# Patent

## Title
Reprocessing method by fluoride volatility process using fractional distillation

## Abstract

Fluorine or a fluorine compound is subjected to a reaction with a spent oxide fuel to produce fluorides of uranium and plutonium, and recovering the fluorides using a difference in volatility behavior. The method includes steps of: subjecting a mixture of UO2 and PuO2 with hydrogen fluoride mixed with hydrogen to HF-fluorinate uranium and plutonium into UF4 and PuF3; subjecting UF4 and PuF3 with a fluorine gas to F2-fluorinate uranium and plutonium into UF6 and PuF6; and fractionating UF6 and PuF6 using a difference in phase change of obtained UF6 and PuF6, removing a part of UF6, and volatilizing the remaining UF6 and PuF6 at the same time. By such a reprocessing method, PuF4 hard to undergo a reaction is prevented from being formed as an intermediate fluoride, the material of a reactor is hard to be corroded, and a consumption of expensive fluorine gas is reduced.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of separating and purifying nuclear fuel substances using a difference in fluorination volatility behavior of uranium, plutonium and other elements in a spent oxide fuel to reprocess the spent oxide fuel.
2. Description of the Related Art
A fluoride volatility process is one of methods for dry reprocessing of a spent fuel, in which nuclear fuel substances such as uranium and plutonium and various kinds of nuclear fission products are separated and recovered using a difference in volatility behavior when they are fluorinated. Techniques for applying the fluoride volatility process to a reprocessing process have been developed in the U.S. and other various countries since 1950s. However, each of those techniques has problem in higher fluorination and purification of plutonium. None of these techniques has reached a practical phase, and there has been no progress since 1970s.
In Japan, Japan Atomic Energy Research Institute has carried out the fluoride volatility process, and many advantages have been found, but development of the technique has been ended without establishing a plutonium purification step. In the fluoride volatility process carried out in that institute, uranium and plutonium are separated by two-stage fluorination using a fluidized bed furnace as a reactor with the temperature and fluorine concentration being changed. For example, in the first stage, uranium is fluorinated with an F2 concentration of 20% at the operating temperature of 330° C., and in the second stage, plutonium is fluorinated with an F2 concentration of 100% at the operating temperature of 330 to 550° C.
However, there is a disadvantage that it takes much time to convert uranium into uranium hexafluoride (UF6) because the reaction temperature in “fluorination of uranium” of the first stage is low, and that plutonium easily forms the most stable plutonium tetrafluoride (PuF4). Further, in “fluorination of plutonium” of the second stage, there is a disadvantage that plutonium is hard to be converted into plutonium hexafluoride (PuF6) (the conversion ratio or conversion rate decreases) from the point of view of thermodynamics and reaction temperature because plutonium forms into PuF4 of an intermediate fluoride in the first stage, and the fluorine concentration is so high that incomplete fluidization easily occurs.
Thus, a reprocessing process according to a fluoride volatility process using a flame furnace as a reactor has been proposed (see, for example, Japanese Patent Laid-Open Specification No. 2001-153991). Unlike the fluidized bed furnace, the flame furnace is a reactor operating under conditions of high temperature and high fluorine gas atmosphere.
If plutonium is converted under the conditions, a direct fluorination reaction of PuO2+3F2 (or 6F)→PuF6+O2 occurs, and therefore PuF4 is never produced as an intermediate fluoride. In addition, because the fluorination temperature and fluorine concentration are high, decomposition reaction of PuF6 is hard to proceed. However, since a corrosive gas at high temperatures and in high concentrations is required for the reaction, and conversion conditions are severe, the reactor is easily corroded and deteriorated, thus causing a problem in terms of materials. In addition, there are disadvantages that temperature adjustment for conversion conditions of a target substance is impossible, a large amount of expensive fluorine gas is used, and so on.
