JPS6136200B2 - - Google Patents
Info
- Publication number
- JPS6136200B2 JPS6136200B2 JP8506478A JP8506478A JPS6136200B2 JP S6136200 B2 JPS6136200 B2 JP S6136200B2 JP 8506478 A JP8506478 A JP 8506478A JP 8506478 A JP8506478 A JP 8506478A JP S6136200 B2 JPS6136200 B2 JP S6136200B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- radioactive waste
- compound
- moo
- zro
- 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
Links
- 239000002901 radioactive waste Substances 0.000 claims description 60
- 150000003755 zirconium compounds Chemical class 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 150000002816 nickel compounds Chemical class 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 150000001553 barium compounds Chemical class 0.000 claims 6
- 229940043430 calcium compound Drugs 0.000 claims 6
- 150000001674 calcium compounds Chemical class 0.000 claims 6
- 150000003438 strontium compounds Chemical class 0.000 claims 6
- 238000001816 cooling Methods 0.000 claims 4
- 229910002674 PdO Inorganic materials 0.000 claims 1
- 229910019603 Rh2O3 Inorganic materials 0.000 claims 1
- 229910018162 SeO2 Inorganic materials 0.000 claims 1
- 229910003069 TeO2 Inorganic materials 0.000 claims 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- 239000002699 waste material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 239000000941 radioactive substance Substances 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910026551 ZrC Inorganic materials 0.000 description 4
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002915 spent fuel radioactive waste Substances 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052778 Plutonium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 208000031872 Body Remains Diseases 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003514 Sr(OH) Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 and as a result Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、放射性廃棄物の固化体およびその製
造方法に関し、詳しくはか焼した放射性廃棄物
（「か焼体」という）を含有するセラミツク固化体
およびか焼体粉末にジルコニウム化合物を混合
後、溶融又は焼結処理により前記セラミツク固化
体を製造する方法に関する。
