JPS6094121A - Improved method for accelerating electron transfer reaction - Google Patents

Abstract

PURPOSE:To increase the reaction velocity of electrons between quadrivalent and hexavalent uranium by allowing an organic compd. contg. nitrogen having a lone-pair electron, an organic compd. having >=2 complex-forming functional groups, and a metallic ion to coexist to separate uranium isotopes. CONSTITUTION:Pyrrole, piperazine, imidazole, a triazine derivative, pyridine, quinoline, 3-aminosalicylic acid, etc. are used as the constituent organic compd. of an accelerator. Rubidium, copper, gold, zinc, etc. having various oxidation numbers excluding zero-valence numbers are used as the metallic ions and the ions of an atomic group contg. metal used in combination with the organic compd. In this case, the organic compd. alone can hardly possess an accelerating effect on electron transfer velocity. When metallic ions coexist with the organic compd., the accelerating effect of the metallic ion is increased. Accordingly, the separation efficiency of the uranium isotopes is increased, and the size of the separator can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of accelerating electron transfer reactions between tetravalent uranium and hexavalent uranium.

Generally, in a solution containing tetravalent uranium and hexavalent uranium, an electron transfer reaction shown by the following chemical equilibrium equation occurs between the two, for example, B, Rona.

It is known from JAC8-Otsunu, 10.4539 (1950), etc.

*U (IV) 10u (vl) 2U (IV) +'U (
VI) However, the X mark indicates that one of the uranium is labeled with an isotope. U(■v) represents all the tetravalent uranium in fa f(+, including complex ions), and U(VI) represents all hexavalent uranium in the solution including complex ions.

mass? In the reaction thread defined by the following equilibrium equation between tetravalent uranium and hexavalent uranium labeled using two uranium isotopes of J255 and 258, the light isotope U -235 is enriched to the hexavalent uranium side, and the heavy isotope U-238
tends to be chained to the tetravalent uranium side.

The number of flat feet in this reaction K - (["5U (VI)] / [238U (VI) month /
([2A5I)(IV))/[”'U(rv) Since the moon is as small as about 1.001, when trying to separate two types of isotopes within a practical range, it is necessary to superimpose the reaction a large number of times.・There is a point.

Chromatography is an effective means to carry out such Okitatabons, and liquid phase chromatography such as adsorption chromatography, partition chromatography, and ion exchange chromatography is considered to be advantageous. For example, U.S.
P3,511. 1520, JP-A-47-12700 and JP-A-54. 42439, it is known that uranium isotopes can be completely separated by superimposing all of these electron transfer reactions by ion exchange chromatography using a packed column of cation exchange resin or anion exchange resin. be.

However, in the above reaction, the electron transfer reaction rate is low, so there is a drawback that the separation apparatus must be large and large.

Conventionally, methods for accelerating all of the above electron transfer reactions include, for example, E, Rona, J, Am, Chem.
,Soc,.

Volume 72, page 4339 (1950), )(, TOm
iyasu.

H, Fukutomi, J, Inorg, Nuc.
l, Chem, vol. 30.

2501 pages (1968), JP, Beuson, J.
r, C, HoBrubaker, Jr., U, S.
, Atomic Energy Comm1ttee.

TID-20147, page 14 (1961), Tokko Sho 5
Methods such as addition of tartaric acid in an acidic solution of hydrochloric acid at a still temperature or high concentration of 1)H in an acidic solution of hydrochloric acid, high concentration of hydrochloric acid, and addition of tartaric acid in an acidic solution of perchloric acid, and addition of various metal ions are known.

[7] Schiff, the above method cannot be said to be a general method for implementing ion exchange chromatography due to the insufficient effect of accelerating electron transfer.

The present invention provides a method for carrying out an electron transfer reaction between tetravalent uranium and hexavalent uranium.
Functional compounds and their salts, functional compounds with complex-forming ability? l
One or more organic compounds selected from the group consisting of organic compounds having 1-2 or more and one or more ions selected from the group consisting of ions of the following metals and ions of atomic groups containing the following metals. , a method for accelerating an electron transfer reaction.