SUMMARY OF THE INVENTION
Problems to be solved by the present invention are to establish a method for producing PuF6 in which PuF4 hard to fluorinate further is prevented from being formed as an intermediate fluoride, to establish a method for producing PuF6 in which the material of a reactor is harder to corrode, to reduce a consumption of expensive fluorine gas, and so on.
According to the present invention, there is provided a reprocessing method by a fluoride volatility process using fractional distillation in which fluorine or a fluorine compound is subjected to a reaction with a spent oxide fuel in two stages to produce fluorides of uranium and plutonium, and recover uranium and plutonium as the fluorides using a difference in volatility behavior, the reprocessing method comprising the steps of:
HF fluorination of the spent oxide fuel containing UO2 and PuO2 in the reaction thereof with hydrogen fluoride mixed with hydrogen to produce UF4 and PuF3 as a first stage;
F2 fluorination of UF4 and PuF3 in the reaction thereof with fluorine gas to produce UF6 and PuF6 as a second stage; and
separation and volatilization of the resulting UF6 and PuF6 by fractionally distillating them (separating a gas and a liquid) due to a difference in phase change therebetween to remove a part of UF6 as gas, and then volatilizing the remaining UF6 and PuF6 at the same time.
In the reprocessing method, the first stage HF fluorination step is carried out preferably by supplying a hydrogen fluoride gas containing 10 to 30 vol % of hydrogen using a fluidized bed furnace operated in the temperature range of 350 to 430° C., and the second stage F2 fluorination step is carried out preferably by supplying a fluorine gas diluted to 20 to 40 vol % using a fluidized bed furnace operated in the temperature range of 500 to 750° C.
The separation and volatilization step is carried out by using at least one cold trap, and the removal of the part of UF6 is carried out by fractional distillation (gas-liquid separation) at the operating temperature and pressure controlled so that UF6 is in a gas region and PuF6 is in a liquid region in the phase diagrams of UF6 and PuF6.
In the reprocessing method by the fluoride volatility process using fractional distillation according to the present invention, the spent oxide fuel is subjected to a reaction with hydrogen fluoride mixed with hydrogen in the first stage, and the resultant fluorides are subjected to a reaction with a fluorine gas in the second stage, and thus PuF4 hard to undergo a reaction into a higher fluoride is never produced as an intermediate fluoride, thus making it possible to improve the ratio and rate of conversion into PuF6 and to reduce a consumption of expensive fluorine gas. In addition, since the fluidized bed furnaces are used to carry out reactions under lenient conditions in both first and second stages, the furnaces are hard to be corroded or deteriorated.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an explanatory diagram showing a basic process of a reprocessing method by a fluoride volatility process using fractional distillation according to the present invention;
FIG. 2 is a process flow showing one example of the reprocessing method by the fluoride volatility process using fractional distillation according to the present invention; and
FIG. 3 is a block diagram of an apparatus for carrying out the reprocessing method by the fluoride volatility process using fractional distillation according to the present invention.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is an explanatory view showing a basic process of a reprocessing method by a fluoride volatility process using fractional distillation according to the present invention. This is a reprocessing method in which fluorine or a fluorine compound is subjected to a reaction with a spent oxide fuel in two stages to produce fluorides of uranium and plutonium, and uranium and plutonium are recovered as UF6 and UF6+PuF6 using a difference in volatility behavior.
