CN108369828A - Application of the aldoxime containing at least five carbon atoms in plutonium reduction reextraction extract operation as anti-nitrous agent - Google Patents
Application of the aldoxime containing at least five carbon atoms in plutonium reduction reextraction extract operation as anti-nitrous agent Download PDFInfo
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- CN108369828A CN108369828A CN201680065527.XA CN201680065527A CN108369828A CN 108369828 A CN108369828 A CN 108369828A CN 201680065527 A CN201680065527 A CN 201680065527A CN 108369828 A CN108369828 A CN 108369828A
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Abstract
This application involves the aldoxime comprising at least five carbon atoms as the application in anti-nitrous agent in plutonium reduction reextraction extract operation.The application is suitable for the processing method of any spentnuclear fuel including one or more plutonium reduction reextraction extract operations, also, is particularly suitable for the PUREX methods implemented in the modern factories such as processing spentnuclear fuel, and by its derivative method.
Description
Technical field
This application involves the fields of processing spentnuclear fuel.
More specifically, this application involves the conducts in plutonium reduction reextraction extract operation of the aldoxime at least five carbon atoms
The application of anti-nitrous agent.
The application is suitable for the processing method of any spentnuclear fuel including one or more plutonium reduction reextraction extract operations.
The operation is especially included in PUREX methods, and PUREX methods are, for example, in modern nuclear fuel treatment plant (that is, France draws
UP3 the and UP2-800 factories in Hague, and Japan factory of the villages Liu Suo) in implement method, the first decontamination cycle is first carried out
U/Pu allocation steps, secondly after the first decontamination cycle improve plutonium decontamination cycle in fission product plutonium purification (usually
Referred to as " the second plutonium cycle ").
The operation is also contained in a certain number of methods derived from PUREX methods, the method example derived from PUREX methods
Method (being known as COEX methods) described in International Application Serial No. PCT WO 2006/072729 [1] in this way or International Application Serial No. PCT WO
Method described in 2011/000844 [2].
Background technology
In the plutonium reduction reextraction extract operation implemented in the processing method of aforementioned spentnuclear fuel, by the way that plutonium is reduced into oxidation state
III (in this state, plutonium is very low to the affinity of organic phase) makes plutonium be in organic phase (or the solvent of oxidation state IV from it
Phase) enter in aqueous phase.
Reducing agent is added in the aqueous phase for back extraction and makes its stabilization with anti-nitrous agent, the reducing agent
Induction plutonium (IV) is reduced into plutonium (III).
The PUREX methods for example in modern nuclear fuel reprocessing plant implemented (will be simply referred to as in this paper rest parts
" PUREX methods ") the first decontamination cycle, it is uranium (IV) (or nitre that reducing agent used in plutonium is stripped in U/Pu allocation steps
Sour uranium), and anti-nitrous agent is hydrazine nitrate (also referred to as hydrazine).
The main chemical reactions to be considered are：
Plutonium (IV) is reduced into plutonium (III) (functional response) using uranium (IV)：
U4++2Pu4++2H2O→UO2 2++2Pu3++4H+
Plutonium (III) is reoxidised into plutonium (IV) (parasitic reaction)：
Pu3++HNO2+1.5H++0.5NO3 -→Pu4++0.5H2O+1.5HNO2
Nitrous acid is broken to hydrazoic acid (useful reaction) using hydrazine：
N2H5NO3+HNO2→N3H+HNO3+2H2O.
The first two reaction is happened in aqueous phase and organic phase, and the nitrous acid of hydrazine destroys reaction and occurs over just aqueous phase
In, this is because hydrazine cannot be formed by the TRI N BUTYL PHOSPHATE (or TBP) by 30% (v/v) in hydrogenation tetrapropylene (or HTP)
Organic extractant phase.
There are plutonium (III) in organic phase, though on a small quantity if can by the oxidation of the first two catalytic reaction uranium (IV), to
Generate nitrous acid.
It can determine, when carrying out experimental study in laboratory centrifuge extractor, even if the extractor residence time is very short
(about several seconds), uranium (IV) consumes also very high as caused by aoxidizing.The oxidation of uranium (IV) occurs mainly in organic phase, because
Hydrazine is only contained in aqueous phase.As a result, plutonium reduction reextraction operation scheme provides a large amount of excessive reducing agents.
According to following reaction, it is anti-with nitrous acid in turn via the destruction reaction of hydrazine to be formed by hydrazoic acid by nitrous acid
It answers：
HN3+HNO2→N2+N2O+H2O。
However, the dynamics of the reaction is more more slowly to the destruction of nitrous acid than hydrazine, it means that hydrazoic acid appears in U/
In the outflow aqueous phase and organic phase of Pu allocation steps.
Therefore, because hydrazine cannot only work in aqueous phase by organic extractant phase and therefore, which results in the height of reagent
Consume and produce the chemical substance for the commercial Application for interfering this method.
In order to solve this problem, use is proposed in International Application Serial No. PCT WO 2008/148863 [3] by butyl aldoxime
The anti-nitrous system of two-phase that (also referred to as butyraldehyde oxime or butyraldoxime) is combined with hydrazine, butyl aldoxime make
Organic phase is stablized, and hydrazine makes aqueous phase stablize.
Although butyl aldoxime is used in combination with hydrazine has the advantages that certain amount, especially it, which can be significantly reduced, carries out plutonium also
The amount of uranium nitrates and hydrazine needed for original reaction, to make and not extract the related disadvantage of hydrazine in machine phase to tail off, this is not fully
It is satisfactory, this is because：
Organic phase is relatively low to the extraction of butyl aldoxime, the butyl aldoxime of effective concentration is if desired obtained in organic phase, then
It needs a large amount of this oximes being added in the extractor that plutonium reduction reextraction occurs；Especially in U/Pu allocation steps, pass through
So that this is mutually saturated the extraction to reduce organic phase significantly to butyl aldoxime with actinides, finally makes the use of this oxime hardly
It is suitable for carrying out the allocation step；
Lasting use of the hydrazine in aqueous phase；In fact, although hydrazine be in aqueous phase most effective anti-nitrous agent it
One, but its use is restricted, not only due to what is be noted above forms related problem, but also because its poison with hydrazoic acid
Property：Hydrazine is actually on CMR list of substances, that is, according to the regulation (EC) 1907/ of chemicals registration, assessment, license and limitation
2006 (REACH regulations) are deemed likely to be or have turned out to be the substance of carcinogenic, mutagenesis and/or genotoxicity, and very may be used
It can enter in the list of substances that regulation annex XIV is authorized energy sooner or later, in this case, unless European chemical balance motion office
(ECHA) specific exemption is given, otherwise its sale and industrial use will be prohibited.