本発明の固化体は放射性廃棄物を効率的に貯蔵
することができ、化学的、機械的に安定で、放射
性廃棄物を半永久的に貯蔵することに適する。
又、この固化体はそのまま貯蔵容器に保存しても
よいが、例えば、適当なしやへい物を設け、放射
線量を制御することで食品に放射線を照射し、輸
送及び貯蔵中の腐敗、虫害及び発芽等の防止、保
存期間の延長等に役立つ。
電力供給に対する原子力発電の寄与が増大する
につれ、特に使用済核燃料の再処理工場から発生
する高濃度の放射性廃液は年々増大する傾向にあ
る。これらの貯蔵において、廃液のままでのタン
ク貯蔵は安全上、管理上のみならず数量および容
積的な点で貯蔵スペースが問題となるため、保管
しやすい固化体およびその製造方法の確立が切望
されている。
一般に、放射性廃棄物の固化体およびその製造
技術に於いては、放射性物質の周囲への漏洩が、
最小限となる形態に廃棄物を変換し、かつ、変換
した形態が化学的、機械的に安定していて長期の
貯蔵によつても、環境汚染の原因にならないこと
が必要である。また、放射性廃棄物の量は将来に
わたつて増大することが予想されることから、貯
蔵を効率的に行うために廃棄物と添加物の重量の
総和に対する廃棄物の重量の比（以下「含有率」
という）は可能な限り大きいことが望まれる。本
発明の放射性廃棄物の固化体およびその製造方法
はこのような要求に応えて開発された。
従来放射性廃棄物の貯蔵のためには、か焼体と
して貯蔵することが提唱されてきた。処理温度
400〜650℃でか焼体を製造し、硝酸塩成分を完全
に除去して、酸化物から成るか焼体は硝酸塩成分
の分解がないので静的にはそれなりに長期的に安
定性が保てるが、次のような欠点があつた。すな
わち、か焼体単独では、焼結性は不良であり、一
部の核種の飛散も生じ易いこと、水に溶け易いた
めに耐浸出性が極めて劣ること、熱伝導性が低い
ために放射性元素の崩壊により生ずる熱の放射性
が悪く、その結果貯蔵時に温度上昇を来し易いこ
と、更にこの温度上昇のために保存容器の破損が
生じやすく、強度的にはくずれ易いこと、等々で
ある。これらの欠点のために、長期の貯蔵上安定
性を欠き、特に地震・洪水等の天災など不慮の災
害を予想すると著しく安全性を欠くという難点が
あつた。
放射性物質の水への耐浸出性、熱的安定性及び
機械的強度を比較的大きいものに改善するため、
放射性廃棄物に何らかの添加物を配合し熱処理を
施した固化体が考えられる。この場合、添加剤の
分量が多くなれば、それだけ放射性廃棄物の含有
率が減少するので安全性は高まるが、それだけ貯
蔵の点では効率が低下することになる。従つて、
より効率的に放射性廃棄物を高密度充填すること
ができる添加剤の選択、およびかかる添加剤を用
いた固化体の開発が切望されていた。
従来、かかる固化体の例として、ガラス固化体
が知られている。ガラス固化体は、高濃度の放射
性廃棄物をリン酸もしくはホウケイ酸ガラス等と
ともに溶融後、一定形状のインゴツトに凝固させ
た固化体である。
この方法によれば、ガラスの組成を検討するこ
とにより、放射性物質の水への浸出性が小さく、
機械的強度も比較的大きいガラス固化体を得るこ
とができるが、安定した構造のガラス固化体を得
るためには、か焼体粉末の添加量は、25〜30重量
％が上限であるとされていた。そのため、熱伝導
率が大きいために放熱性がよく、しかして放射性
物質の崩壊熱に対して耐久力があり、しかも、よ
り高密度で放射性廃棄物を充填・固化し得る固化
体、およびその製造方法の開発が望まれていた。
また、固化体中に、モリブデン単体又は、
Na2O・MoO3、K2O・MoO3、Cs2O・MoO3等の
相が構成相として存在すると、これらの相は水に
対する耐浸出性が極めて小さいために、放射性物
質の溶出、更にこれを起点とする固化体の劣化を
もたらすので、特にこれらの相が存在しない固化
体およびその製造方法の確立が望まれていた。
本発明の目的は、放射性廃棄物に金属塩を用
い、セラミツク固化体とすることにより、含有率
が大きくて放射性廃棄物を効率的に貯蔵すること
ができる固化体で、モリブデン相又はNa2O・
MoO3、K2O・MoO3もしくはCs2O・MoO3等の相
を含まないために放射性物質の水への浸出性が小
さく、放熱性・耐熱性に優れ、さらに機械的強度
において優れた固化体を提供することにある。か
かる固化体は放射性廃棄物の安全かつ半永久的な
貯蔵に適するものである。
本発明の固化体は、酸化物に換算してNa2O5〜
40重量％、Fe2O35〜20重量％、MoO35〜15重量
％、ZrO25〜15重量％、CeO22〜10重量％、
Cs2O2〜10重量％、BaO1〜５重量％、SrO1〜５
重量％、Rb2O0.2〜２重量％、Y2O30.2〜２重量