The first stage is an HF-fluorination step, where HF fluorination of a spent oxide fuel containing UO2 and PuO2 is conducted in the reaction thereof with hydrogen fluoride mixed with hydrogen to produce UF4 and PuF3. The HF-fluorination step is carried out by supplying a hydrogen fluoride gas (supply: 1.1 to 1.3 times the stoichiometric ratio, concentration: 60 to 90 vol %) containing 10 to 30 vol % of hydrogen using a fluidized bed furnace operated in the temperature range of 350 to 430° C. For the H2 gas, dependency on the concentration is not significant as long as a sufficient amount is supplied, and its concentration may be 5 vol % or greater, but is preferably 10 to 30 vol % when the HF concentration is 70 vol %. For the supply of hydrogen fluoride gas, an optimum amount was found to be 1.15 times the stoichiometric ratio from thermodynamic calculation and empirically, and the supply of hydrogen fluoride gas which is 1.1 to 1.3 times the stoichiometric ratio brought about a preferred result. Both UF4 and PuF3 produced in this way tend to form into hexafluorides easily from a thermodynamic viewpoint. The used amount of expensive fluorine gas can be reduced by about 60% compared to conventional methods because an HF gas is used in the HF fluorination.
The second stage is an F2 fluorination step, where F2 fluorination of UF4 and PuF3 is conducted in the reaction thereof with a fluorine gas to produce UF6and PuF6. The F2 fluorination step is carried out by supplying a fluorine gas (supply: 1.1 to 1.3 times the stoichiometric ratio) diluted to 20 to 40 vol % using a fluidized bed furnace operated in the temperature range of 500 to 750° C. Conversion of UF4 by the fluorine gas is not particularly cumbersome because it has been already performed on a commercial scale, and conversion of PuF3 into PuF6 can be carried out at a low temperature (500 to 750° C.) easily, speedily and stably compared to the conversion of PuF4 into PuF6. In the above two-stage fluorination process according to the present invention has an advantage that PuF6 can be produced without the intermediation of PuF4.
The resulting UF6 and PuF6 are fractionally distillated using a difference in phase change thereof to remove a part of UF6 as gas, and then the remaining UF6 and PuF6 are volatilized at the same time (separation and volatilization step). Cold traps are used in this step, and a part of UF6 is removed by fractional distillation at the operating temperature and pressure controlled so that UF6 is in a gas region and PuF6 is in a liquid region in the well-known phase diagrams of UF6 and PuF6. Conditions for the separation are set so that the pressure is about 83.6 kPa in the temperature range of 53 to 56.5° C. (about 85.01 kPa at 53.4 to 57° C.). Consequently, UF6 is vaporized and PuF6 is liquefied, thus making it possible to separate them. The conditions are set in consideration of an operation on the negative pressure side, and therefore have a quite limited range, but if a separation operation is possible on the positive pressure side as well, an allowable range of pressure and temperature is wider. Then, the pressure is reduced to about 50 kPa, whereby the remaining UF6 and PuF6 are vaporized at the same time.
In this way, the fluoride volatility process can be applied to recover uranium and plutonium as UF6 and UF6+PuF6. This reprocessing process can be used for a light water reactor nuclear fuel cycle, FBR nuclear fuel cycle or the like. If the processing object is a spent metal fuel, the method of the present invention can be applied by oxidizing the metal fuel as preprocessing.
EXAMPLES 
FIG. 2 is a process flow showing one example of the reprocessing method by the fluoride volatility process using fractional distillation according to the present invention. This is an example of a process of reprocessing a spent oxide fuel. The spent oxide fuel as a raw material has been subjected to decladding processing, and its main constituent elements include U, Pu, O, Zr, Nb, Mo, Tc, Ru, Sb, Te, Cs, Np, Am and Cm, and uranium exists in a form of UO2 and plutonium exits in a form of PuO2. These raw materials are fluorinated in two stages.
<HF Fluorination>
In the first-stage HF fluorination, a raw material (spent oxide fuel) is subjected to a reaction with an HF gas (supply: 1.15 times the stoichiometric ratio, concentration: 70 vol %) using a fluidized bed furnace (operating temperature: 400° C.). At this time, an H2 gas is also supplied, and the supply thereof is greater than 0.5 times the stoichiometric ratio to PuO2, and the concentration may be any of 5 to 100 vol %, but should be 30 vol % if the H2 gas is supplied along with 70 vol % HF. Consequently, UF4 and PuF3 are produced. Most impurities in the raw material remain oxides without undergoing a reaction, or form into fluorides or oxyfluorides. Resulting reactions are as shown below.

