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Nuclear reprocessing separates any usable elements (e.g., Uranium and Plutonium ) from Fission Product s and other materials in Spent Nuclear Reactor Fuels . Usually the goal is to recycle the Reprocessed Uranium or place these elements in new Mixed Oxide Fuel (MOX) , but some reprocessing is done to obtain plutonium for weapons. It is the process that closes the loop in the Nuclear Fuel Cycle . 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 Weapon s. The only reprocessing required, therefore, was the extraction of the Plutonium (free of Fission-product contamination) 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 (ORNL) in the 1943-1945 period to produce quantities of plutonium for evaluation and use in Weapons Programs . ORNL produced the first macroscopic quantities (grams) of separated plutonium with these processes. The Bismuth Phosphate process was first operated on a large scale at Hanford, Washington , in the latter 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 both uranium and plutonium in decontaminated form was developed at ORNL in 1949. It was this process, named PUREX, (see below) which became the current standard method. In March 1977, fear of nuclear weapons proliferation (especially after India demonstrated nuclear weapons capabilities using reprocessing technology) led President Jimmy Carter to issue a Presidential Directive to indefinitely suspend the commercial reprocessing and recycling of plutonium in the U.S. Other nations did not copy the policy and continued to reprocess spent nuclear fuel. However, in March 1999, the U.S. Department Of Energy (DOE) signed a contract with a Consortium comprised of Duke Energy, COGEMA, and Stone & Webster (DCS) to design and operate a Mixed Oxide (MOX) Fuel fabrication facility. Site preparation at the Savannah River Site (South Carolina) began in October of 2005. {Link without Title} The Global Nuclear Energy Partnership , announced by the secretary of the Department of Energy, Samuel Bodman , on February 6 , 2006 , is a plan to form an international partnership to reprocess Spent Nuclear Fuel in a way that renders the plutonium in it usable for Nuclear Fuel but not for Nuclear Weapons . OLD METHODS WHICH ARE NO LONGER USED Bismuth phosphate The bismuth phosphate process is a very old process which adds lots of material to the final highly active Waste , it was replaced by solvent extraction processes. The process was designed to extract Plutonium from Aluminium clad Uranium metal fuel. The fuel was declad by boiling it in Caustic Soda , after decladding the uranium metal was dissolved in Nitric Acid . The plutonium at this point is in the +4 oxidation state, it was then precipitated by the addition of Bismuth nitrate and Phosphoric Acid to form the bismuth phosphate. The plutonium was co-precipitated with this. The supernatant liquid (containing many of the Fission Products ) was separated from the solid. The precipitate was then dissolved in nitric acid before the addition of an Oxidant such as Potassium Permanganate which converted the plutonium to PuO22+ (Pu VI), then a Dichromate salt was added to maintain the plutonium in the +6 oxidation state. The bismuth phosphate was then re-precipitated leaving the plutonium in solution. Then a Iron (II) salt such as ''ferrous sulfate'' was added and the plutonium re-precipitated again using a bismuth phosphate carrier precipitate. Then Lanthanum salts and Fluoride were added to create solid lanthanum fluoride which acted as a carrier for the Pu. This was converted to the oxide by the action of a base. The lanthanum plutonium oxide was then collected and extracted with nitric acid to form plutonium nitrate. {Link without Title} Hexone or Redox This is a liquid-liquid extraction process which uses methyl isobutyl ketone as the extractant, the extraction is by a ''solvation'' mechanism. This process has the disadvantge of requiring the use of a salting out reagent ( Aluminium Nitrate ) is required to increase the nitrate concentration in the aqueous phase to obtain a resonable distribution ratio (D value). Also hexone is degraded by concentrated nitric acid. This process has been replaced by PUREX. {Link without Title} {Link without Title} Pu4+ + 4NO3- + 2S --> {Link without Title} Butex, β,β'-dibutyoxydiethyl ether A process based on a solvation extraction process using the triether extractant named above. This process has the disadvantge of requiring the use of a salting out reagent ( Aluminium Nitrate ) is required to increase the nitrate concentration in the aqueous phase to obtain a resonable distribution ratio. This process was used at Windscale many years ago. This process has been replaced by PUREX. THE CURRENT MAIN METHOD WHICH IS IN USE See Also: PUREX Overview of PUREX This process can be used to recover Weapon-grade materials from spent Nuclear Reactor fuel, and as such, its component chemicals are monitored. PUREX is an acronym standing for '''P'''lutonium and '''U'''ranium '''R'''ecovery by '''EX'''traction. The PUREX process is a Liquid-liquid Extraction method used to reprocess spent Nuclear Fuel , in order to extract Uranium and Plutonium , independent of each other, from the Fission products. This is currently the most completely developed and most widely used process in the industry at present. POSSIBLE METHODS FOR FUTURE USE Aqueous methods UREX The PUREX process can be modified to make a UREX ('''UR'''anium '''EX'''traction) process which could be used to save space inside high level Nuclear Waste disposal sites, such as Yucca Mountain , 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 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 (AHA) to the extraction and scrub sections of the process. The addition of AHA greatly diminishes the extractability of Plutonium and Neptunium , providing greater proliferation resistance than with the plutonium extraction stage of the PUREX process. TRUEX Adding a second extraction agent, octyl(phenyl)-N, N-dibutyl carbamoylmethyl phosphine oxide(CMPO) in combination with tributylphosphate, (TBP), the PUREX process can be turned into the TRUEX ('''TR'''ans'''U'''ranic '''EX'''traction) process this is a process which was invented in the USA by Argonne National Laboratory, and is designed to remove the transuranic metals (Am/Cm) 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 (DIAMide'''EX'''traction) 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 '''A'''cti'''N'''ide '''EX'''raction. 