％、NiO0.2〜２重量％、希土類酸化物５〜20重
量％、Cr2O30.2〜２重量％、及びその他の元素酸
化物の組成を含有する放射性廃棄物のか焼体に、
ジルコニウム化合物を30重量％以上（ZrO2とし
て）配合し、溶融又は焼結の熱処理を施し固化さ
せて成り、モリブデン単体、Na2O・MoO3、
K2O・MoO3およびCs2O・MoO3を構成相として
含まないセラミツク固化体であることを特徴とす
る。（か焼体中に含まれるその他の酸化物として
は、Tc2O7、RuO2、Rh2O3、PdO、Ag2O、
CdO、SnO、SeO2、TeO2およびアクチニド元素
酸化物等があげられる。）
本発明における放射性廃棄物のか焼体は、例え
ば使用済核燃料を処理した後、Ｕ、Puを回収し
た残りの放射性廃棄物の他、混床式脱塩器の再生
廃液の濃縮液、建屋から発生する床ドレン・機器
ドレンの濃縮廃液等の放射性物質を含む各種の廃
液又は、原子炉浄化系・燃料プール系・復水系・
ドレン系の各系統から生ずる使用済イオン交換樹
脂やフイルタースラツジ、廃液の凝集沈澱処理に
よつて生じる沈澱スラツジ等の各種の固化廃棄物
をか焼することによつて得られる高濃度または中
低濃度の放射性物質であり、本発明は広い範囲の
放射性廃棄物の処理に利用することができる。
又、本発明で使用するジルコニウム化合物は、
ZrO2又は溶融もしくは焼結処理によりZrO2に変
化する化合物であればよい。溶融、焼結により
ZrO2に変化するジルコニウム化合物としては、
例えば窒化ジルコニウム（ZrN）炭化ジルコニウ
ム（ZrC）等があげられる。
ジルコニウム化合物をか焼体中に30重量％以上
（ZrO2に換算して）配合し、溶融又は焼結により
製造したセラミツク固化体は、1000℃以上の高温
においても、極めて安定で、か焼体単独で焼結さ
せたものに較べ、耐浸出性、熱伝導性、および機
械的強度の点で極めて優れている。しかも、これ
らの優れた特性を損うことなく、含有率を最高70
重量％まで高めることができる。
本発明の固化体に関する第２の発明は、放射性
廃棄物のか焼体にジルコニウム化合物を30重量％
以上（ZrO2として）、ニツケル化合物１〜10重量
％（NiOとして）を配合し、固化させたことを特
徴とする。すなわち、ニツケル化合物を１〜10重
量％（NiOとして）配合させると、固化体の機械
的強度を更に向上させることができる。配合比を
１〜10重量％に制限したのは10重量％を越えた場
合、固化体の耐浸出性の劣化をもたらし、１重量
％未満を配合させてもその効果があらわれないか
らである。ニツケル化合物としては、NiO又は溶
融もしくは焼結処理によりNiOとなる化合物、ニ
ツケルアセテート（C10H14NiO4・4H2O）、ニツ
ケルアセチルアセトネート（C10H14NiO4）、炭酸
ニツケル（NiCO3・2Ni（OH）2・4H2O）等を使
用することができる。本発明の固化体に関する第
３の発明は、放射性廃棄物のか焼体にジルコニウ
ム化合物を30重量％以上（ZrO2として）と、カ
ルシウム、ストロンチウムおよびバリウムのうち
少なくとも一種の金属化合物を１〜10重量％
（CaO、SrO、BaOとして）を配合し、固体させ
たことを特徴とする。すなわち、カルシウム、ス
トロンチウム、およびバリウムのうち少なくとも
一種の金属化合物を１〜10重量％（CaO、SrO、
BaOとして）配合させると、固化体の耐浸出性を
更に高めることができる。配合比を１〜10重量％
に制限したのは10重量％を越えた場合、固化体の
耐浸出性の劣化をもたらし、１重量％未満を配合
させてもその効果があらわれないからであらる。
これらのカルシウム等の化合物としても最終的に
酸化物となるものであれば使用できる。例えば、
炭酸ストロンチウム（SrCO3）ストロンチウム・
ハイドロオキサイド（Sr（OH）2・8H2O）炭酸バ
リウム（BaCO3）バリウムアセテート
（C4H6O4Ba）バリウムハイドロオキサイド（Ba
（OH）2・8H2O）炭酸カルシウム（CaCO3）又は水
酸化カルシウム（Ca（OH）2）等があげられる。
本発明の固化体に関する第４の発明は、放射性廃
棄物のか焼体にジルコニウム化合物を30重量％以
上（ZrO2として）と、ニツケル化合物１〜10重
量％（NiOとして）と、カルシウム、ストロンチ
ウムおよびバリウムのうち少なくとも一種の金属
化合物を１〜10重量％（CaO、SrO、BaOとし
て）配合し、固化させたことを特徴とする。そし
て、その作用効果、各化合物の具体例および配合
割合の限定理由は上記した通りである。
本発明の固化体は、次のようにして容易に製造
することができる。
放射性廃棄物のか焼体に、前述のジルコニウム
化合物を所定量配合し、必要に応じてニツケル化
合物および／またはCa、Sr、Baのうち少なくと