Rubidium, copper, gold, zinc, cadmium, scandium, aluminum, gallium, indium, thallium, zirconium, hafnium, kermanium, tin, vanadium, niobium, arsenic, bismuth, chromium, molybdenum, manganese, rhenium, iron, Nickel, ruthenium, rhodium, palladium, lanthanide group metals and thorium.

The electron transfer reaction system between tetravalent uranium and hexavalent uranium in the present invention can be freely selected from a homogeneous liquid phase, a liquid-liquid phase, and a homogeneous liquid phase. As a medium in a homogeneous liquid phase, a solution of an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid or the like having a concentration of 0.01 normal or more or a mixed acid solution thereof can be used. One liquid phase in the liquid-liquid phase is a liquid ion exchanger (
For example, hexavalent uranium or tetravalent uranium may be selectively retained throughout the entire circumference (for example, triophthylamine, tributyl phosphate, etc.). Similarly, an ion exchange resin or the like can be used as the same phase in the same liquid phase.

In the present invention, the electron transfer reaction rate between tetravalent uranium and hexavalent uranium can be totally accelerated regardless of whether the reaction system is homogeneous or heterogeneous.

The organic metal component 7 of the accelerator that can be used in the present invention includes compounds containing nitrogen having a lone pair of electrons, salts thereof, and organic compounds having two or more functional groups capable of forming a complex.

Suitable compounds include:

Virol, 2-methylvirol, 3-methylvirol,
N-#-f-ruvirol, virol visiting conductors such as 2-virolcarboxylic acid, imidazole derivatives such as piperazine, imidazole, 1-methylimidazole, 4-methylimidazole, 1) 1-1.2.3-) Riazole , 2H-1,2,3
-triazole, 1H-1,2,4-)riazole, 4
H', +2+4 i''J triazole derivatives such as azole, pyridine, 2-methylpyridine, 3-methylbilicine, 4-methylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-hydroxypyridine, 5 -Hydroxypyridine, 4-hydroxypyridine, 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,5-pyridinecarboxylic acid, 2,4-pyridinedicarboxylic 2,2.s-pyridinedicarboxylic acid , 2,6-pyridinedicarboxylic acid, 3,
4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2.3.4-pyridinetricarboxylic acid, 2,4.
Pyridine derivatives such as 5-pyridinetricarboxylic acid, 2,4.6-pyridinetricarboxylic acid, 5,4.5-pyridinetricarboxylic acid, quinoline, 2-methylquinoline, 3-methylquinoline,
4-methylquinoline, 6-methylquinoline, 8-methylquinoline, 2-methyl-4-hydroxyquinoline, 4-
Methyl-2-hydroxyquinoline, 2-hydroxyquinoline, 4-hydroxyquinoline, 5-hydroxyquinoline, 6-hydroxyquinoline, 7-hydroxyquinoline, 8-hydroxyquinoline, 2-aminoquinoline, 5-
Aminoquinoline, 4-aminoquinoline, 2-quinolinecarboxylic acid, 5-quinolinecarboxylic acid, 4-quinolinecarboxylic acid, 5-quinolinecarboxylic acid, 2.4-dihydroxyquinoline, 2,3-quinolinedicarboxylic acid, 2.4 −
quinoli/dicarboxylic acids, quinoline derivatives such as inquinoline, 3-amine salicylic acid, 4-7 minosalicylic acid, 5-amine salicylic acid, 0-amine benzene nulpon (f, m
--7 Minobenzenesulfonic acid, p-aminobenzenesulfonic acid, hydroquinone, pyrogallol, m-benzenedicarboxylic acid, p-benzenesulfonic acid, 1,2,3-
Benzenetricarboxylic acid, 1.2.4-benzenetricarboxylic acid, 1.5.5-benzenetricarboxylic m, 1+
2+3+4-benzenetetracarboxylic acid, 1,2,5,
5-Benzenetetracarboxylic acid f) I'2.1,2,4.
Benzene derivatives such as 5-benzenetetracarboxylic acid.

