JPH0458417B2 - - Google Patents
Info
- Publication number
- JPH0458417B2 JPH0458417B2 JP62117793A JP11779387A JPH0458417B2 JP H0458417 B2 JPH0458417 B2 JP H0458417B2 JP 62117793 A JP62117793 A JP 62117793A JP 11779387 A JP11779387 A JP 11779387A JP H0458417 B2 JPH0458417 B2 JP H0458417B2
- Authority
- JP
- Japan
- Prior art keywords
- uranyl nitrate
- powder
- range
- uranium
- nitrate solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 229910002007 uranyl nitrate Inorganic materials 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 229910052770 Uranium Inorganic materials 0.000 claims description 14
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000008188 pellet Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 125000005289 uranyl group Chemical group 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- -1 ADU precipitation Chemical compound 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G43/00—Compounds of uranium
- C01G43/01—Oxides; Hydroxides
- C01G43/025—Uranium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
（産業分野）
本発明は硝酸ウラニル系溶液から重ウラン酸ア
ンモン（ADU）を経由し、単独でのペレツト成
形加工を可能ならしめる硝酸ウラニル系からの
UO2粉末製造方法に関する。Detailed Description of the Invention (Industrial Field) The present invention is a process for forming pellets from a uranyl nitrate solution by converting the uranyl nitrate solution into ammonium deuterate (ADU).
Regarding UO 2 powder manufacturing method.
（従来技術とその問題点）
核燃料ペレツト加工工程では少なからぬスクラ
ツプラウンが発生する。このスクラツプラウンを
単独で再使用する場合、粉末物性としては不活性
なため、通常硝酸溶液で溶解し、硝酸ウラニル
UO2（NO3）2の溶液とした後、アンモニア水を添
加し、ADUの化学組成を経由し、UO2粉末に転
換して使用する。この方法では、まず硝酸ウラニ
ル溶液にアンモニア水を添加し、ADUの沈殿を
生成させ、このスラリー液を別し乾燥・焙焼・
還元してUO2粉末とする。(Prior art and its problems) In the process of processing nuclear fuel pellets, a considerable amount of scrap prawns are generated. When reusing this Scraps Prawn alone, since it is inactive as a powder, it is usually dissolved in a nitric acid solution and uranyl nitrate is dissolved in a nitric acid solution.
After making a solution of UO 2 (NO 3 ) 2 , aqueous ammonia is added and the chemical composition of ADU is converted into UO 2 powder for use. In this method, aqueous ammonia is first added to a uranyl nitrate solution to form a precipitate of ADU, and this slurry liquid is separated and dried, roasted, and
Reduce to UO2 powder.
この硝酸ウラニル系のUO2粉末は、UF6から転
換して得られるUO2粉末と比較すると、活性過ぎ
るため、単独でペレツトの製造を行うと、キヤツ
ピング（かけ）が発生しやすく、また焼結密度
（％TD）が上りすぎる等の問題があり、大量生
産には不適であつた。 This uranyl nitrate-based UO 2 powder is too active compared to the UO 2 powder obtained by converting it from UF 6 , so if pellets are produced alone, capping tends to occur and sintering There were problems such as an excessively high density (%TD), making it unsuitable for mass production.
（発明の目的）
本発明者らは上記の従来方法の問題点を解決
し、硝酸ウラニル系から単独でペレツト成形加工
を可能ならしめるUO2粉末の製造方法を提供すべ
く、種々検討した結果、ADU沈殿生成等のアン
モニア（水）の添加速度を制御することによつ
て、上記目的を達成しうることを見出し、この知
見に基づいて本発明を完成するに到つた。(Objective of the Invention) The present inventors have conducted various studies in order to solve the problems of the above-mentioned conventional methods and provide a method for producing UO 2 powder that can be formed into pellets from uranyl nitrate alone. The inventors have discovered that the above object can be achieved by controlling the rate of addition of ammonia (water) such as ADU precipitation, and have completed the present invention based on this knowledge.