も一種の金属化合物を所定量配合し、十分に混合
する。放射性廃棄物と金属化合物の混合方法は通
常の粉体混合の他、配合すべき金属化合物の粉末
の表面に被膜を形成する方法。例えば、この粉末
に水を加えて混練してスラリー状にした後、篩を
通して造粒したものを流動床として例えば600℃
程度の温度で放射性廃棄物を粒子の表面に吹きつ
けてもよい。この配合物を容器に装入し、約1800
〜2500℃で溶融し、次に一定形状のインゴツトに
凝固させることにより、セラミツク固化体とする
ことができる。または、配合物を、圧縮成形後
800〜1500℃で焼結することによつてセラミツク
固化体とすることもできる。圧縮成形を容易にす
るために、水、パラフイン、ポリビニル アルコ
ール等の粘結剤を配合物に添加しておくことがで
きる。配合する金属化合物が、窒化ジルコニウム
（ZrN）炭化ジルコニウム（ZrC）等である場合に
は、焼結又は溶融処理により、セラミツク固化体
中で最終的に酸化物（例えばZrO2、NiO、CaO
等）に変化するように、空気中等の酸化性雰囲気
で焼結又は溶融を行う必要がある。
本発明の固化体は正常、加圧を問わず既存の焼
結方法により、また外部加熱または内部加熱を問
わず既存の溶融方法により製造することができ
る。
本発明の放射性廃棄物の固化体、および固化体
の製造方法により、次のような効果を得ることが
できる。
(1) 放射性廃棄物のか焼体は、例えば第１〜３表
に模擬的に組成を示したように、一般に金属酸
化物から成り、それ自体では焼結固化は比較的
不良であるが、本発明によれば、ZrO2のため
に、緻密で強固なセラミツク固化体を得ること
ができる。特に、ニツケル化合物を配合した場
合には、一層機械的強度に優れた固化体を得る
ことができる。
(2) 本発明の固化体中においては、か焼体は、
ZrO2、NiO、CaO等とともに熱的に安定な相を
有している。その結果、長期にわたり放射性廃
棄物を安全に貯蔵することができる。
(3) 本発明の固化体は、耐浸出性においても優れ
ており、特にCa、Sr、Ba等の金属化合物を配
合、固化させた場合には、一層耐浸出性の優れ
たものとなる。
(4) 本発明の固化体には、放射性廃棄物のか焼体
を最高70重量％まで充填することができる。す
なわち、従来のガラス固化体に比し、含有率が
大幅に向上し、その結果、放射性廃棄物を、貯
蔵容器（キヤニスタ）中に高密度充填すること
ができ、キヤニスタの数量を低減することがで
きる。
(5) 固化体をそのまま貯蔵容器に保存してもよい
が、例えば適当なしやへい物を設け、放射線量
を制禦することで食品に放射線を照射し、輸送
及び貯蔵中の腐敗、虫害及び発芽等の防止、保
存期間の延長等の用途に適する。
次に、本発明の実施例および比較例について説
明する。
なお、実施例および比較例で使用する放射性廃
棄物のか焼体として、使用済核燃料を処理した
後、Ｕ、Puを回収した残りの放射性廃棄物のか
焼体の組成を模擬して第１〜３表の組成を有する
３種の粉末を調整した（以下「模擬か焼体」とい
う）。
The present invention relates to a solidified body of radioactive waste and a method for producing the same, and more specifically, the present invention relates to a solidified body of radioactive waste and a method for producing the same, and more specifically, after mixing a zirconium compound into a solidified ceramic body containing calcined radioactive waste (referred to as "calcined body") and powder of the calcined body, The present invention relates to a method for producing the solidified ceramic body by melting or sintering. The solidified material of the present invention can efficiently store radioactive waste, is chemically and mechanically stable, and is suitable for semi-permanently storing radioactive waste.