UO2(solid)+4HF═UF4(solid)+2H2O

PuO2(solid)+3HF+1/2 H2═PuF3(solid)+2H2O

<F2 Fluorination>

In the second-stage F2 fluorination, the intermediate fluorides produced in the first-stage HF fluorination are converted into the hexafluorides. The operating temperature of the fluidized bed furnace is set to 500 to 750° C., and the intermediate fluoride is subjected to a reaction with a fluorine gas to produce the hexafluorides of uranium and plutonium. The supplied fluorine gas is diluted with an N2 gas to adjust the concentration of the fluorine gas to 20 to 40 vol % and the excess fluorine gas ratio to 1.15 times the stoichiometric ratio. By F2 fluorination, uranium (UF6) and plutonium (PuF6) are volatilized along with many impurities, but ZrF4, CsF, PuF4, AmF3, CmF3 and the like remain along with a bed material because of the low vapor pressure. Some oxides that are not completely fluorinated (UO2, etc.), oxyfluorides (UO2 F2, etc.) and double salts (Cs2 UF8, etc.) also remain.
<Condensation of UF6.PuF6>
Volatilized UF6and PuF6 are condensed in cold traps. The operating temperature is −70 to 0° C., and the working pressure is about 50 kPa. Many volatile substances are condensed under the conditions, but most of F2 (boiling point: −188.24° C.), HF (melting point: −84.79° C., boiling point: 19.67° C.) and TeF6 (boiling point: −39.55° C.) each having a low melting or boiling point remains gaseous, and therefore solids and gases are separated from condensates.
<Separation of UF6/PuF6>
If the cold traps are decompressed to about 83.6 kPa at 53.1 to 56.5° C. (about 85.01 kPa at 53.4 to 57° C.), for example, UF6 is vaporized and PuF6 is liquefied (for this purpose, the temperature and pressure are set so that UF6 is in a gas region and PuF6 is in a liquid region in the phase diagrams of UF6 and PuF6). UF6 and PuF6 can be fractionally distillated under the conditions. Volatilized amount of UF6 can be optionally set by appropriately controlling the temperature and pressure in actual operations. In light of the melting or boiling point of each substance, a part of PuF6, and impurities having relatively low boiling points, such as NbF5, MoF6, TcF6, RuF5, SbF5, TeF6 and NpF6, likely behave in conjunction with UF6.
<Volatilization of UF6.PuF6>
A certain amount of UF6 is volatilized, and then the pressure is reduced to about 50 kPa with the temperature of the cold traps unchanged, whereby UF6 and PuF6 can be vaporized at the same time. The temperature and pressure can be set in accordance with characteristics of the cold traps referring to the phase diagrams of UF6 and PuF6.
<Refinement of UF6>
UF6 produced by F2 fluorination contains a very small amount of PuF6 and volatile impurities. These impurities are made to pass through chemical traps filled with a substance having an action of chemically adsorbing the impurities, whereby the impurities can be removed to purify UF6. Chemical traps are installed in multiple stages as required.
(1) LiF—UO2 F2 Traps
In this process, chemical traps using lithium fluoride (LiF) and uranyl fluoride (UO2F2) either alone or in combination as a filler are used in the first stage for the purpose of removal of PuF6. Instead thereof, any filler having an action of reducing PuF6 may be used, and use of UF4 and UF5 can be considered as well. The reaction between LiF and PuF6 is a reversible reaction, PuF6 is adsorbed to LiF at the operating temperature of 300° C., and detached from LiF by heating it to 450° C. Thus, LiF is used at the operating temperature of 300° C. CsF is adsorbed at the temperature, too. PuF6 adsorbed to UO2F2 can be used in an MOX (mixed oxide) reconverting process as a raw material without being detached.
(2) MgF2 Traps
Chemical traps using MgF2 as a filler are provided in the second stage. MgF2 has an action of adsorbing NbF6, MoF6, TcF6, RuF5, SbF5 and NpF6, and is used at the operating temperature of 120° C. here.
(3) NaF Traps
Chemical traps using NaF as a filler are installed in the third stage. NaF is known to adsorb UF6 through the reaction of UF6+2NaF→Na2 UF8 at 25 to 250° C. Na2UF8 decomposes into NaF and UF6 again at 300 to 400° C., but NaF forms double salts with RuF5 and NbF6. It has an action of adsorbing ZrF4, but most of ZrF4 remains in the fluidized bed furnace as a nonvolatile substance along with the bed material, and only a very small amount thereof is removed by the NaF traps.
<Adjustment of Pu Enrichment>
A mixed gas of volatilized UF6 and PuF6 and UF6 purified by the chemical traps are mixed together in a desired ratio using a gas mixer, and the plutonium enrichment is adjusted. For operating conditions of the gas mixer, a slightly negative pressure and a temperature of about 70 to 80° C. are adopted.
<Condensation of UF6/UF6.PuF6>
UF6 not used for adjustment of the plutonium enrichment, of UF6 purified by the chemical traps, or a mixed gas of UF6 after adjustment of the plutonium enrichment and PuF6 is condensed. The operating temperature is −70 to 0° C., and the pressure is about 50 kPa.
<Volatilization of UF6/UF6.PuF6>
The temperature is increased to 70 to 80° C. with the pressure (50 kPa) unchanged, whereby the condensed UF6 or mixture of UF6 and PuF6 is vaporized and provided for a reconversion process.
If vaporized simple UF6 is filled in a cylinder for UF6, it can be used as a raw material for uranium enrichment, and this process can be used in a light water reactor fuel cycle. As an option, by setting conditions for liquefying UF6, in which the temperature of the cold traps trapping UF6 is 64° C. or higher and the pressure is 152 kPa or greater, UF6 can be liquefied and filled in the cylinder.
FIG. 3 is a block diagram of an apparatus for carrying out the above reprocessing method by a fluoride volatility process using fractional distillation. A raw material (spent oxide fuel) in a raw material supply tank 10 is fed to an HF fluorination furnace (fluidized bed furnace) 12, reacts with an HF+H2 gas into an intermediate material, and is stored in an intermediate fluoride supply tank 14. The intermediate fluoride in the intermediate fluoride supply tank 14 is fed to an F2 fluorination furnace (fluidized bed furnace) 16, and reacts with an F2 gas into a hexafluoride.
The obtained hexafluoride is introduced into first cold traps 18, where UF6.PuF6 is condensed, UF6/PuF6 is separated, and UF6.PuF6 is volatilized. UF6 is purified through LiF/UO2 F2 traps 20, MgF2 traps 22 and NaF traps 24. UF6 and UF6.PuF6 are introduced into second cold traps 26, where UF6 is condensed and volatilized, and UF6.PuF6 is condensed and volatilized, and they are provided for the reconversion process.