（発明の構成）
すなわち、本発明によれば、50〜100ｇ／の
ウラン濃度と０〜2.5Nのフリー硝酸濃度とを有
する硝酸ウラニル溶液に20〜35％濃度のアンモニ
ア水を添加して重ウラン酸アンモン（ADU）の
沈殿を生成させ、その際該硝酸ウラニル溶液のPH
が3.5〜4.5の範囲では該アンモニア水の添加速度
をおそくして１ｇウランあたり0.01ｇNH3／mm〜
0.025ｇNH3／mmの範囲に保ち、かつ該硝酸ウラ
ニル溶液のPHが4.5を越えた時は該アンモニア水
の添加速度を１ｇウランあたり0.1ｇNH3／mm〜
0.5ｇNH3／mmの範囲に保つとともに生成した
ADU沈殿物を分離・乾燥した後、空気中におい
て660〜760℃の範囲で焙焼し、次いで、還元雰囲
気中において660〜760℃の範囲で還元してUO2粉
末に転換することを特徴とする硝酸ウラニル系か
らのUO2粉末製造方法、が得られる。(Structure of the Invention) That is, according to the present invention, heavy uranium is added by adding ammonia water with a concentration of 20 to 35% to a uranyl nitrate solution having a uranium concentration of 50 to 100 g/ and a free nitric acid concentration of 0 to 2.5N. Precipitation of acid ammonium (ADU) is produced, during which the pH of the uranyl nitrate solution is
In the range of 3.5 to 4.5, the rate of addition of the ammonia water is slowed down to 0.01 g NH 3 /mm per 1 g uranium.
When the pH of the uranyl nitrate solution exceeds 4.5 , the ammonia water addition rate should be kept at 0.1 g NH 3 /mm per 1 g uranium.
While maintaining the range of 0.5gNH 3 /mm,
After separating and drying the ADU precipitate, it is roasted in the air at a temperature of 660-760℃, and then reduced in a reducing atmosphere at a temperature of 660-760℃ to convert it into UO2 powder. A method for producing UO 2 powder from uranyl nitrate system is obtained.
本発明は以上のように、ADU沈殿生成時のア
ンモニア水の添加速度を制御することにより、
ADUでの粉末物性を不活性側にうつすことによ
り、UO2粉末の物性を押え、単独でのペレツト成
形加工を可能ならしめる製造方法である。 As described above, the present invention controls the rate of addition of ammonia water during ADU precipitation.
This is a production method that suppresses the physical properties of UO 2 powder by transferring the physical properties of the powder in ADU to the inactive side, making it possible to mold the powder into pellets by itself.
本発明方法では、50〜100ｇ／のウラン濃度
と０〜2.5Nのフリー硝酸濃度とを有する硝酸ウ
ラニル溶液に20〜35％濃度のアンモニア水を徐々
に添加する。アンモニア水添加前の硝酸ウラニル
溶液のPHは0.5前後である。PH3.5までのアンモニ
ア水の添加速度はUO2粉末の物性に大きな影響を
与えるものでないが、この場合生産性の問題から
は１ｇウランあたり0.1ｇNH3／mm〜0.5NH3／mm
の範囲が適度な量である。アンモニア水の添加に
より、PH曲線は第１図のように上昇し、PH3.5〜
PH4.5の間でプラトー部があらわれる。 In the method of the invention, ammonia water with a concentration of 20-35% is gradually added to a uranyl nitrate solution having a uranium concentration of 50-100 g/1 and a free nitric acid concentration of 0-2.5N. The pH of the uranyl nitrate solution before adding ammonia water is around 0.5. The rate of addition of ammonia water up to pH 3.5 does not have a large effect on the physical properties of UO 2 powder, but in this case, from the viewpoint of productivity, it is recommended to add 0.1 g NH 3 /mm to 0.5 NH 3 /mm per 1 g uranium.
range is a reasonable amount. With the addition of ammonia water, the PH curve rises as shown in Figure 1, and PH3.5~
A plateau appears between pH4.5.
本発明方法では、この時のアンモニア水の添加
速度を１ｇウランあたり0.01ｇNH3／mm〜
0.025NH3／mmの範囲に押えることとPH4.5以上で
は該添加速度を１ｇウランあたり0.1ｇNH3／mm
〜0.5ｇNH3／mmの範囲に保つことを特徴とする
ものである。PH3.5〜PH4.5の間でのアンモニア水
の添加速度を、この値に保つのは、ADU沈殿時
の粒子生成を目的の粒子にするためであり、また
PH4.5以上での添加速度を、この値に保つのは、
ADU沈殿粒子の二次凝集を目的とする凝集粒子
にするためである。アンモニア水の添加によるPH
の上昇限度は9.0〜9.5程度とする。得られたADU
沈殿は別・乾燥した後、まず空気（空気流量：
0.3〜0.5M3／ｈ・KgＵ）中で660〜760℃の範囲で
２〜４時間焙焼し、次いで還元雰囲気（H2流
量：２〜5M3／ｈ・KgＵ）中で20分〜１時間還元
することによつて、UO2粉末が得られる。 In the method of the present invention, the rate of addition of ammonia water at this time is 0.01 gNH 3 /mm per 1 g of uranium.