Although this solidified product may be stored in a storage container as it is, for example, the food may be irradiated with radiation by providing an appropriate container or a container to control the radiation dose to prevent spoilage, insect damage, and damage during transportation and storage. It is useful for preventing germination, etc., and extending storage period. As the contribution of nuclear power generation to the electricity supply increases, the amount of highly concentrated radioactive waste fluid generated, especially from spent nuclear fuel reprocessing plants, tends to increase year by year. When storing these waste liquids in tanks, storage space becomes a problem not only in terms of safety and management, but also in terms of quantity and volume, so there is a strong desire to establish a solidified substance that is easy to store and a method for producing it. ing. In general, in solidified radioactive waste and its manufacturing technology, leakage of radioactive materials to the surroundings is
It is necessary to convert waste into a minimum form, and to ensure that the converted form is chemically and mechanically stable and does not cause environmental pollution even after long-term storage. In addition, since the amount of radioactive waste is expected to increase in the future, in order to store it efficiently, the ratio of the weight of waste to the total weight of waste and additives (hereinafter referred to as "contained rate"
) is desired to be as large as possible. The radioactive waste solidified body and its manufacturing method of the present invention were developed in response to such demands. Conventionally, it has been proposed to store radioactive waste as a calcined body. Processing temperature
The calcined body is manufactured at 400 to 650℃, and the nitrate component is completely removed.The calcined body made of oxides does not decompose the nitrate component, so it can maintain static stability for a long time. , it had the following drawbacks: In other words, the calcined body alone has poor sintering properties and is prone to scattering of some nuclides, has extremely poor leaching resistance because it is easily soluble in water, and has low thermal conductivity, so it is difficult to sinter radioactive elements. The heat generated by the decay of the container has poor radioactivity, and as a result, the temperature tends to rise during storage.Furthermore, this temperature rise tends to cause damage to the storage container, making it easy to collapse in terms of strength. Because of these shortcomings, it lacks stability in long-term storage, and is particularly unsafe in the face of unexpected natural disasters such as earthquakes and floods. In order to improve the resistance to leaching of radioactive substances into water, thermal stability and mechanical strength to a relatively large degree,
A possible solidified material is radioactive waste mixed with some additives and subjected to heat treatment. In this case, the greater the amount of additive, the lower the content of radioactive waste and the higher the safety, but the lower the efficiency in terms of storage. Therefore,
There has been a strong desire to select additives that can more efficiently pack radioactive waste at high density, and to develop solidified materials using such additives. Conventionally, a vitrified body is known as an example of such a solidified body. The vitrified material is a solidified material obtained by melting highly concentrated radioactive waste together with phosphoric acid or borosilicate glass, and then solidifying it into an ingot of a certain shape. According to this method, by considering the composition of the glass, the leachability of radioactive substances into water is small.