In addition, it was further observed that butyl aldoxime is reacted with hydrazine, to form hydrazone.This reacts the performance for reducing butyl aldoxime,
And result in consuming excessively for both reagents.
In view of the foregoing, therefore the applicant sets about finding the high compound of anti-nitrous performance, but not using it
Have by using disadvantage caused by hydrazine (such as used at present in PUREX methods), or by using two-phase butyl aldoxime/hydrazine system
Disadvantage caused by (such as proposition in bibliography [3]).
More specifically, they set such target：Even if in the case where actinides makes the organic phase be saturated,
These compounds should be easier by organic phase (type especially used in PUREX methods) extraction compared with hydrazine (in identical temperature
Under degree and pressure condition), with can：(1) amount of these compounds needed for plutonium reduction reaction is reduced, and (2) use these
Second plutonium of the compound for plutonium back extraction and this method in the U/Pu allocation steps of the first decontamination cycle of PUREX methods follows
Plutonium back extraction in ring.
They also set such target：These compounds should completely evade using hydrazine.
Invention content
These targets and other targets are realized by the application, and the application proposition makes in plutonium reduction reextraction extract operation
Use at least one aldoxime at least five carbon atom as anti-nitrous agent, it is at least one at least five carbon atom
The oxime of aldoxime, that is, general formula R-CH=N-OH, wherein R are the hydrocarbon chains for having at least four carbon atom.
Preferably, aldoxime meets R and includes at most 12 carbon atoms and advantageously comprise the above logical of at most 8 carbon atoms
In formula.
It is preferred that aldoxime meets the formula above that R is the linear alkyl chain with 4~8 carbon atoms.
The aldoxime is that formula is n-C4H9The valeraldehyde oxime (pentanal oxime) of-CH=N-OH is (also referred to as
Valeraldehyde oxime or valeraldoxime), formula n-C5H11Hexanal oxime, the formula n-C of-CH=N-OH6H13-CH
Heptaldoxime, the formula n-C of=N-OH7H15The octanal oxime and formula of-CH=N-OH is n-C8H17The pelargonic aldehyde oxime of-CH=N-OH.
In these aldoximes, particularly preferred valeraldehyde oxime and hexanal oxime.
According to the application, plutonium reduction reextraction extract operation preferably includes：
Make in organic diluent organic non-water miscibility phase comprising extractant and the plutonium in oxidation state IV with comprising
Can plutonium (IV) be reduced into the reducing agent of plutonium (III) and the aqueous of nitric acid is in contact, aldoxime is according to its solubility in water
And included in organic phase or included in aqueous phase；Then
By the organic phase so contacted and aqueous phase separation.
Therefore, it is partially soluble in water (under the conditions of the temperature and pressure that these operating routines use) and is partially soluble in energy
It can be added in aqueous phase or be added to organic phase for the valeraldehyde oxime in the organic diluent of plutonium reduction reextraction extract operation
In, and the aldoxime with 6 or more more carbon atoms for not dissolving in or being practically insoluble in (under these conditions) water is added to
In organic phase.
In this application, reducing agent contained in aqueous phase is preferably selected from uranium (IV), hydroxylamine nitrate (also referred to as azanol nitric acid
Salt), the alkyl derivative of azanol, ferrous sulfamate or sulfamic acid.
In these reducing agents, particularly preferred uranium (IV) and hydroxylamine nitrate, they are to restore plutonium (IV) in PUREX methods
At two kinds of reagents used in plutonium (III), the first reagent is in the U/Pu allocation steps of decontamination cycle, and second of reagent is
In the second plutonium cycle.
Moreover, extractant is preferably tricresyl phosphate nalka base ester and more preferably TBP, and organic diluent be preferably straight chain or
The dodecane (such as n-dodecane or HTP) of branch, isoparaffic solvent (such as Isane IP185, Isane IP165 or
Isopar L) or kerosene, in this case, the extractant preferably ratio contained in the organic diluent is 30% (v/v).
No matter situation why, the concentration that aldoxime uses in organic phase or aqueous phase is preferably 0.01mol/L~3mol/L,
More preferably 0.05mol/L~0.5mol/L；And the concentration that reducing agent uses in aqueous phase be preferably 0.02mol/L~
0.6mol/L, and still more preferably 0.2mol/L~0.4mol/L.
About nitric acid, its concentration contained in aqueous phase is advantageously 0.05mol/L~2mol/L.
In this application, if aldoxime has when organic phase and aqueous phase contact with each other between organic phase and aqueous phase
The distribution of balance, then aldoxime can be used as unique anti-nitrous agent in plutonium reduction reextraction extract operation.However, if due to aldehyde
Oxime extracts (under conditions of the temperature and pressure that plutonium reduction reextraction operating routine uses) by organic phase height --- for tool
Have 6 or more more carbon atoms aldoxime (such as hexanal oxime or octanal oxime) this would generally occur, situation is really not so, then should
Aldoxime is advantageously used in combination with the second anti-nitrous agent, which is (in identical temperature and pressure item
Under part) it cannot be by the oxime of the organic extractant phase.
In this case, this oxime that cannot be extracted for including in aqueous phase is preferably that formula is CH2The formaldehyde of=N-OH
Oxime (also referred to as formaldehyde oxime) or formula are CH3Acetaldoxime (the also referred to as acetaldehyde of-CH=N-OH
Oxime), and its concentration for being used in aqueous phase is advantageously 0.01mol/L~1mol/L and still more preferably
0.05mol/L~0.2mol/L.
According to the application particularly preferred embodiment, plutonium reduction reextraction extract operation be preferably PUREX methods or
One of plutonium back extraction extract operation of COEX methods.