The addition rate should be kept within the range of 0.025NH 3 /mm and at pH 4.5 or higher, the addition rate should be reduced to 0.1gNH 3 /mm per 1g uranium.
It is characterized in that it is maintained within a range of ~0.5 gNH 3 /mm. The reason why the ammonia water addition rate between PH3.5 and PH4.5 is maintained at this value is to ensure that the particles generated during ADU precipitation become the desired particles.
To maintain the addition rate at this value at pH 4.5 or higher,
This is to form agglomerated particles for the purpose of secondary aggregation of ADU precipitated particles. PH due to addition of ammonia water
The upper limit of increase is approximately 9.0 to 9.5. Obtained ADU
Sedimentation is separate. After drying, first air (air flow rate:
0.3 to 0.5 M 3 /h・KgU) at a temperature of 660 to 760°C for 2 to 4 hours, and then roasted in a reducing atmosphere (H 2 flow rate: 2 to 5 M 3 /h・KgU) for 20 minutes to 1 hour. By time reduction, UO2 powder is obtained.
このUO2粉末は、UF6より転換して得られる粉
末と同等で単独でのペレツト成形加工を可能なら
しめるものである。 This UO 2 powder is equivalent to the powder obtained by converting UF 6 , and can be processed into pellets by itself.
次に、本発明を実施例によつて、より具体的に
説明するが、以下の実施例は本発明の範囲を限定
するものではない。 Next, the present invention will be explained in more detail with reference to Examples, but the following Examples do not limit the scope of the present invention.
実施例
第２図に示す撹拌機をそなえたタンクに、ウラ
ン濃度80ｇ／、フリー硝酸濃度1.8Nの硝酸ウ
ラニル溶液200を張り込み、液温を40℃±２℃
に保温する。この硝酸ウラニル溶液に28％濃度の
アンモニア水を、図中Ａのバルブを開いて、下記
の２種の条件で添加する。Example 200 of a uranyl nitrate solution with a uranium concentration of 80 g/free nitric acid concentration of 1.8 N was poured into a tank equipped with a stirrer as shown in Figure 2, and the liquid temperature was adjusted to 40°C ± 2°C.
Keep warm. Aqueous ammonia with a concentration of 28% is added to this uranyl nitrate solution under the following two conditions by opening the valve A in the figure.
条件：添加速度を常に一定で添加する。Conditions: Always add at a constant rate.
添加速度は１ｇウランあたり0.1ｇNH3／mmで
ある。 The addition rate is 0.1 gNH 3 /mm per gram of uranium.
条件：添加速度をPHによつて変化させる。PH
3.5まで0.1ｇNH3／mm、PH3.5以上4.5以下は0.02ｇ
NH3／mm、PH4.5を越えると0.1ｇNH3／mmであ
る。これら２種の条件で得られたADUスラリー
をそれぞれバルブＢを開け、別工程におくる。
得られた２種のADUを120℃で２時間程度乾燥し
た後まず焙焼温度700℃、焙焼時間３時間で焙焼
する。この時の雰囲気は空気流量0.3M3／ｈ・Kg
Ｕである。焙焼によつて得られたUO2粉末を還元
温度680℃、還元時間30分で還元する。この時の
雰囲気はH2流量：2M3／ｈ・KgＵである。Conditions: Addition rate varies depending on pH. PH
0.1gNH 3 /mm up to 3.5, 0.02g for PH3.5 or higher and 4.5 or lower
NH 3 /mm, and when it exceeds PH4.5, it is 0.1gNH 3 /mm. The ADU slurry obtained under these two conditions is sent to a separate process by opening valve B.
The two types of ADUs obtained are dried at 120°C for about 2 hours and then roasted at a temperature of 700°C for 3 hours. The atmosphere at this time is an air flow rate of 0.3M 3 /h・Kg
It is U. The UO 2 powder obtained by roasting is reduced at a reduction temperature of 680°C and a reduction time of 30 minutes. The atmosphere at this time was H 2 flow rate: 2M 3 /h·KgU.
得られた２種のUO2粉末の比表面積は、条件
のものについては、4.0m2／ｇ以上であり、条件
のものについては、1.0〜4.0m2／ｇの範囲にあ
る。 The specific surface areas of the two types of UO 2 powders obtained are 4.0 m 2 /g or more under the conditions, and are in the range of 1.0 to 4.0 m 2 /g under the conditions.
