Large-Particle-Size Ammonium Uranate Hydrate Crystal, and Preparation Method and Apparatus Therefor

Abstract

A large-particle-size ammonium uranate hydrate crystal and a method of manufacturing the same, in which the reaction rate is controlled by injecting ammonia gas into a uranyl nitrate aqueous solution, thereby increasing the particle size of the ammonium uranate hydrate crystal, and the average particle size of a final ammonium uranate hydrate crystal is 9.32 to 14.68 m, which is 100 times or more that of a conventional crystal, and uranium content is less than 1 ppm. Since this ammonium uranate hydrate crystal has a very large particle size, handling thereof in subsequent filtration, drying and calcination/reduction processes is very easy, and moreover, the design of devices for subsequent processes is simple, and little uranium is contained in the filtrate of the filtration process, thus obviating an additional chemical treatment process for uranium recovery, which can greatly reduce facility investment costs.

Claims

1. A method of manufacturing an ammonium uranate hydrate crystal, suitable for precipitation and separation of uranium, the method comprising: (1) placing a uranyl nitrate aqueous solution as a mother liquor in a crystallizer; (2) foaming crystals by injecting ammonia gas into the mother liquor and carrying out a crystallization reaction; and (3) stopping the crystallization reaction when a pH of the mother liquor is in a range of 7 to 8.

2. The method of claim 1, wherein in step (1), a uranium concentration of the mother liquor is 5 to 100 g/L.

3. The method of claim 1, wherein in step (2), the ammonia gas is injected at a flow rate of 0.1 to 5.0 Nm.sup.3/hr.

4. The method of claim 1, wherein in step (2), air is supplied together with the ammonia gas, and a flow rate of the air is 10 to 100 times a flow rate of the ammonia gas.

5. An ammonium uranate hydrate crystal manufactured by the method of claim 1.

6. An ammonium uranate hydrate crystallizer, comprising: a crystallizer chamber having a mother liquor circulation pipe; and an ammonia distributor directly provided to the mother liquor circulation pipe.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 is a concept view of a crystallizer according to the present invention;

[0020] FIG. 2 is a concept view of the ammonia distributor of FIG. 1;

[0021] FIGS. 3a to 3d are scanning electron microscopy (SEM) images showing an ammonium uranate hydrate powder manufactured in each experiment of the present invention;

[0022] FIG. 4 is a concept view of the crystallizer in a conventional ADU process; and

[0023] FIG. 5 is an SEM image showing an ammonium uranate hydrate powder manufactured using the conventional ADU process.

DETAILED DESCRIPTION

[0024] Hereinafter, a detailed description will be given of the present invention.

[0025] Accordingly, the present invention pertains to a method of manufacturing an ammonium uranate hydrate crystal, suitable for the precipitation and separation of uranium, the method comprising (1) placing a uranyl nitrate aqueous solution as a mother liquor in a crystallizer, (2) forming crystals by injecting ammonia gas into the mother liquor and carrying out a crystallization reaction, and (3) stopping the crystallization reaction when the pH of the mother liquor is in the range of 7 to 8.

[0026] In step (1), the uranium concentration of the mother liquor is preferably 5 to 100 g/L.

[0027] In step (2), the ammonia gas is preferably injected at a flow rate of 0.1 to 5.0 Nm.sup.3/hr.

[0028] In step (2), air is supplied together with the ammonia gas, and the flow rate of air is preferably 10 to 100 times the flow rate of the ammonia gas.

[0029] In addition, the present invention pertains to an ammonium uranate hydrate crystal manufactured by the aforementioned method.

[0030] In addition, the present invention pertains to an ammonium uranate hydrate crystallizer, comprising a crystallizer chamber 1 having a mother liquor circulation pipe 2; and an ammonia distributor 3 directly provided to the mother liquor circulation pipe 2.

[0031] The present invention is focused on a method of increasing the crystal size of ammonium uranate hydrate in order to solve the problems with the conventional process.

[0032] The major factor affecting the crystal growth of ammonium uranate hydrate is the reaction rate. The reaction rate is associated with the uranium concentration in the uranyl nitrate aqueous solution and with the flow rate of ammonia that is injected. It is advantageous for the reaction rate to be slow for sufficient crystal growth. The reaction rate is slower with a decrease in uranium concentration and in ammonia flow rate.

[0033] Accordingly, instead of the conventional reaction of a uranyl nitrate aqueous solution and ammonia water, in the present invention, the reaction between the uranyl nitrate aqueous solution and the ammonia gas was induced as follows.