## Claims

1. A reprocessing method by a fluoride volatility process using fractional distillation in which fluorine or a fluorine compound is subjected to a reaction with a spent oxide fuel in two stages to produce fluorides of uranium and plutonium, and recover uranium and plutonium as the fluorides using a difference in volatility behavior, the reprocessing method comprising the steps of:
HF fluorination of the spent oxide fuel containing UO2 and PuO2 in the reaction thereof with hydrogen fluoride mixed with hydrogen to produce UF4 and PuF3 as a first stage, the HF fluorination step being carried out by supplying a hydrogen fluoride gas in a supply amount of 1.1 to 1.3 times the stoichiometric ratio and containing 10 to 30 vol % of hydrogen to a fluidized bed furnace operated in the temperature range of 350 to 430° C.;
F2 fluorination of UF4 and PuF3 in the reaction thereof with fluorine gas to produce UF6 and PuF6 as a second stage; and
separation and volatilization of the resulting UF6 and PuF6 by fractionally distillating them due to a difference in phase change therebetween to remove a part of UF6 as gas, and then volatilizing the remaining UF6 and PuF6 at the same time.

2. The reprocessing method by a fluoride volatility process using fractional distillation according to claim 1, wherein the second stage F2 fluorination step is carried out by supplying a fluorine gas diluted to 20 to 40 vol % to a fluidized bed furnace operated in the temperature range of 500 to 750° C.

3. The reprocessing method by a fluoride volatility process using fractional distillation according to claim 1, wherein the separation and volatilization step is carried out by using at least one cold trap, and the removal of the part of UF6 is carried out by fractional distillation at an operating temperature and pressure controlled so that UF6 is in a gas region and PuF6 is in a liquid region in the phase diagrams of UF6 and PuF6.

4. The reprocessing method by a fluoride volatility process using fractional distillation according to claim 2, wherein the separation and volatilization step is carried out by using at least one cold trap, and the removal of the part of UF6 is carried out by fractional distillation at an operating temperature and pressure controlled so that UF6 is in a gas region and PuF6 is in a liquid region in the phase diagrams of UF6 and PuF6.