1. Metal ions and metal-containing atomic group ions used in combination with the quasi-organic compound of above ii) include rubidium, copper, <a, zinc, cadmium, scandium, aluminum, gallium, indium, and thallium. ,
Zero among various oxidation numbers of each gold moiety of zirconium, hafnium, kermanium, tin, vanadium, niobium, Mti, binumuth, chromium, molybdenum, manganese, rhenium, iron, nickel, ruthenium, rhodium, palladium, lanthanide group and thorium. (For example, vanadium has cations with valences of 2, 3, and 4.5), and metal oxide salt ions [For example, vanadium has meta(VO3 -), Ortho (VO3
-''), pyro(vtoq-'), poly(V2O6-2
) (7) containing each vanadate ion], and complex ions made of these ions and various complexing agents.

The above ions are actually added as salts, and chlorides of the above ions are usually convenient as they are cheap and easily available, but other halides as well as non-acid salts such as sulfates and nitrates are useful. Organic acid salts such as oxalate and acetate can also be used. However, it is an essential requirement that these salts be soluble in inorganic acid solutions.

Metals generally have multiple valence ion associations, and any 111
Acceleration can be achieved by adding several 1I ions, but if the redox potential of the metal is higher than that of uranium, the oxidant will oxidize tetravalent uranium, so the tetravalent uranium in the reaction solution will The difference in the composition ratio of hexavalent uranium is 1. Therefore, in this case, it is preferable to add a reduced form of Kasa group ion gold. If oxidizers are unavoidable: When used, it is added at a sufficiently small amount of 4 degrees relative to tetravalent uranium. On the other hand, the redox potential is the same as that of uranium. If it is lower and total reduction of hexavalent uranium is inconvenient, it is preferable to add oxidant metal ions.

In general, the larger the ratio of the concentration of the added total condensation ion accelerator to the product of the a degree of tetravalent uranium and the concentration of hexavalent uranium, the i
j); The particle transfer reaction rate constant increases, and if the degree of uranium is constant, k increases as the concentration of the added metal ion accelerator increases, and the acceleration effect te1.bi
However, by coexisting with the above-mentioned compound, the electron transfer reaction rate can be significantly accelerated compared to the case where only the ion compound is present.

The metal ions used in the present invention are effective even when used alone; however, since the metal ions are added as metal salts,
Concentration of counter ion (for example, chloride ion in case of chloride)
The skin will increase by the amount added. Generally, gold kJ4
has a certain constraint on the solubility product, so increasing the counterion will significantly decrease the solubility of the metal. In short, due to solubility limitations, 1. The amount added cannot be increased indefinitely. Furthermore, when attempting to completely separate uranium isotopes by ion-exchange chromatography using one cation-exchange phase or an anion-exchange resin packed column, the ion Adsorption of uranium ions to the exchange resin may be completely inhibited, and satisfactory romatography may not be possible.

The organic compound used in the present invention has almost no effect of accelerating the electron transfer layer when used alone, but when it coexists with the metal ions mentioned above, the total accelerating effect of metal ions is significantly increased, so the uranium isotope separation efficiency is In addition to the advantage that the separation device can be made smaller and the concentration of the added metal ion is lower than before, it has a more accelerating effect than before in the low p range, so it is possible to completely avoid the above-mentioned problems in the development of romatography. can.

In the method of the present invention, it is possible to achieve at least the total acceleration effect when each of the ions or specific compounds is used alone without the inner sphere as described above, and furthermore, it is possible to achieve a synergistic effect by combining them. can.

In the present study ψ], the acceleration effect was determined by the method described below.

McKay's 1i1ii sentence (HoA, C, McKay,
Nature, 142.

9.97 (1938)), h- is an isotopically labeled example of 235U(IV)-1j! 38U (VT); 238
U(m + 235U(VI), Table 7je equilibrium 'electron transfer reaction rate constant ki'; I, U-235 and I
The time t (minutes) between when tetravalent uranium and hexavalent uranium, which have different isotopic ratios with J-238, are mixed and the reaction is started, until electron exchange equilibrium is completely reached, is t (minutes). By taking the exchange rate F in , it can be calculated using the following formula.

Here, CTJ (IV)] and CU (VI)) are the molar concentrations of Shixian-1 uranium and Sixxian-1 uranium in the mixed solution, respectively.

Furthermore, the exchange rate F is given by the following equation as in a normal reaction. .

(X~-Xo) This X. .