Although it is possible to obtain a vitrified body with relatively high mechanical strength, in order to obtain a vitrified body with a stable structure, the upper limit of the amount of calcined body powder added is 25 to 30% by weight. was. Therefore, we need a solidified material that has good heat dissipation due to its high thermal conductivity, is resistant to the decay heat of radioactive materials, and can be filled and solidified with radioactive waste at a higher density, and its production. Development of a method was desired. In addition, in the solidified body, molybdenum alone or
When phases such as Na 2 O・MoO 3 , K 2 O・MoO 3 , and Cs 2 O・MoO 3 are present as constituent phases, these phases have extremely low leaching resistance to water, resulting in the elution of radioactive substances, Furthermore, since these phases cause deterioration of the solidified product, it has been particularly desired to establish a solidified product in which these phases are not present and a method for producing the same. The object of the present invention is to use metal salts for radioactive waste to form a solidified ceramic material, which has a high content and can efficiently store radioactive waste, and which has a molybdenum phase or Na 2 O.・
Because it does not contain phases such as MoO 3 , K 2 O・MoO 3 or Cs 2 O・MoO 3 , it has low leachability of radioactive substances into water, excellent heat dissipation and heat resistance, and excellent mechanical strength. The objective is to provide a solidified product. Such solidified bodies are suitable for safe and semi-permanent storage of radioactive waste. The solidified material of the present invention has Na 2 O 5 ~
40% by weight, Fe2O3 5-20% by weight, MoO3 5-15% by weight, ZrO2 5-15% by weight, CeO2 2-10% by weight,
Cs 2 O2 ~ 10% by weight, BaO 1 ~ 5% by weight, SrO 1 ~ 5
% by weight, Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight, NiO 0.2-2% by weight, rare earth oxides 5-20% by weight, Cr 2 O 3 0.2-2% by weight, and other elemental oxides in the calcined body of radioactive waste,
It is made by blending 30 % by weight or more of a zirconium compound (as ZrO 2 ) and solidifying it by heat treatment of melting or sintering .
It is characterized by being a ceramic solidified body that does not contain K 2 O · MoO 3 and Cs 2 O · MoO 3 as constituent phases. (Other oxides contained in the calcined body include Tc 2 O 7 , RuO 2 , Rh 2 O 3 , PdO, Ag 2 O,
Examples include CdO, SnO, SeO 2 , TeO 2 and actinide element oxides. ) The calcined bodies of radioactive waste in the present invention include, for example, radioactive waste remaining after processing spent nuclear fuel and recovering U and Pu, as well as concentrated liquid of recycled waste liquid from a mixed-bed desalination machine, and waste from a building. Various waste liquids containing radioactive substances, such as concentrated waste liquid from floor drains and equipment drains, or reactor purification systems, fuel pool systems, condensate systems, etc.
High concentration or medium-low concentration obtained by calcining various solidified wastes such as used ion exchange resin and filter sludge generated from each drain system, and precipitated sludge generated by coagulation and sedimentation treatment of waste liquid. This invention can be used to treat a wide range of radioactive wastes. Moreover, the zirconium compound used in the present invention is
Any compound may be used as long as it is ZrO 2 or a compound that changes to ZrO 2 by melting or sintering treatment. By melting and sintering
Zirconium compounds that change to ZrO 2 include:
Examples include zirconium nitride (ZrN) and zirconium carbide (ZrC). Solidified ceramic bodies manufactured by melting or sintering a calcined body containing 30% by weight or more of a zirconium compound (calculated as ZrO 2 ) are extremely stable even at high temperatures of 1000°C or higher, and the calcined body remains stable. Compared to those sintered alone, it has extremely superior leaching resistance, thermal conductivity, and mechanical strength. Moreover, the content can be increased to up to 70% without compromising these excellent properties.
% by weight. The second invention regarding the solidified body of the present invention is to add 30% by weight of a zirconium compound to the calcined body of radioactive waste.
The above material is characterized in that 1 to 10% by weight of a nickel compound (as NiO) is blended and solidified (as ZrO 2 ). That is, when 1 to 10% by weight (as NiO) of a nickel compound is blended, the mechanical strength of the solidified body can be further improved. The reason why the blending ratio is limited to 1 to 10% by weight is because if it exceeds 10% by weight, the leaching resistance of the solidified product deteriorates, and if it is blended at less than 1% by weight, no effect will be obtained. Nickel compounds include NiO or a compound that becomes NiO by melting or sintering, nickel acetate (C 10 H 14 NiO 4 4H 2 O), nickel acetylacetonate (C 10 H 14 NiO 4 ), nickel carbonate (NiCO 3・2Ni(OH) 2・4H 2 O) etc. can be used. The third invention regarding the solidified body of the present invention is that 30% by weight or more of a zirconium compound (as ZrO 2 ) and 1 to 10% by weight of at least one metal compound among calcium, strontium, and barium are added to the calcined body of radioactive waste. %
(as CaO, SrO, BaO) and solidified. That is, 1 to 10% by weight of at least one metal compound among calcium, strontium, and barium (CaO, SrO,
When combined (as BaO), the leaching resistance of the solidified product can be further improved. Mixing ratio 1-10% by weight
The reason for limiting the amount to 10% by weight is that if it exceeds 10% by weight, the leaching resistance of the solidified product deteriorates, and if it is incorporated in less than 1% by weight, no effect will be obtained.
