As there are some downsides to the PUREX process, there have been efforts to develop alternatives to the process, some of them compatible with PUREX (i.e. the residue from one process could be used as feedstock for the other) and others wholly incompatible. None of these have (as of the 2020s) reached widespread commercial use, but some have seen large scale tests or firm commitments towards their future larger scale implementation.
Pyroprocessing , suggested as part of the depicted metallic-fueled,
Integral fast reactor (IFR) a
sodium fast reactor concept of the 1990s. After the spent fuel is dissolved in molten salt, all of the recyclable
actinides, consisting largely of plutonium and uranium though with important minor constituents, are extracted using electrorefining/
electrowinning. The resulting mixture keeps the plutonium at all times in an unseparated
gamma and alpha emitting actinide form, that is also mildly self-protecting in theft scenarios.
Pyroprocessing is a generic term for high-temperature methods. Solvents are
molten salts (e.g. LiCl + KCl or LiF + CaF2) and molten metals (e.g. cadmium, bismuth, magnesium) rather than water and organic compounds.
Electrorefining,
distillation, and solvent-solvent extraction are common steps. These processes are not currently in significant use worldwide, but they have been pioneered at
Argonne National Laboratory with current research also being developed in Russia, as well, taking place at
CRIEPI in Japan, the Nuclear Research Institute of
Řež in Czech Republic,
Indira Gandhi Centre for Atomic Research in India and
KAERI in South Korea.
Advantages of pyroprocessing • The principles behind it are well understood, and no significant technical barriers exist to their adoption. • Readily applied to high-
burnup spent fuel and requires little cooling time, since the
operating temperatures are high already. • Does not use solvents containing hydrogen and carbon, which are
neutron moderators creating risk of
criticality accidents and can absorb the
fission product tritium and the
activation product carbon-14 in dilute solutions that cannot be separated later. • Alternatively, voloxidation) In contrast the PUREX process was designed to separate plutonium only for weapons, and it also leaves the
minor actinides (
americium and
curium) behind, producing waste with more long-lived radioactivity. • Most of the radioactivity in roughly 102 to 105 years after the use of the nuclear fuel is produced by the actinides, since there are no fission products with half-lives in this range. These actinides can fuel
fast reactors, so extracting and reusing (fissioning) them increases energy production per kg of fuel, as well as reducing the long-term radioactivity of the wastes. •
Fluoride volatility (see
below) produces salts that can readily be used in molten salt reprocessing such as pyroprocessing • The ability to process "fresh" spent fuel reduces the needs for
spent fuel pools (even if the recovered short-lived radionuclides are "only" sent to storage, that still requires less space as the bulk of the mass, uranium, can be stored separately from them). Uranium – even higher-specific-activity
reprocessed uranium – does not need cooling for safe storage. • Short-lived radionuclides can be recovered from "fresh" spent fuel, allowing either their direct use in industry science or medicine or the recovery of their decay products without contamination by other isotopes (for example: ruthenium in spent fuel decays to rhodium, all isotopes of which other than further decay to stable
isotopes of palladium. Palladium derived from the decay of fission ruthenium and rhodium will be nonradioactive, but fission palladium contains significant contamination with long-lived . Ruthenium-107 and rhodium-107 both have half-lives on the order of minutes and decay to palladium-107 before reprocessing under most circumstances) • Possible fuels for
radioisotope thermoelectric generators (RTGs) that are mostly decayed in spent fuel, that has significantly aged, can be recovered in sufficient quantities to make their use worthwhile. Examples include materials with half-lives around two years such as , , . While those would perhaps not be suitable for lengthy space missions, they can be used to replace
diesel generators in off-grid locations where refueling is possible once a year. Antimony would be particularly interesting because it forms a stable alloy with lead and can thus be transformed relatively easily into a partially self-shielding and chemically inert form. Shorter-lived RTG fuels present the further benefit of reducing the risk of
orphan sources as the activity will decline relatively quickly if no refueling is undertaken.
Disadvantages of pyroprocessing • 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 pyrometallurgical systems, although there could be if the
Generation IV reactor programs become reality. • The used salt from pyroprocessing is less suitable for conversion into glass than the waste materials produced by the PUREX process. • If the goal is to reduce the longevity of spent nuclear fuel in burner reactors, then better recovery rates of the minor actinides need to be achieved. • Working with "fresh" spent fuel requires more shielding and better ways to deal with heat production than working with "aged" spent fuel does. If the facilities are built in such a way as to
require high specific activity material, they cannot handle older "legacy waste" except blended with fresh spent fuel
Electrolysis The electrolysis methods are based on the difference in the
standard potentials of uranium, plutonium and minor actinides in a molten salt. The standard potential of uranium is the lowest, therefore when a potential is applied, the uranium will be reduced at the cathode out of the molten salt solution before the other elements.
PYRO-A and -B for IFR These processes were developed by
Argonne National Laboratory and used in the
Integral Fast Reactor project.