This application provides many advantages.It provides a series of anti-nitrous agents, and (some anti-nitrous agents are independent
It uses, and other anti-nitrous agents oxime inextractable with organic phase is used in combination), it can most effectively block in organic phase
It is reoxidised into plutonium (IV) with plutonium in aqueous phase (III).
Therefore, in addition to the application can be carried out without using hydrazine the fact that plutonium reduction reextraction extract operation it
Outside, either the operation implemented in the U/Pu separating steps of such as PUREX methods still follows the second plutonium of such as same procedure
The operation implemented in ring, it can also make the amount of reducing agent and anti-nitrous agent needed for these operations and in anti-nitrousization
Agent amount required when being hydrazine is compared to reduction highly significant.
Therefore, the application consideration, which can make these anti-nitrous agents being added to, is exclusively used in plutonium reduction reextraction extract operation
Points (number of points) needed for equipment are reduced, and therefore simplify the equipment.
Further, since compared with using the case where hydrazine is as anti-nitrous agent, plutonium back extraction is more effective and thereby anti-
The higher aqueous phase of plutonium concentration is obtained at the end of extracting operation, the application can also imagine reduction and carry out plutonium reduction reextraction at present
Equipment size used in extract operation.
When reading following embodiment, other feature and other advantages of the application will become more significantly.
Obviously, these embodiments are only provided as the explanation of subject matter, do not limit the application in any way.
Description of the drawings
Fig. 1 gives valeraldehyde oxime (■ symbols) and hexanal oxime (● symbol) in the organic phase of the TBP included in n-dodecane
With the breadth coefficient between the aqueous phase comprising various concentration nitric acid；In order to compare, which gives butyl aldoxime (▲ symbol)
The breadth coefficient obtained under the same conditions.
Fig. 2A and Fig. 2 B give valeraldehyde oxime (■ symbols) and hexanal oxime (● symbol) between organic phase and aqueous phase
Breadth coefficient, for uranium (VI) concentration and concentration of nitric acid, the organic phase and aqueous phase simulation detach step in the U/Pu of PUREX methods
The organic phase and aqueous phase obtained in rapid.
Fig. 3 shows that valeraldehyde oxime (curve A) is to the destruction dynamics of nitrous acid in nitric acid aqueous phase；It, should in order to compare
Figure also shows the destruction dynamics of the butyl aldoxime (curve B) obtained under the same conditions and acetaldoxime (curve C) to nitrous acid.
Fig. 4 shows that in containing n-dodecane, valeraldehyde oxime (curve A) and hexanal oxime (curve B) are to Asia in the organic phase of TBP
The destruction dynamics of nitric acid；In order to compare, also shown is the butyl aldoximes (curve C) obtained under the same conditions to nitrous acid
Destruction dynamics.
Fig. 5 is shown after so that these organic phases is contacted with nitric acid aqueous solution and these phases are subsequently isolated containing positive ten
The oxidation of the uranium (IV) obtained in the presence of valeraldehyde oxime (curve A) and hexanal oxime (curve B) in the organic phase of TBP in dioxane is dynamic
Mechanics；In order to compare, also shown is in the presence of butyl aldoxime (curve C) and in the presence of no any oxime (curve D)
The oxidation kinetics of the uranium (IV) obtained under the same conditions.
Fig. 6 shows the oxidation kinetics of the uranium (IV) obtained in the presence of valeraldehyde oxime (curve A) in nitric acid aqueous solution
It learns；In order to compare, also shown is in the presence of butyl aldoxime (curve B), acetaldoxime (curve C) and hydrazine (curve D) identical
Under the conditions of the oxidation kinetics of uranium (IV) that obtains.
Fig. 7 shows the organic phase (TBP/ after the plutonium reduction reextraction experiment that hexanal oxime is used as anti-nitrous agent
HTP the oxidation kinetics for the uranium (IV) for including in).
Fig. 8 is shown in the plutonium reduction reextraction examination that hexanal oxime is used as anti-nitrous agent and technetium is stripped jointly with plutonium
The oxidation kinetics for the uranium (IV) for including in organic phase (TBP/HTP) after testing.
Fig. 9 shows the organic phase (TBP/ after the plutonium reduction reextraction experiment that valeraldehyde oxime is used as anti-nitrous agent
HTP the oxidation kinetics of the uranium (IV) in).
Figure 10 is shown in the nitric acid aqueous phase containing 100mg/L (■ symbols) or 200mg/L (× symbol) technetium in acetaldoxime
In the presence of uranium (IV) oxidation kinetics；In order to compare, also shown is in hydrazine and 100mg/L (▲ symbol) or 200mg/L
The oxidation kinetics of the uranium (IV) obtained under the same conditions in the presence of (● symbol) technetium.
Figure 11 gives the scheme of processing spentnuclear fuel lysate, including hexanal oxime/acetaldoxime joint is used as anti-nitrousization
The U/Pu allocation steps of system；In the figure, the rectangle for being labeled as 1~7 indicates multi-stage extractor, and it is conventional such as to handle spentnuclear fuel
The multi-stage extractor (mixer-settler, pulsed column, centrifugal extractor) used；And enter and leave the organic phase of extractor by
Solid line indicates, and the aqueous phase for entering and leaving these extractors is represented by dashed line.
Figure 12 is shown by calculating uranium in the aqueous phase recycled in the extractor 5 and 6 of scheme shown in the Figure 11 obtained
(IV) distribution curve (curve A) of concentration；In order to compare, when giving in this scenario with hydrazine replacement hexanal oxime and acetaldoxime
It the distribution curve (curve B) of uranium (IV) concentration obtained and is obtained in reoxidizing when reaction is fully neutralized for plutonium (III)
The distribution curve (curve C) of uranium (IV) concentration obtained.
Figure 13 show through experiment (× symbol) and Figure 11 for being obtained by calculating (curve -) shown in scheme extractor
The distribution curve of plutonium concentration in the aqueous phase recycled in 5 and 6.