■For the gold side of the homogeneous liquid phase reaction system, since the isotopic mole fraction is known, a bath solution of hexavalent depleted uranium with a known isotope mole fraction is used, and a bath solution of tetravalent natural uranium is used. Prepare all the solutions, heat them at the same temperature, quickly mix them, add cold hydrochloric acid after a few minutes to stop the reaction, and then completely separate and purify the tetravalent uranium using an ion exchange resin. The resulting sample is analyzed using a surface ionization mass spectrometer to determine the isotopic molar fraction X1. Calculate all of F from Xt, and use this value to calculate k according to the above-mentioned McKay formula. Calculate all. For the mixed solution to which all the accelerators have been added, the velocity constant kfI is determined in the same way, and the cooling effect is determined by comparing it with k. As is clear from McKay's equation, if the concentrations of tetravalent uranium and hexavalent uranium are fixed separately,
The time t required to reach a certain paternity conversion rate is inversely proportional to the candy k. Therefore, in a system where k is a person, that is, there is a force U speed effect, the required time t (minutes) is reduced. For example, if k doubles, the time required to reach the same reaction rate at 1 will be halved.

This is 11! In the chemical enrichment process of uranium using the particle transfer reaction, the production amount per unit time will be doubled, which is second in the world, and the industrial benefits will be extremely large.

For liquid-liquid applications, the entire acceleration effect can be measured in the same manner even in reaction systems with the same liquid phase. For example, a phase in which depleted uranium is present as hexavalent uranium (in the case of a liquid-liquid reaction system) or adsorbed (in the case of a liquid-phase reaction system), and a phase in which natural uranium is present as total tetravalent uranium. After all preparations and preheating to the reaction temperature, the reaction is carried out by stirring and mixing them in a reaction container in a constant temperature bath, and after a predetermined time, the reaction is stopped by pouring into a cold hydrochloric acid solution, and immediately the liquid is separated ( The hexavalent uranium phase is removed by filtration (for liquid-liquid reaction systems) or filtration (for liquid-liquid reaction systems). The obtained tetravalent uranium is purified in the same manner as in the case of the homogeneous liquid phase, and the isotope ratio (X, )k is measured. From this, the exchange rate CF) is calculated. In the same reaction system, the exchange rate (F) 'i at any reaction time (1)
= measured and plotted against time (1) An(1-F)k, a graph of a straight line passing through the origin (t=0.F=OJ' with a constant slope according to the exchange rate) is obtained. The steeper the slope, the faster the electron transfer reaction rate.Create a straight line graph of the exchange rate Fi measured at a predetermined reaction time (t;) versus tn (1-F). death,
Time to reach F = 1/2 (t1/2),
Based on the so-called half-life, this value was used to determine the acceleration effect.

In order to specifically explain the present invention, all examples of the present invention will be described below. These are not intended to limit the scope of the invention.

Real M11 Examples 1-25 Natural isotope ratio (isotope molar fraction of uranium-265 0.0
A concentrated 1,00 M tetravalent uranium solution (referred to as uranus stock solution) was obtained by dissolving Kinzo uranium (07200) in total a-a hydrochloric acid, removing the dissolved residue by filtration, and diluting the mother liquor with deionized water. Prepared.

Commercially available uranyl nitrate bath solution (manufactured by Merck & Co., depleted uranium with an isotopic molar fraction of uranium-235 of 0.004214) was dissolved in deionized water to a concentration of about 0.1 M, water-based ion The solution was passed through a type of cation exchange resin column to create a uranyl adsorption zone. This was washed with a large amount of de-imensed water to remove all the nitrate roots, and then 4M hydrochloric acid was passed through the entire bath to remove uranyl. A total of n cycles were manufactured.

A total of tetravalent uranium reaction solutions containing tetravalent uranium at a concentration of 0.1M and the acids shown in Table 1 at the concentrations shown in Table 1 were prepared using the above Uranus stock solution. Similarly, using the above uranyl stock solution, it contains hexavalent uranium at a concentration of 0.1M, the acid ligation shown in Table 1, the concentration shown in Table 1, and all the accelerators shown in Table 1, as shown in Table 1. A reaction solution containing hexavalent uranium at various concentrations was prepared. They were placed in each base of a double microfeeder.