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. In order 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 has 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-triaiznyl pyridine (BTP) based process. References:
Other systems such as the dithiophosphinic acids are being worked on by some other workers. UNEX This is the ''UNiversal'' '''EX'''traction process which was developed in Carborane Anion (known as chlorinated cobalt dicarbollide) . The actinides are extracted by CMPO, and the Diluent is a polar Aromatic such as Nitrobenzene . Other dilents such as ''meta''-nitrobenzotri Fluoride and phenyl trifluoromethyl Sulfone {Link without Title} have been suggested as well. Non aqueous methods Pyroprocessing is a generic term for Pyrometallurgy processes. These processes are not currently in significant use worldwide, but they have been researched and developed at Argonne National Laboratory and elsewhere. The principles behind them are well understood, and no significant technical barriers exist to their adoption. The primary economic hurdle to widespread adoption is that reprocessing as a whole is not currently ( 2005 ) in favor, and places that do reprocess already have PUREX plants constructed. Consequently, there is little demand for new pyrometalurgical systems, although there could be if the Generation IV Reactor programs become reality. Advantages
Disadvantages
PYRO-A In nuclear engineering, PYRO-A refers to a type of Basket which is in contact with the molten salt. Then an electrical current is applied, the uranium will plate out as the conductive Uranium Dioxide on a solid metal cathode while the other actinides (and the rare earths) can be absorbed into a liquid Cadmium cathode. Many of the fission products (such as Cesium , Zirconium and Strontium ) remain in the salt. As alternatives to the moltern cadmium electrode it is possible to use a molten Bismuth cathode or a solid aluminium cathode[http://www.nea.fr/html/pt/docs/iem/jeju02/session2/Summary_sessionII.pdf . As an alternative to electrowinning, the wanted Metal can be isolated by using a Molten Alloy of an Electropositive metal and a less reactive metal. {Link without Title} Since the majority of the long term Radioactivity , and volume, of spent fuel comes from actinides, removing the actinides produces waste that is more compact, and not nearly as dangerous over the long term. The radioactivity of this waste will then drop to the level of various naturally occurring minerals and ores within a few hundred, rather than thousands of, years. The mixed actinides produced by pyrometallic processing can be used again as nuclear fuel, as they are virtually all either Fissile , or Fertile , though many of these materials would require a Fast Breeder Reactor in order to be burned efficiently. In a Thermal Neutron spectrum, the concentrations of several heavy actinides ( Curium-242 and Plutonium-240 ) can become quite high, creating fuel that is substantially different from the usual Uranium or mixed oxides (MOX) that most current reactors were designed to use. PYRO-B Another pyrochemical process, the PYRO-B process, has been developed for the processing and recycling of fuel from a Transmuter Reactor . A typical transmuter fuel is free of uranium and contains recovered Transuranic s in an inert matrix such as metallic Zirconium . In the PYRO-B processing of such fuel, an Electrorefining step is used to separate the residual transuranic elements from the fission products and recycle the transuranics to the reactor for fissioning. Newly-generated technetium and iodine are extracted for incorporation into transmutation targets, and the other fission products are sent to waste. Fluoride volatility A related process exists in which the Uranium is distilled away after conversion to Uranium Hexaflouride , this is the Fluoride Volatility process. ECONOMICS OF REPROCESSING NUCLEAR FUEL The relative Economics of reprocessing-waste disposal and interim storage-direct disposal has been the focus of much debate over the past ten years. Many approaches have been used and to a certain extent the approach taken has determined the outcome of the assessment. These studies model the total fuel cycle costs of a reprocessing-recycling system based on thermal recycling of plutonium and compare this to the total costs of an open fuel cycle with direct disposal. The range of results produced by these studies is very wide, but all are agreed that under current (2005) economic conditions the reprocessing-recycle option is the more costly. If reprocessing is undertaken only to reduce the radioactive level of spent fuel it should be taken into account that spent nuclear fuel becomes less radioactive over time. After 40 years its radioactivity drops by 99.9% though it still takes over a 1000 years for the level of radioactivity to approach that of natural uranium [http://www.world-nuclear.org/education/phys.htm . LIST OF NUCLEAR REPROCESSING SITES
SEE ALSO
REFERENCES
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