Figure 14 shows and is for example followed by experiment and by calculating in the extractor 5 and 6 of scheme shown in the Figure 11 obtained
The uranium (IV) of the aqueous phase of ring, the distribution curve of uranium (VI) and total uranium concentration；In the figure, symbol ×, ◆ and ■ corresponds to respectively
In the distribution curve by testing the uranium (VI) obtained, uranium (IV) and total uranium concentration, and curve A, B and C do not correspond to the pass meter
Calculate the uranium (VI) obtained, uranium I V) and total uranium concentration.
Specific implementation mode
Embodiment 1：The property of valeraldehyde oxime and hexanal oxime
1.1–Breadth coefficient
By following two campaigns, the breadth coefficient (being expressed as D) of valeraldehyde oxime and hexanal oxime is determined：
First Series, for measuring in the organic phase comprising 30% (v/v) TBP in n-dodecane and including 0.2mol/L
These breadth coefficients between the aqueous phase of~2mol/L nitric acid；With
Second series, for measuring these breadth coefficients between organic phase and aqueous phase, with regard to uranium (VI) concentration and nitre
For acid concentration, it simulates the organic phase and aqueous phase obtained in the U/Pu allocation steps of PUREX methods, the series with
Implement in mixing-settler unit of 8 stages (being expressed as BX1 to BX8).
For the two campaigns, keep each organic phase and nitric acid aqueous under environment temperature (20~25 DEG C) and stirring
Liquor capacity contacts 15 minutes.Valeraldehyde oxime is added in aqueous phase, and hexanal oxime is added in organic phase, the two is in phase
In concentration be 0.1mol/L.
So that the organic phase contacted and aqueous phase is separated from each other by centrifugation, and passes through the high-efficient liquid phase color for aqueous phase
It composes (HPLC) and concentration of the aldoxime in these phases is measured by the gas-chromatography (GPC) for organic phase.
The breadth coefficient obtained in being tested table 1 below gives First Series.They are also presented in Fig. 1, wherein should
It is worth transposition shown in table, and the breadth coefficient of valeraldehyde oxime is indicated by symbol ■, and the breadth coefficient of hexanal oxime is by according with
Number ● it indicates.In order to compare, Fig. 1 gives the breadth coefficient (▲) of the butyl aldoxime obtained under the same conditions.
Table 1
Following table 2 gives the breadth coefficient obtained in second series experiment.They are also provided in Fig. 2A and Fig. 2 B,
Wherein, the breadth coefficient value (Y-axis) of aqueous phase and acidity value (X-axis) transposition (transpose), and the distribution of valeraldehyde oxime
Coefficient corresponds to symbol ■, and the breadth coefficient of hexanal oxime corresponds to symbol ●.Ordinate in Fig. 2A is decimal number, and is schemed
Ordinate in 2B is logarithm.
Table 2
As shown in table 1 and Fig. 1, valeraldehyde oxime and hexanal oxime show that breadth coefficient is apparently higher than the breadth coefficient of butyl aldoxime,
This means that they are more easy to be extracted in organic phase than butyl aldoxime.
If aqueous phase contains actinides (table 2 and Fig. 2A and Fig. 2 B), the breadth coefficient of valeraldehyde oxime and hexanal oxime with
There is no values when actinides compared to decline；However, they are still sufficiently high so that valeraldehyde oxime and hexanal oxime are still shown
Write extraction.Under the same conditions, the breadth coefficient of butyl aldoxime is less than 1.
The breadth coefficient of valeraldehyde oxime and hexanal oxime allows：
For valeraldehyde oxime：Balanced distribution between organic phase and aqueous phase, it is thus possible to which developing valeraldehyde oxime can be independent
Scheme for the plutonium reduction reextraction for stablizing organic phase and aqueous phase；And
For hexanal oxime：The extraction almost quantitative in organic phase, it is thus possible to which developing hexanal oxime can be with considerably less
Usage amount stablizes the scheme of the plutonium reduction reextraction of organic phase, and in this case, aqueous phase can be by hydrophily oxime (such as second
Aldoxime) stablize；And
For both aldoximes：Their possibility in U/Pu allocation steps use.
1.2-Anti-nitrousization acts on
Valeraldehyde oxime is assessed in following two campaigns and hexanal oxime destroys nitrous acid (HNO2) ability：
First Series, for measuring destruction dynamics of the valeraldehyde oxime to nitrous acid, and, in order to compare, containing 0.1mol/
Destruction dynamics of the butyl aldoxime to nitrous acid in the aqueous phase of L nitric acid；With
Second series, the destruction dynamics for measuring valeraldehyde oxime and hexanal oxime to nitrous acid, also, in order to compare,
Including destruction dynamics of the butyl aldoxime to nitrous acid in the organic phase of (v/v) TBP 30% in n-dodecane.
In First Series experiment, the initial concentration of nitrous acid and valeraldehyde oxime or butyl aldoxime in phase in nitric acid aqueous phase
Respectively 0.005mol/L and 0.025mol/L.Pass through the spectrophotometry (HNO at λ=370nm2The continuous measurement at peak), inspection
Nitrous acid concentration in these aqueous phases is surveyed to change with time.
In second series experiment, make under environment temperature (20~25 DEG C) and stirring first in advance with 1M nitric acid balance
First organic phase contacts 10 minutes with the aqueous phase volume of nitric acid containing 1mol/L and 0.002mol/L nitrous acid, then by from
The heart is isolated from the aqueous phase.Nitrous acid almost quantified extract in organic phase.
Make that 1M nitric acid is used to balance and added with dense in organic phase in advance under environment temperature (20~25 DEG C) and stirring
Degree is the aqueous phase volume of the second batch organic phase and the nitric acid containing 1mol/L of the valeraldehyde oxime of 0.15mol/L, hexanal oxime or butyl aldoxime
Then contact 10 minutes is isolated by centrifuging from the phase.Oxime separates between organic phase and aqueous phase.
Mixture is quickly prepared by first organic phase (therefore including nitrous acid) of 1mL and 8mL second batch organic phases.Pass through
Spectrophotometry (λ=370nm), concentration variation of the monitoring nitrous acid in these mixtures.
These experiment results provide in graph form in figs. 3 and 4, indicate residual nitrous acid percentage about
The function of time (in Fig. 3 in seconds, in Fig. 4 as unit of minute).
