of organic waste which contains elements other than carbon, hydrogen, nitrogen, and oxygen. Such an organic waste can be burned without the formation of acidic gases which could contribute to acid rain. The DIAMEX process is being worked on in Europe by the French CEA. The process is sufficiently mature that an industrial plant could be constructed with the existing knowledge of the process. In common with PUREX this process operates by a solvation mechanism.SANEX
Selective ActiNide EXtraction. As part of the management of minor actinides it has been proposed that the lanthanides and trivalent minor actinides should be removed from the PUREX raffinate by a process such as DIAMEX or TRUEX. To allow the actinides such as americium to be either reused in industrial sources or used as fuel, the lanthanides must be removed. The lanthanides have large neutron cross sections and hence they would poison a neutron driven nuclear reaction. To date the extraction system for the SANEX process has not been defined, but currently several different research groups are working towards a process. For instance the French CEA is working on a bis-triazinyl pyridine based process.Other systems such as the dithiophosphinic acids are being worked on by some other workers.