PYRO-A is a means of separating actinides (elements within the
actinide family, generally heavier than U-235) from non-actinides. The spent fuel is placed in an
anode basket which is immersed in a molten salt electrolyte. An electric current is applied, causing the uranium metal (or sometimes oxide, depending on the spent fuel) to plate out 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
caesium,
zirconium and
strontium) remain in the salt. As alternatives to the molten cadmium electrode it is possible to use a molten
bismuth cathode, or a solid aluminium cathode. 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. 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 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 uranium-plutonium oxides (MOX) that most current reactors were designed to use. Another pyrochemical process, the
PYRO-B process, has been developed for the processing and recycling of fuel from a
transmuter reactor ( a
fast breeder reactor designed to convert transuranic nuclear waste into fission products ). A typical transmuter fuel is free from uranium and contains recovered
transuranics 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.
Voloxidation Voloxidation (for
volumetric oxidation or
volatile oxidation) involves heating oxide fuel with oxygen, sometimes with alternating oxidation and reduction, or alternating oxidation by
ozone to
uranium trioxide with decomposition by heating back to
triuranium octoxide.
Advantages • Requires no chemical processes at all • Can in theory be done "self heating" via the
decay heat of sufficiently "fresh" spent fuel •
Caesium-137 has uses in
food irradiation and can be used to power
radioisotope thermoelectric generators. However, its contamination with stable and long lived reduces efficiency of such uses while contamination with in relatively fresh spent fuel makes the curve of overall radiation and heat output much steeper until most of the has decayed • Can potentially recover elements like
ruthenium whose ruthenate ion is particularly troublesome in PUREX and which has no isotopes significantly longer lived than a year, allowing possible recovery of the metal for use • A "third phase recovery" can be added to the process if substances that melt but don't vaporize at the temperatures involved are drained to a container for liquid effluents and allowed to re-solidify. To avoid contamination with low-boiling products which melt at low temperatures, a melt plug could be used to open the container for liquid effluents only once a certain temperature is reached by the liquid phase. • Strontium, which is present in the form of the particularly troublesome mid-lived fission product is liquid above . However,
Strontium oxide remains solid below and if strontium oxide is to be recovered with other liquid effluents, it has to be
reduced to the native metal before the heating step. Both Strontium and Strontium oxide form soluble
Strontium hydroxide and hydrogen upon contact with water, which can be used to separate them from non-soluble parts of the spent fuel. • As there are little to no chemical changes in the spent fuel, any chemical reprocessing methods can be used following this process
Disadvantages • At temperatures above the native metal form of several
actinides, including
neptunium (melting point: ) and
plutonium (melting point: ), are molten. This could be used to recover a liquid phase, raising proliferation concerns, given that uranium metal remains a solid until . While neptunium and plutonium cannot be easily separated from each other by different melting points, their differing solubility in water can be used to separate them. • If "nuclear self heating" is employed, the spent fuel with have much higher
specific activity, heat production and radiation release. If an external heat source is used, significant amounts of external power are needed, which mostly go to heat the uranium. • Heating and cooling the vacuum chamber and/or the piping and vessels to collect volatile effluents induces
thermal stress. This combines with radiation damage to material and possibly
neutron embrittlement if
neutron sources such as
californium-252 are present to a significant extent. • In the commonly used oxide fuel, some elements will be present both as oxides and as native elements. Depending on their chemical state, they may end up in either the volatalized stream or in the residue stream. If an element is present in both states to a significant degree, separation of that element may be impossible without converting it all to one chemical state or the other • The temperatures involved are much higher than the melting point of lead () which can present issues with radiation shielding if lead is employed as a shielding material • If filters are used to recover volatile fission products, those become
low- to intermediate level waste.
Fluoride volatility , not considering later
neutron capture, fraction of 100% not 200%.
Beta decay Kr-85→
Rb,
Sr-90→
Zr,
Ru-106→
Pd,
Sb-125→
Te,
Cs-137→
Ba,
Ce-144→
Nd,
Sm-151→
Eu,
Eu-155→
Gd visible. In the fluoride volatility process,
fluorine is reacted with the fuel. Fluorine is so much more reactive than even
oxygen that small particles of ground oxide fuel will burst into flame when dropped into a chamber full of fluorine. This is known as flame fluorination; the heat produced helps the reaction proceed. Most of the
uranium, which makes up the bulk of the fuel, is converted to
uranium hexafluoride, the form of uranium used in
uranium enrichment, which has a very low boiling point.
Technetium, the main
long-lived fission product, is also efficiently converted to its volatile hexafluoride. A few other elements also form similarly volatile hexafluorides, pentafluorides, or heptafluorides. The volatile fluorides can be separated from excess fluorine by condensation, then separated from each other by
fractional distillation or selective
reduction.