The tetravalent uranium reaction liquid and the hexavalent uranium reaction liquid contained in the two towers of the microfeeder are mixed in the reaction tube made of Teflon tube through the mix pump joint by the drive of the piston part. All parts including the mixing joint and the reaction tube were sealed in a heat-retaining tube kept at the measurement temperature, and the outlet of the reaction tube was placed in a hydrochloric acid solution that had been cooled in advance in ice. The hydrochloric acid concentration of the water-cooled hydrochloric acid solution is 6.
It was like becoming an M. This operation stops the electron transfer reaction.

A jacketed column with an inner diameter of 'Cms and a height of 20 L is fully filled with a chloride ion type anion exchange resin, and while cold water is circulated through the jacket, the mixed reaction solution of tetravalent uranium and hexavalent uranium is completely passed through. did. Under these conditions, hexavalent uranium, which has a strong adsorption power to the ion exchange resin, forms an adsorption zone and remains in the column, while tetravalent uranium, which has a weak adsorption power, takes on a green color and quickly moves out. By subsequently developing the entire amount of 6M hydrochloric acid solution, it was possible to completely collect 111 pieces of tetravalent uranium outside the column.

After the obtained tetravalent uranium solution was sufficiently purified by a conventional method, the isotopic molar fraction of uranium oxide was measured using a surface ionization mass spectrometer. From this, we get the exchange rate F, M
The value of k was calculated using the ckay formula.

However, except that no additives were added, the same experiment as in the example was carried out, and the values obtained for the speed foot 2 were all ko, and the values are shown in Table 1. Furthermore, the rapid expansion constants were obtained in the same manner as in this example except that the Ariiso compound was not added, and k/ was set to 6, which is shown in Table 1.

Example 26 A jacketed developing column V having an inner diameter of 20 n+u+φ and a length of 1000+rrrh was filled with an anion exchange resin which had been subjected to lolomethylation of a nutylene-divinylbenzene copolymer and then converted to quaternary ammonium with trimethylamine.

Hydrochloric acid2. Photolaminated gold conditioning was performed by supplying 5 t of an aqueous solution containing o M'/lk using a metering pump.

Hydrochloric acid jOM/l, ferrous chloride o, 6M/V, ferric chloride
Iron o, i is fed from the upper part of the oxidation 111m oxidation tower containing q/l, 2-aminopyridine 0.5M/4, and the 1'11i, output 1 yen composition from 1 part is fed e, the composition. Fe (l old ions were all adsorbed on an anion exchange resin) with an equal amount of acid 2.OM/l, ferrous chloride 0.
3M/l, 2-aminopyridine o,s M/L
% e, containing 0.15M/lk urana ion, 12
The uranium absorption zone was completely formed by supplying 0rnl. after that,
Hydrochloric acid 2.0M/l, 1'tkO chloride, 5M/t
%2-aminopyridi70.5 M/L%Cr (
IJ) The adsorption zone was vigorously developed while resisting a reducing agent bath containing 0.3 M/l'(z) of ions.

Uranium 2 used for adsorption in the Mokufu example and the following examples
The isotope ratio of 65 (hereinafter referred to as U-235) to uranium-238 (hereinafter referred to as U-238) is Cjo 07
It was 252.

Solution i flowing out as it develops 2. The uranium concentration near the reduction interface was measured using a spectrophotometer, and after purification, the isotopic ratio of [J-235 to [J-238] was measured using a mass spectrometer. , 0.007508 was obtained.

Example 27 Conditioning was carried out in the same manner as in Example 26 using the apparatus described in Example 26 and the same anion exchange resin as in Example 26.

Tutuite hydrochloric acid 2.0 M/t, FeC1!40.
3M/L.

5-hydroxypyridine 0. s M/L, Fe
(lf) An oxidant solution containing 0.1M/4i ions is supplied from the top of the entire developing tower, and Fe(III) ions are exchanged with anion exchange (vJJ Adsorbed to fat.Continued with 2.0M hydrochloric acid.
/L.

A uranium adsorption zone was formed by supplying 120 ml of a solution containing 1,0°3 M/'L of FeCl, 0.5 M/L of 3-hydroxypyridine, and 15 M/L of U(IV) ions.