In figure 3, about First Series test, curve A correspond to valeraldehyde oxime obtain as a result, and curve B corresponds to
The result that butyl aldoxime is obtained.Also shown is acetaldoximes to the destruction dynamics (curve C) of nitrous acid, and the dynamics is
Simulation by testing the rate constant measured is measured.
In Fig. 4, it is tested about second series, curve A corresponds to the result to valeraldehyde oxime；Curve B corresponds to hexanal
The result that oxime obtains；And curve C corresponds to the result obtained to butyl aldoxime.
The figures illustrate：
In aqueous single_phase system, although valeraldehyde oxime including carbon atom more compared with butyl aldoxime and acetaldoxime,
But it shows to act on (Fig. 3) with butyl aldoxime and comparable anti-nitrousization of acetaldoxime；And
In organic single_phase system, wherein the organic phase containing valeraldehyde oxime, hexanal oxime or butyl aldoxime contacts in advance with aqueous phase
(so that these oximes separate between organic phase and aqueous phase, therefore they are reduced in the concentration of organic phase), observes：For first
Begin the oxime for being added to same concentrations in organic phase, and destruction of the nitrous acid in organic phase is compared in the presence of butyl aldoxime in valeral
In the presence of oxime or hexanal oxime significantly accelerated (Fig. 4).
Embodiment 2：The stabilization of valeraldehyde oxime and hexanal oxime to actinides
Valeraldehyde oxime and hexanal oxime are assessed in following two campaigns stablizes actinides in aqueous phase or organic phase
Ability：
First Series, for measuring uranium (IV) in the presence of valeraldehyde oxime, hexanal oxime and butyl aldoxime for comparing and
Oxidation kinetics in the presence of no any oxime 30% in containing n-dodecane in the organic phase of (v/v) TBP, in the organic phase
With the nitric acid containing 1.8mol/L it is aqueous be in contact after, these phases are subsequently isolated；With
Second series, for measuring uranium (IV) in the presence of valeraldehyde oxime and butyl aldoxime, acetaldoxime and hydrazine for comparing
Oxidation kinetics in the aqueous phase of the nitric acid containing 1.3mol/L.
In First Series experiment, make to use in advance under environment temperature (20~25 DEG C) and stirring 1.8M nitric acid balance and
Each organic phase of a concentration of 0.1mol/L oximes and the aqueous nitric acid of uranium containing 6g/L (IV) are added in the appropriate case mutually with O/A volumes
Than being contacted 10 minutes for 2 mode.The organic phase contacted and aqueous phase is set to be separated from each other by centrifugation, and by being divided light
Degree method (λ=653nm) is changed with concentration of the 200 hours time interval monitoring uranium (IV) in organic phase.
In second series experiment, uranium (IV) and anti-nitrousization reagent (oxime or hydrazine) are initial dense in nitric acid aqueous phase
Degree is respectively 66g/L and 0.2mol/L.Existed with 300 days time interval monitoring uranium (IV) by spectrophotometry (λ=653nm)
Concentration in these aqueous phases changes with time.
These experiment results provide in graph form in fig. 5 and fig., indicate residual uranium (IV) percentage about
The function of time (in Fig. 5 as unit of hour, in Fig. 6 as unit of day).
In Figure 5, it is related to First Series experiment, curve A corresponds to the result obtained to valeraldehyde oxime；Curve B correspond to pair
The result that hexanal oxime obtains；Curve C correspond to butyl aldoxime obtains as a result, and curve D corresponding to obtaining in the presence of no oxime
The result obtained.
In figure 6, it is related to second series experiment, curve A corresponds to the result obtained to valeraldehyde oxime；Curve B correspond to pair
The result that butyl aldoxime obtains；Curve C corresponds to the result obtained to acetaldoxime；And curve D corresponds to the result obtained to hydrazine.
As shown in figure 5, in the presence of oxime, uranium (IV) complete stability at least 15 hours in organic phase；And do not appointing
In the presence of what oxime, oxidation is completed in less than 8 hours.In addition, valeraldehyde oxime and hexanal oxime stablize uranium (IV) in organic phase
Ability be more than butyl aldoxime in organic phase stablize uranium (IV) ability because in the presence of valeraldehyde oxime and hexanal oxime be less than 10%
Uranium (IV) in 100 hours internal oxiditions, and situation is really not so in the presence of butyl aldoxime.
In aqueous phase, valeraldehyde oxime stablizes ability of the ability also greater than butyl aldoxime stabilization uranium (IV) of uranium (IV).However, penta
Aldoxime stablizes the ability of uranium (IV) not as good as acetaldoxime and hydrazine stablize the ability (Fig. 6) of uranium (IV).
All these periods as unit of day still deposit than being stripped organic phase and aqueous phase in extract operation in plutonium industry
Time it is much longer.
These results indicate that can with the monoxime scheme of valeraldehyde oxime or with (example in double oxime schemes that acetaldoxime is used together
Such as with the hexanal oxime in organic phase) so that the aqueous nitric acid containing high concentration uranium (IV) is mutually stablized, to avoid using hydrazine.
Embodiment 3：Anti-nitrousization of valeraldehyde oxime and hexanal oxime under the electrochemical conditions for representing plutonium reduction reextraction extract operation
Property
Anti-nitrousization of assessment valeraldehyde oxime and hexanal oxime in a series of experiment (being expressed as BX1 to BX10)
Matter, these experiments represent the electrochemical conditions for carrying out plutonium reduction reextraction in PUREX methods, are related to：
Plutonium (IV) is reduced into plutonium (III) with uranium (IV), and plutonium (III) is reduced into plutonium (IV) with nitrous acid；
The destruction of a pair of nitrous acid of above-mentioned oxime；And
Distribution of the substance of target between aqueous phase and organic phase.
For this purpose, having used following substance：
As aqueous phase：Solution with 1mol/L or 2mol/L nitric acid includes the uranium of concentration shown in the following table 3 and table 4
(VI), uranium (IV) (as plutonium (IV) reducing agent) and optional hydrazine and technetium；And
As organic phase：30% (v/v) solution of TBP in HTP, including the oxime of concentration, uranium (VI) shown in the following table 3 and table 4
With plutonium (IV).