UO.sub.2(NO.sub.3).sub.2 (aq)+(x+2)NH.sub.3 (g)+(y+1)H.sub.2O (l)

.fwdarw.UO.sub.3.xNH.sub.3.yH.sub.2O (s)+2NH.sub.4NO.sub.3 (aq)

[0034] A better understanding of the present invention will be given through the following examples. These examples are merely set forth to illustrate the present invention but are not to be construed as limiting the scope of the present invention, as is apparent to those skilled in the art.

Example 1. Reactor Preparation

[0035] In the present invention, a crystallizer 1 in which the crystallization reaction is carried out is schematically shown in (FIG. 1), and as shown in (FIG. 2), the ammonia gas and the mother liquor may be reacted in an ammonia distributor. The reactor of the present invention is different from a conventional reactor shown in (FIG. 4) in which ammonia water (liquid) and a uranyl nitrate aqueous solution are placed together in a crystallizer.

[0036] The mother liquor, that is, the uranyl nitrate aqueous solution, is placed in a predetermined amount in the crystallizer 1. Here, the term mother liquor refers to a solution in which the crystallization process is performed. When the uranium concentration in the aqueous solution is high, it may be adjusted through the addition of distilled water. As such, the uranium concentration of the mother liquor is preferably 5 to 100 g/L. If the uranium concentration of the mother liquor is lower than 5 g/L, the operation time is too long, and thus operation becomes undesirable and the capacity of subsequent processes for treating the filtrate becomes excessively large relative to the amount of uranium recovered. On the other hand, if the uranium concentration is higher than 100 g/L, the reaction rate is excessively increased. After completion of the preparation of the mother liquor, the temperature of the mother liquor is gradually elevated by heating the reactor while circulating the mother liquor in the reactor. The circulation of the mother liquor continues until the reaction is terminated.

Example 2. Crystal Formation Through Crystallization Reaction

[0037] The temperature of the mother liquor is kept constant within the range of 50 to 85 C., and the ammonia gas is injected into the ammonia distributor 3 provided to the mother liquor circulation pipe 2. Here, ammonia may be injected in the state of being diluted in combination with air. The flow rate of ammonia that is injected is preferably 0.1 to 5.0 Nm.sup.3/hr, and the flow rate of air that is injected is preferably 10 to 100 times that of ammonia. If the flow rate of ammonia that is injected is less than 0.1 Nm.sup.3/hr, the operation time is increased and operation becomes undesirable. On the other hand, if the flow rate thereof exceeds 5.0 Nm.sup.3/hr, the reaction rate is excessively increased. If the injection rate of air is less than 10 times that of ammonia, the reaction rate is excessively increased. On the other hand, if the injection rate of air is greater than 100 times that of ammonia, the capacity of subsequent processes for off-gas treatment becomes excessively large. Through the above process, an ammonium uranate hydrate crystal is formed by reacting ammonia gas with uranyl nitrate in the mother liquor.

Example 3. Crystal Recovery

[0038] After completion of the crystallization reaction in the mother liquor, the supply of ammonia gas is stopped and the solution is cooled, after which the slurry containing the formed crystal is transferred to a subsequent process (filtration).

[0039] During the precipitation reaction, it is not necessary to supply additional substances other than ammonia and air, and the pH of the mother liquor gradually increases with the progression of the precipitation reaction. Also, whether the process is terminated is judged depending on the pH of the mother liquor, and it is preferable that the reaction be terminated when the pH of the mother liquor ranges from 7 to 8. Here, in addition to the adjustment of the flow rate of the ammonia that is supplied, there is no need for an additional operation to control the pH.

Experiment Example 1. Confirmation of Manufactured Crystal Powder

[0040] The experiment for preparation and confirmation of the ammonium uranate hydrate according to the above examples was performed four times at different reaction rates. The shape of the manufactured powder is shown in FIGS. 3a to 3d. Through this experiment, it was confirmed that the particle size varies with the reaction rate.

[0041] The conventional crystal had a small particle size, as shown in FIG. 5, whereas the crystal according to the present invention had a large particle size, as shown in FIGS. 3a to 3d. Specifically, the average particle size was 9.32 to 14.68 m, which was 100 times or more the size of the crystal manufactured through the conventional ADU process. Based on filtrate analysis results, the uranium content of the filtrate was less than 1 ppm.

[0042] Although preferred embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that variations or modifications of process variables in the method of the present invention are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

[0043] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0044] The use of the terms a and an and the and similar referents in the context of describing the invention (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms comprising, having, including, and containing are to be construed as open-ended terms (i.e., meaning including, but not limited to,) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., such as) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0045] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.