条件で得られたUO2粉末は単独でペレツト成
形加工した場合、キヤツピングが発生したり、ま
た焼結後の密度が上りすぎる等の問題がある。 When the UO 2 powder obtained under these conditions is processed into pellets alone, there are problems such as capping occurring and the density after sintering becoming too high.
条件で得られたUO2粉末は、UF6から転換して
得られるUO2粉末と同様に単独でペレツト成形加
工ができる。The UO 2 powder obtained under these conditions can be processed into pellets by itself in the same way as the UO 2 powder obtained by conversion from UF 6 .
（発明の効果）
本発明は上記の構成をとることによつて次の効
果を示す。(Effects of the Invention) The present invention exhibits the following effects by adopting the above configuration.
(1) 本発明で得られたUO2粉末は活性度が抑制さ
れ、かつ焼結密度が上がりすぎることがないの
で単独でペレツト成形加工が可能である。(1) The UO 2 powder obtained in the present invention has suppressed activity and does not increase sintered density too much, so it can be processed into pellets by itself.
(2) (1)によつて残材ウランの有効利用が可能とな
る。(2) (1) makes it possible to effectively utilize residual uranium.
第１図は硝酸ウラニル溶液にアンモニア水を添
加した場合のアンモニア水添加総量と硝酸ウラニ
ル溶液のPHとの関係を示すPH曲線図、第２図は本
発明の基本実験装置の一例を示す断面図である。
Fig. 1 is a PH curve diagram showing the relationship between the total amount of ammonia water added and the PH of the uranyl nitrate solution when ammonia water is added to the uranyl nitrate solution, and Fig. 2 is a sectional view showing an example of the basic experimental apparatus of the present invention. It is.
Claims (1)
リー硝酸濃度とを有する硝酸ウラニル溶液に20〜
35％濃度のアンモニア水を添加して重ウラン酸ア
ンモン（ADU）の沈殿を生成させ、その際該硝
酸ウラニル溶液のPHが3.5〜4.5の範囲では該アン
モニア水の添加速度をおそくして１ｇのウランあ
たり0.01ｇNH3／mm〜0.025ｇNH3／mmの範囲に
保ち、かつ該硝酸ウラニル溶液のPHが4.5を越え
た時は該アンモニア水の添加速度を１ｇのウラン
あたり0.1ｇNH3／mm〜0.5ｇNH3／mmの範囲にに
保つとともに生成したADU沈殿物を分離・乾燥
した後、空気中において660〜760℃の範囲で焙焼
し、次いで、還元雰囲気中において660〜760℃の
範囲で還元してUO2粉末に転換することを特徴と
する硝酸ウラニル系からのUO2粉末製造方法。1 Add 20 to 20 g of uranyl nitrate solution with a uranium concentration of 50 to 100 g/1 and a free nitric acid concentration of 0 to 2.5 N.
Aqueous ammonia with a concentration of 35% is added to form a precipitate of ammonium deuterate (ADU), and when the pH of the uranyl nitrate solution is in the range of 3.5 to 4.5, the rate of addition of the ammonia water is slowed down and 1 g of ammonia is added. Maintain the amount of uranium in the range of 0.01 g NH 3 /mm to 0.025 g NH 3 /mm, and when the PH of the uranyl nitrate solution exceeds 4.5, the ammonia water addition rate is set to 0.1 g NH 3 /mm to 0.5 per 1 g of uranium. After separating and drying the ADU precipitate produced while maintaining the temperature within the range of gNH 3 /mm, it is roasted in the range of 660 to 760°C in air, and then reduced in the range of 660 to 760°C in a reducing atmosphere. 1. A method for producing UO 2 powder from uranyl nitrate, characterized by converting it into UO 2 powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117793A JPS63282127A (en) | 1987-05-14 | 1987-05-14 | Production of uo2 powder from uranyl nitrate series |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62117793A JPS63282127A (en) | 1987-05-14 | 1987-05-14 | Production of uo2 powder from uranyl nitrate series |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63282127A JPS63282127A (en) | 1988-11-18 |
| JPH0458417B2 true JPH0458417B2 (en) | 1992-09-17 |
Family
ID=14720431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62117793A Granted JPS63282127A (en) | 1987-05-14 | 1987-05-14 | Production of uo2 powder from uranyl nitrate series |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63282127A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514306A (en) * | 1993-02-01 | 1996-05-07 | General Electric Company | Process to reclaim UO2 scrap powder |
-
1987
- 1987-05-14 JP JP62117793A patent/JPS63282127A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63282127A (en) | 1988-11-18 |
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