Oxime is added in organic phase (additive amount of oxime is controlled by weighing) in solid form.
Organic phase is set to be contacted in such a way that O/A volume ratios are 2 with aqueous phase under environment temperature (20~25 DEG C) and stirring
15 minutes (time of contact be only 5 minutes experiment BX3 except), later it is separated from each other these stages.
After the separation, uranium (VI), uranium (IV) and plutonium (III) are measured in aqueous phase by ultravioletvisible spectroscopy
Concentration, and pass through α-spectrophotometry and measure total concentration of the plutonium in aqueous phase.It is surveyed by UV-VIS spectrophotometry
The concentration of uranium (VI) and uranium (IV) in organic phase is measured, and total dense in organic phase by α-spectrophotometry measurement plutonium
Degree.
According to these measurements as a result, determining the ratio between the consumption of uranium (IV) and plutonium back extraction taken amount to each experiment
(it is expressed as U (IV)Consumption/PuBack extraction) and the separation factor of plutonium (be expressed as FDPu)。
Results of these experiments provide in following table 3 and table 4, and table 3 corresponds to hexanal oxime (BX1 to BX5, BX8
And BX10) carry out experiment obtain as a result, and table 4 correspond to valeraldehyde oxime (BX6 and BX7) carries out experiment acquisition knot
Fruit.
Table 3
Table 4
As shown in these tables：
For hexanal oxime, a concentration of 0.1mol/L and initial weight ratio (U (IV)/Pu) are 0.8~1.5 in organic phase
When, uranium (IV) consumption and plutonium back extraction amount (ratio U (IV)Consumption/PuBack extraction) between 0.5 and 0.6；The parasitism that plutonium reoxidizes is existing
As also very low, or even it is not present；For aqueous phase (experiment BX1 to BX5) observation that concentration of nitric acid is 1mol/L or 2mol/L
To these results；
There are technetiums to lead in the concentration reduction half (0.05mol/L is to 0.1mol/L) and aqueous phase of hexanal oxime in organic phase
Cause consumption higher (the ratio U (IV) of uranium (IV)Consumption/PuBack extraction=1), but it is also to maintain medium (experiment BX8 and experiment BX10)；
Valeraldehyde oxime, which can also limit, leads to the additional redox phenomenon for consuming uranium (IV), but the performance compared with hexanal oxime
It is relatively low, because of the ratio U (IV) obtained with valeraldehyde oximeConsumption/PuBack extractionBetween 0.6 and 0.8 (experiment BX8 and BX10).
By spectrophotometry (λ=653nm) with the time interval monitoring of a few hours after testing BX5, BX10 and BX6
Concentration variation of the uranium (IV) of acquisition in organic phase.
The result of this monitoring is shown in Fig. 7, Fig. 8 and Fig. 9, corresponds respectively to organic phase BX5, BX10 and BX6.
These figures confirm that valeraldehyde oxime and hexanal oxime can stablize uranium (IV) in organic phase.This stabilization is deposited in technetium
Lower smaller, but the oxidation kinetics of uranium (IV) is relatively slow, because uranium (IV) concentration reduces half in 50 minutes.
Embodiment 4：It is included in the processing scheme without using the lysate of the spentnuclear fuel of U/Pu allocation steps in the case of hydrazine
Exploitation
A kind of processing scheme of the lysate for spentnuclear fuel is developed, the U/Pu carried out in the case of being included in no hydrazine divides
The anti-nitrousization system that is combined as is formed with step, but using hexanal oxime/acetaldoxime, hexanal oxime is used for organic phase, and acetaldehyde
Oxime is used for aqueous phase.
Before developing the program, it has already been proven that：
First, in the presence of technetium, acetaldoxime can actually replace hydrazine as the anti-nitrous agent in aqueous phase；And
Secondly, hexanal oxime can also stablize the uranium (IV) in the organic phase for carrying out so-called " Np washings " operation, should
It is to be stripped extract operation (in the operating process from removing in aqueous solution by plutonium to operate the target in PUREX and COEX methods
It has been stripped) neptunium of generation.
The anti-nitrousization property of 4.1- acetaldoximes in the presence of aqueous phase and technetium
It is tested to compare anti-nitrousization property of the acetaldoxime in aqueous phase and anti-nitrous of hydrazine in the presence of technetium
Acidifying qualities.
For these experiments, following operation scheme is applied：
Prepare the aqueous solution of uranium containing 9g/L (IV) and 2mol/L nitric acid and 0.2mol/L acetaldoximes or hydrazine, these solution
Thermostatic control is at 35 DEG C；
Aqueous solution of the addition containing 8.88g/L (i.e. 0.09mol/L) technetium (VII) into these solution, to reach 100mg/L
Or the final technetium concentration of 200mg/L；And after stirring
Uranium (IV) in the aqueous solution was monitored within 100 minutes periods by spectrophotometry (λ=653nm)
Oxidation kinetics.
The result of these experiments is presented in Fig. 10, wherein the Tc for acetaldoxime in 100mg/L and 200mg/L exists
Under result correspond respectively to symbol ■ and ×, and it is right respectively for result of the hydrazine in the presence of Tc of 100mg/L and 200mg/L
Should in symbol ▲ and ●.
As shown in the drawing, anti-nitrousization property of acetaldoxime in the presence of aqueous phase and 100mg or 200mg technetiums and hydrazine phase
When.
Therefore, acetaldoxime can be used to replace hydrazine as anti-nitrous agent.
4.2- stablizes uranium (IV) in " Np washings " operation
Following two experiments (being expressed as BS16 and BS17) are carried out, by using：
As organic phase：The solution of (v/v) TBP 30% in HTP, including or not comprising 0.1mol/L hexanal oximes；With
As aqueous phase：Aqueous solution with 1.3mol/L nitric acid, including the uranium (IV) that concentration is as shown in table 5 below, second
Aldoxime, plutonium (III) and technetium；They with before organic be in contact just in the form of concentration Tc (VII) solution of 8.88g/L by technetium
It is added in aqueous phase.
Environment temperature (20~25 DEG C) and stirring under make organic phase with and aqueous phase volume contact 15 minutes, then by this
It is mutually separated from each other a bit.