After that, hydrochloric acid 2.0 M/L, FeC4,0,3M/
L.

6-hydro xybilidi70.5 M/LSCr
(11) A reducing agent solution containing 0.3 M/L of ions was supplied to develop the adsorption zone in a displacement manner. The total uranium isotope ratio near the reduced part was measured in the same manner as in Example 26, and it was found to be 0.0075.
I got o1.

Example 28 Conditioning was carried out in the same manner as in Example 26 using the apparatus described in Example 26 and the same anion exchange resin as in Example 26.

Next, hydrochloric acid 2.0 M/l, FeC, 40j M/l
L.

8-Hydroxyquinoli 70.5 M/L, Fe(
1. An oxidizing agent solution containing 0.1 M/lk of old ions is supplied from the upper part of the developing tower, and Fe (river) ions are adsorbed onto the anion exchange resin at a point where the composition of the effluent from the lower part is equal to the composition of the feed solution. Ta. Continued hydrochloric acid 2.0M/L, FeCIA
o, 5 M/L, 8-hydroxyquinoline 0.5 M/L
L, U(IV) Io70,15M/Lf<Containing solution 1
20 me was supplied to completely form the uranium adsorption zone.

Then, hydrochloric acid 2.0 M/L, FeC/, 0.3
M/L.

Supply the entire reducing agent solution containing 70.5M/L of 8-hydroxyquinol, Cr(TI) ions, and 3MILk to the adsorption zone! It was developed in exchange. The total uranium isotope ratio near the reduction part was measured in the same manner as in Example 26, and 0.007536 was obtained.

Example 29 Using the apparatus described in Example 26 and the same ion exchange resin as in Example 26, the same procedures as in Example 26 were used to carry out conditioning.

Next, hydrochloric acid 2.0 M/L, FeC/, 0
．． 3M/L.

Bio Kao -/I10.5 M/ L* Fe (1
11) The oxidizing agent solution containing 0.1 M/if of ions is supplied from the top of the developing tower, and the effluent composition from the bottom is equal to the feed solution composition, and the Fe(Ill) ions are completely converted to the anion exchange resin. It was adsorbed. Continued hydrochloric acid 2.0 M/L
% FeC40, 3M/L, pyrogallol 0.5M/
Solution 120 containing 0.15 M/L of L, U (IV) ions
All ml of uranium was supplied to form a uranium band.

After that, salt fA22. OM/L, FcC40j M/
L, pyrogallol 0.5 M/L, Cr (11
A reducing agent solution containing 0.3 M/L of 1 io:y was completely supplied and the adsorption zone was developed in a reactive manner. The uranium isotope ratio near the reduced part was measured in the same manner as in Example 26, and 0.007477f was obtained.

Example 60 All conditioning was performed using the same apparatus as in Example 26 and the same anion exchange resin as in Example 26, and by sweeping in the same manner as in Example 26.

Tsutsuite I;j3self122. OM/t, VC40
j M/L, 2-aminopyridine 0.5 M/L
An oxidizing agent solution containing 0.1 M/lk of Fe(Ni1) ions was supplied from the top of the developing column until the composition of the effluent from F became equal to the composition of the feed solution.
) Ions were absorbed into an anion exchange resin. Twitching hydrochloric acid 2. OM/L.

VCl30.3 M/L, 2-aminopyridine Oj M
A solution containing 15 M/L of 15 M/L of U(IV) ions was supplied to form a complete uranium adsorption zone.

Then, hydrochloric acid 2. OM/L, VCl, 0.3M/
L% 2-Aminopyridine J5 M/L, Cr (
The entire reducing agent solution containing 0.6 M/L k of old ions was supplied to develop the adsorption zone in a displacement manner. The total uranium isotope ratio near the reduced amount was measured in the same manner as in Example 26, and it was found to be 0.0074.
90 i get/ko.

Example 31 Anion exchange between the device described in Example 26 and Example 26? Using A resin, the same 8Ri W as in Example 26
Conditioning was performed by the work.