Uranium hexafluoride and
technetium hexafluoride have very similar boiling points and vapor pressures, which makes complete separation more difficult. Many of the
fission products volatilized are the same ones volatilized in non-fluorinated, higher-temperature volatilization, such as
iodine,
tellurium and
molybdenum; notable differences are that
technetium is volatilized, but
caesium is not. Some transuranium elements such as
plutonium,
neptunium and
americium can form volatile fluorides, but these compounds are not stable when the fluorine partial pressure is decreased. Most of the plutonium and some of the uranium will initially remain in ash which drops to the bottom of the flame fluorinator. The plutonium-uranium ratio in the ash may even approximate the composition needed for
fast neutron reactor fuel. Further fluorination of the ash can remove all the uranium,
neptunium, and plutonium as volatile fluorides; however, some other
minor actinides may not form volatile fluorides and instead remain with the alkaline fission products. Some
noble metals may not form fluorides at all, but remain in metallic form; however
ruthenium hexafluoride is relatively stable and volatile. Distillation of the residue at higher temperatures can separate lower-boiling
transition metal fluorides and
alkali metal (Cs, Rb) fluorides from higher-boiling
lanthanide and
alkaline earth metal (Sr, Ba) and
yttrium fluorides. The temperatures involved are much higher, but can be lowered somewhat by distilling in a vacuum. If a carrier salt like
lithium fluoride or
sodium fluoride is being used as a solvent, high-temperature distillation is a way to separate the carrier salt for reuse.
Molten salt reactor designs carry out fluoride volatility reprocessing continuously or at frequent intervals. The goal is to return
actinides to the molten fuel mixture for eventual fission, while removing
fission products that are
neutron poisons, or that can be more securely stored outside the reactor core while awaiting eventual transfer to permanent storage.
Chloride volatility and solubility Many of the elements that form volatile high-
valence fluorides will also form volatile high-valence chlorides. Chlorination and distillation is another possible method for separation. The sequence of separation may differ usefully from the sequence for fluorides; for example,
zirconium tetrachloride and
tin tetrachloride have relatively low boiling points of and . Chlorination has even been proposed as a method for removing zirconium fuel cladding, instead of mechanical decladding. Chlorides are likely to be easier than fluorides to later convert back to other compounds, such as oxides. Chlorides remaining after volatilization may also be separated by solubility in water. Chlorides of alkaline elements like
americium,
curium,
lanthanides,
strontium,
caesium are more soluble than those of
uranium,
neptunium,
plutonium, and
zirconium.
Advantages of halogen volatility • Chlorine (and to a lesser extent fluorine) is a readily available
industrial chemical that is produced in mass quantity • Fractional distillation allows many elements to be separated from each other in a single step or iterative repetition of the same step • Uranium will be produced directly as
Uranium hexafluoride, the form used in enrichment • Many volatile fluorides and chlorides are volatile at relatively moderate temperatures reducing thermal stress. This is especially important as the boiling point of uranium hexafluoride is below that of water, allowing to conserve energy in the separation of high boiling fission products (or their fluorides) from one another as this can take place in the absence of uranium, which makes up the bulk of the mass • Some fluorides and chlorides melt at relatively low temperatures allowing a "liquid phase separation" if desired. Those low melting salts could be further processed by molten salt electrolysis. • Fluorides and chlorides differ in water solubility depending on the cation. This can be used to separate them by aqueous solution. However, some fluorides violently react with water, which has to be taken into account.
Disadvantages of halogen volatility • Many compounds of fluorine or chlorine as well as the native elements themselves are toxic, corrosive and react violently with air, water or both •
Uranium hexafluoride and
Technetium hexafluoride have very similar boiling points ( and respectively), making it hard to completely separate them from one another by distillation. • Fractional distillation as used in
petroleum refining requires large facilities and huge amounts of energy. To process thousands of tons of uranium would require smaller facilities than processing billions of tons of petroleum however, unlike petroleum refineries, the entire process would have to take place inside radiation shielding and there would have to be provisions made to prevent leaks of volatile, poisonous and radioactive fluorides. •
Plutonium hexafluoride boils at this means that any facility capable of separating uranium hexafluoride from Technetium hexafluoride is capable of separating plutonium hexafluoride from either, raising proliferation concerns • The presence of
alpha emitters induces some (α,n) reactions in fluorine, producing both radioactive and neutrons. This effect can be reduced by separating alpha emitters and fluorine as fast as feasible. Interactions between chlorine's two stable isotopes and on the one hand and alpha particles on the other are of lesser concern as they do not have as high a cross section and do not produce neutrons or long lived radionuclides. • If carbon is present in the spent fuel it'll form
halogenated hydrocarbons which are extremely potent
greenhouse gases, and hard to chemically decompose. Some of those are toxic as well.
Radioanalytical separations To determine the distribution of radioactive metals for analytical purposes,
Solvent Impregnated Resins (SIRs) can be used. SIRs are porous particles, which contain an extractant inside their pores. This approach avoids the liquid-liquid separation step required in conventional
liquid-liquid extraction. For the preparation of SIRs for radioanalytical separations, organic Amberlite XAD-4 or XAD-7 can be used. Possible extractants are e.g. trihexyltetradecylphosphonium chloride(CYPHOS IL-101) or N,N0-dialkyl-N,N0-diphenylpyridine-2,6-dicarboxyamides (R-PDA; R = butyl, octy I, decyl, dodecyl). == Economics ==