The concentration of uranium (IV) in aqueous phase and organic phase is measured, and measures the percentage of the uranium (IV) consumed in each experiment
Than (being expressed as U (IV)Consumption)。
As a result it is listed in following table 5.
The table show there are hexanal oximes (experiment BS16), and the consumption of uranium (IV) can be made to be deposited with without the oxime in organic phase
Consumption (experiment BS17) compared to reducing by 50%.
Table 5
4.3- processing scheme
Figure 11 shows the processing scheme of the spentnuclear fuel lysate of exploitation.
In this scenario, it was found that two key steps of first purification cycle of COEX methods, i.e.,：
(1) uranium of purification actinides (III) (americium and curium) and plutonium and the step of a certain number of fission products, packet
It includes：
In Figure 11 be known as " U/Pu coextractions " operation, for by the organic phase comprising in HTP 30% (v/v) TBP from
The neptunium of the uranium of oxidation state VI, the plutonium and oxidation state VI of oxidation state IV is extracted in lysate jointly；
It is known as the operation of " FP washings " in Figure 11, is split for being removed from the organic phase that " U/Pu is extracted jointly " operation generates
Become the ruthenium and zirconium extracted in product, especially " U/Pu is extracted jointly "；
It is known as the operation of " Tc washings " in Figure 11, for being removed from the organic phase that " FP washings " generates by aqueous phase
The technetium extracted in " U/Pu coextractions "；With
In Figure 11 be known as " additional U/Pu coextractions " operation, in organic phase recycle uranium (VI), plutonium (IV) and
The technetium in the aqueous phase of " technetium washing " is then recycled in the part of neptunium；And
(2) the step of uranium and plutonium being divided into two aqueous flows, a uranium-bearing, containing plutonium and uranium, (U/Pu weight ratios are about for another
It is 20:80 to 30:70), and include：
It is known as the operation of " Pu/U back extraction " in Figure 11, for being stripped plutonium from the organic phase that " Tc washings " generates and being somebody's turn to do
Plutonium can be reduced into the reduction of oxidation state III by being used as comprising uranium (IV) by a part of uranium contained in organic phase, the operation
The aqueous phase of agent carries out；
It is known as the operation of " Np washings ", for removing uranium from the aqueous phase that " Pu/U back extraction " generates, its phase in Figure 11
For expected 20:80 to 30:70 U/Pu weight ratios are excessive, then remove the neptunium portion in the aqueous phase of " Pu/U back extraction "
Point；With
The referred to as operation of " U back extraction ", for being stripped from the organic phase that " Pu/U back extraction " generates by aqueous phase
Uranium and neptunium.
However, in the scheme shown in Figure 11, the anti-nitrous agent (that is, hydrazine) that COEX methods use is by hexanal oxime/acetaldehyde
Oxime is combined and is substituted.
As shown in figure 11, it is contemplated that hexanal oxime (HexOx is expressed as in Figure 11) is added to entrance by its strong lipophilicity
In the organic phase of the extractor 5 of " Np washings ", and enter extractor 6 before be added to " Tc washings " generate organic phase
In.
In view of its hydrophily, acetaldoxime (being expressed as AcOx in fig. 11) is added to recycled in extractor 6 it is aqueous
Xiang Zhong, this addition are three different phases in the extractor：Stage 8, in this stage, acetaldoxime are injected into for anti-
In the aqueous phase of extraction；And the stage 1 and 4, in this stage, acetaldoxime, which is injected into, mutually supplies uranium (IV) for hydrotropism
In aqueous flow.
Basic acquisition in relation to the oxime that is used in aqueous phase and organic phase two-phase be used to develop initial model, with being capable of mould
The kinetics of separation and they and nitrous acid between the aqueous phase and organic phase that are used in quasi- this method.These moulds
Type is with PAREX code implementations, that is, software can in simulated operation target substance distribution, uranium and plutonium are such as distributed into two
Aqueous flow.On the basis of simulating herein, for the experimental test of scheme shown in Figure 11, it is determined that operating parameter.
Figure 12 compares the concentration profile in the aqueous phase that uranium (IV) recycles in extractor 5 and 6, such as needle first
Scheme (curve A) shown in Figure 11 is calculated, is secondly calculated for using the similar scheme (curve B) of hydrazine.It also shows logical
Cross the ideal distribution curve (curve C) for reoxidizing reaction and obtaining that plutonium (III) is neutralized (in PAREX codings).
As shown in the drawing, hexanal oxime/using for acetaldoxime combination makes the concentration ratio of uranium (IV) distribution curve be obtained with hydrazine
Higher, thereby confirm the uranium (IV) in the presence of these oximes consumption reduce.
Scheme shown in Figure 11 in ATALANTE shieldings production line for manufacturing battery (a kind of real spentnuclear fuel solution) at
Work(is implemented.The program can not have any uranium (IV) in highly concentrated uranium (IV) (16g/L) and in " Np washings " operation
Additive in the case of generate the plutonium stream of a concentration of 10g/L, and this additive is required in the similar scheme using hydrazine
's.The consumption of uranium (IV) is also below the scheme for using hydrazine.
Figure 13, which is shown, such as to be extracted by the plutonium tested (symbol ×) that obtains and calculated by PAREX codings (curve -)
The concentration profile in the aqueous phase recycled in device 5 and extractor 6 is taken, and Figure 14 is shown such as by testing and calculating acquisition
The aqueous phase that is recycled in these identical extractors of uranium (IV), uranium (VI) and total uranium in concentration profile；In the figure
In, symbol ×, ◆ and ■ corresponds respectively to the uranium (IV) that experiment obtains, the concentration profile of uranium (VI) and total uranium, and curve
A, B and C corresponds respectively to the concentration profile by calculating the uranium (IV) obtained, uranium (VI) and total uranium.