Poke hydrochloric acid jOM/l, VCt, 0.3 M/L
'Q 2-Bi IJ Schiff JJ Rupho7 Acid 0.5 M/
L, Fe(Ill) ion containing 0.1 M/lk oxidizer bath #, supplied from the top right 1 of the total development tower, in a trench where the composition of the effluent from the bottom is equal to the composition of the feed solution.
l) Ions were adsorbed onto anion exchange 4tI4 fat. Continue with hydrochloric acid 2. OM/L, VCl, 0.3 M/L
, 2-pyridinecarboxylic acid 0.5M/L, U(IV) ion o, 1sM/L containing 120+n/! A uranium adsorption zone was formed.

Then, hydrochloric acid 2.0 M/L, VCl, 0.3 M
/L, 2-pyridinecarboxylic acid o,s M/L
, cr (H) ions of 0.3 M/L were supplied to the reducing agent M solution, and the mixture was developed in a manner that the adsorption and d9 borrows and the total lids were exchanged. The uranium isotope ratio near the reduced part was measured in the same manner as in Example 26, and 0.007470 was obtained.

Example 62 The same anion exchange resin as in Example 26 was used in the apparatus described in Example 26, and all conditioning was performed in the same manner as in Example 26.

Pecked with hydrochloric acid 2.0 M/l, MoC 0. I
M/L.

Bio power o-k O,5hi/L,Fe (IJI)
An oxidizing agent solution containing 0.1 M/L gold ions is supplied from the top of the developing column, and the Fe (fill ions are anion-exchanged) with the effluent volume from the first part being equal to the feed liquid composition. It was adsorbed on the resin.Hydrochloric acid 2.OM/]
, MoCmuOjM/L, pyrogallol tl, 5M/L,
U(IV) ion 0. +5M/'L'e containing solution 120
m1k was supplied to form uranium absorption M11.

Then, hydrochloric acid 2. OM/L, MoCmu0. iM
/L, pyrogallol 0.5 M/L, Cr □i
) The entire reducing agent solution containing 0.5 M/L of ions was supplied, and the adsorption zone was developed with total displacement. The total uranium isotope ratio near the reduced amount was measured in the same manner as in Example 26, and it was found to be 0.007424Q.
Obtained.

COMPARISON EXAMPLES Described in Examples 26-32/This device and Examples 26-6
Example 26-6 using the same anion exchange resin as in Example 2
2 and [p2 conditioning by bJ-like operation 1
It's been a long time.

Poking with hydrochloric acid 2. OM/L, Fe (■) ion o,
The entire oxidizer solution containing IM/Li was supplied, and the Fe(Ill) ion anion exchange resin was sucked into the tank at a point where the composition of the effluent at the bottom was equal to the composition of the feed solution. Continue with hydrochloric acid 2. A uranium adsorption zone was formed by supplying 120 mJi of a solution containing 0.15 M/L of OM/L, U(IV)' (off).

Then, hydrochloric acid 2. o M/L, Cr(TI)
The entire reducing agent solution containing 0.5 M/L of ions was supplied to develop the adsorption zone in a displacement manner. The total uranium isotope ratio near the reduced amount was measured in the same manner as Examples 26 to 62, and it was found to be 0.00727.
I had 4 meetings.

Claims (3)

[Claims] (1) In addition to conducting an electron transfer reaction between tetravalent uranium and hexavalent uranium, it is possible to conduct an electron transfer reaction between tetravalent uranium and hexavalent uranium. From the group consisting of two or more organic compounds, one or more organic compounds having two or more ions, and the following metal ions and the following V
A method for accelerating an electron transfer reaction characterized by coexisting with one or more types of ions selected from the group consisting of ions of atomic groups including the genus. Metals> Ruhiscium, 'il'Js gold, zinc, cadmium, scandium, aluminum, gallium, indium, thallium, zirconium, hafnium, kermanium, tin,
Vanadium, niobium, arsenic, bismuth, chromium, molybdenum, manganese, rhenium, sand, nickel, ruthenium, rhodium, palladium, ranknid metals and thorium. (2) The method according to claim 1, wherein the metal is copper, vanadium, molybdenum, manganese, iron, or tin. (3) The type of organic compound is pyrrole and its derivatives, piperazine, imidazole and its derivatives, triazole and its derivatives, pyridine and its derivatives, gynoline and its derivatives, and benzene derivatives having two or more functional groups capable of forming a complex. A method according to claim 1.