In addition, the following table 6 gives：The uranium that the experiment of scheme as shown in figure 11 obtains is in the aqueous phase that extractor 5 generates
Concentration (be expressed as [U (IV)]Pu generates stream), concentration of the plutonium in the aqueous phase that extractor 5 generates (is expressed as [Pu]Pu generates stream), into
Enter the uranium (IV) of extractor 6 flow and enter the identical extractor Pu flow between ratio (be expressed as U (IV)/
PuInto), the percentage of uranium (IV) of consumption (be expressed as U (IV)Consumption) and uranium consumed flow and plutonium between inbound traffics
Ratio (be expressed as U (IV)Consumption/Pu)。
In order to compare, this table shows such as using the similar scheme of hydrazine by testing these the identical concentration obtained, ratio
Rate and percentage.
Table 6
The bibliography of reference
[1]WO-A-2006/072729
[2]WO-A-2011/000844
[3]WO-A-2008/148863
Claims (12)
1. the aldoxime that at least one general formula is R-CH=N-OH answering as anti-nitrous agent in plutonium reduction reextraction extract operation
With, wherein R is the linear chain or branched chain hydrocarbon chain for having at least four carbon atom.
2. application according to claim 1, wherein R is with 4~12 carbon atoms and even more preferably from 4~8 carbon atoms
Linear chain or branched chain hydrocarbon chain.
3. application according to claim 2, wherein R is the linear alkyl chain with 4~8 carbon atoms.
4. application according to claim 3, wherein the aldoxime is valeraldehyde oxime or hexanal oxime.
5. application according to any one of claims 1 to 4, wherein the plutonium reduction reextraction extract operation includes：
Organic non-water miscibility phase is set to be in contact with aqueous, organic non-water miscibility mutually includes extraction in organic diluent
The plutonium of agent and oxidation state IV, the aqueous phase includes that plutonium (IV) can be reduced into the reducing agent and nitric acid of plutonium (III), described to have
One of machine phase and aqueous phase also include the aldoxime；Then
By the organic phase so contacted and aqueous phase separation.
6. application according to claim 5, wherein the reducing agent is selected from the alkylation of uranium (IV), hydroxylamine nitrate, azanol
Derivative, ferrous sulfamate or sulfamic acid.
7. application according to claim 6, wherein the reducing agent is uranium (IV) or hydroxylamine nitrate.
8. the application according to any one of claim 5~7, wherein the extractant is tricresyl phosphate nalka base ester, preferably
For TRI N BUTYL PHOSPHATE.
9. according to application according to any one of claims 1 to 8, wherein the aldoxime uses in organic phase or aqueous phase
A concentration of 0.01mol/L~3mol/L.
10. the application according to any one of claim 5~9, wherein the aqueous phase also includes cannot be by described organic
The mutually oxime of extraction.
11. application according to claim 10, wherein described cannot be acetaldoxime by the oxime of the organic extractant phase.
12. the application according to any one of claim 1~11, wherein the plutonium reduction reextraction extract operation is PUREX methods
Or one of the plutonium back extraction extract operation of COEX methods.
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| PCT/EP2016/074987 WO2017067933A1 (en) | 2015-10-21 | 2016-10-18 | Use of aldoximes comprising at least five carbon atoms as anti-nitrous agents in operations for the reductive back-extraction of plutonium |
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| JP2003526769A (en) * | 1998-08-28 | 2003-09-09 | ブリティッシュ・ニュークリア・フューエルズ・パブリック・リミテッド・カンパニー | Nuclear fuel reprocessing including reduction of Np (VI) to Np (V) by oxime |
| WO2007118904A1 (en) * | 2006-04-19 | 2007-10-25 | Commissariat A L'energie Atomique | Grouped separation of actinides from a highly acidic aqueous phase |
| CN101088129A (en) * | 2004-12-29 | 2007-12-12 | 通用核材料公司 | Improvement of the purex method and uses thereof |
| CN101765890A (en) * | 2007-06-07 | 2010-06-30 | 法国原子能委员会 | Use of butyraldehyde oxime as anti-nitrous agent in an operation for the reducing back-extraction of plutonium |
| CN103325431A (en) * | 2013-06-21 | 2013-09-25 | 中国原子能科学研究院 | PUREX process for separating technetium |
| CN103451455A (en) * | 2012-05-28 | 2013-12-18 | 中国原子能科学研究院 | Uranium (U) and plutonium (Pu) separation technology in Purex process |
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| WO2000013187A1 (en) * | 1998-08-28 | 2000-03-09 | British Nuclear Fuels Plc | Nuclear fuel reprocessing including reduction of np(vi) to np(v) with an oxime |
| FR2862804B1 (en) * | 2003-11-20 | 2006-01-13 | Commissariat Energie Atomique | PROCESS FOR SEPARATING URANIUM (VI) FROM ACTINIDES (IV) AND / OR (VI) AND USES THEREOF |
| FR2907346B1 (en) * | 2006-10-23 | 2009-01-30 | Commissariat Energie Atomique | (EN) GROUP SEPARATION OF ACTINIDES FROM A HIGHLY ACIDIC AQUEOUS PHASE USING A SOLVING EXTRACTOR IN A RELAXING MEDIUM. |
| FR2947663B1 (en) | 2009-07-02 | 2011-07-29 | Areva Nc | IMPROVED PROCESS FOR TREATING US NUCLEAR FUELS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003526769A (en) * | 1998-08-28 | 2003-09-09 | ブリティッシュ・ニュークリア・フューエルズ・パブリック・リミテッド・カンパニー | Nuclear fuel reprocessing including reduction of Np (VI) to Np (V) by oxime |
| CN101088129A (en) * | 2004-12-29 | 2007-12-12 | 通用核材料公司 | Improvement of the purex method and uses thereof |
| WO2007118904A1 (en) * | 2006-04-19 | 2007-10-25 | Commissariat A L'energie Atomique | Grouped separation of actinides from a highly acidic aqueous phase |
| CN101765890A (en) * | 2007-06-07 | 2010-06-30 | 法国原子能委员会 | Use of butyraldehyde oxime as anti-nitrous agent in an operation for the reducing back-extraction of plutonium |
| CN103451455A (en) * | 2012-05-28 | 2013-12-18 | 中国原子能科学研究院 | Uranium (U) and plutonium (Pu) separation technology in Purex process |
| CN103325431A (en) * | 2013-06-21 | 2013-09-25 | 中国原子能科学研究院 | PUREX process for separating technetium |
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