Compounds such as calcium can be used as long as they eventually become oxides. for example,
Strontium carbonate (SrCO 3 ) Strontium
Hydroxide (Sr(OH) 2・8H 2 O) Barium carbonate (BaCO 3 ) Barium acetate (C 4 H 6 O 4 Ba) Barium hydroxide (Ba
(OH) 2.8H 2 O) calcium carbonate (CaCO 3 ) or calcium hydroxide (Ca(OH) 2 ).
The fourth invention related to the solidified body of the present invention is that 30% by weight or more of a zirconium compound (as ZrO 2 ), 1 to 10% by weight of a nickel compound (as NiO), calcium, strontium and It is characterized by containing 1 to 10% by weight (as CaO, SrO, BaO) of at least one metal compound among barium and solidifying it. The effects, specific examples of each compound, and reasons for limiting the blending ratio are as described above. The solidified product of the present invention can be easily produced as follows. A predetermined amount of the above-mentioned zirconium compound is blended into the calcined body of radioactive waste, and if necessary, a predetermined amount of a nickel compound and/or a metal compound of at least one of Ca, Sr, and Ba is blended and thoroughly mixed. The method of mixing radioactive waste and metal compounds is not only the usual powder mixing, but also the method of forming a film on the surface of the metal compound powder to be mixed. For example, water is added to this powder and the mixture is kneaded to form a slurry, which is then granulated through a sieve and placed in a fluidized bed at, for example, 600°C.
Radioactive waste may be sprayed onto the surface of the particles at a temperature of This mixture is charged into a container, and approximately 1800
A solidified ceramic can be obtained by melting at ~2500°C and then solidifying into an ingot of a certain shape. Alternatively, the formulation can be compressed after molding.
It can also be made into a solidified ceramic body by sintering at 800-1500°C. Binders such as water, paraffin, polyvinyl alcohol, etc. can be added to the formulation to facilitate compression molding. When the metal compound to be mixed is zirconium nitride (ZrN), zirconium carbide (ZrC), etc., oxides (e.g. ZrO 2 , NiO, CaO
etc.), it is necessary to perform sintering or melting in an oxidizing atmosphere such as air. The solidified body of the present invention can be produced by any existing sintering method, whether normal or pressurized, or by any existing melting method, whether external heating or internal heating. By the solidified body of radioactive waste and the method for producing the solidified body of the present invention, the following effects can be obtained. (1) Calcined bodies of radioactive waste are generally made of metal oxides, for example, as shown in the simulated compositions in Tables 1 to 3, and are relatively poorly sintered and solidified by themselves. According to the invention, a dense and strong ceramic solidified body can be obtained because of ZrO 2 . In particular, when a nickel compound is blended, a solidified product with even better mechanical strength can be obtained. (2) In the solidified body of the present invention, the calcined body is
It has a thermally stable phase together with ZrO 2 , NiO, CaO, etc. As a result, radioactive waste can be safely stored for a long period of time. (3) The solidified product of the present invention is also excellent in leaching resistance, and in particular, when a metal compound such as Ca, Sr, Ba, etc. is blended and solidified, the leaching resistance becomes even more excellent. (4) The solidified body of the present invention can be filled with up to 70% by weight of calcined radioactive waste. In other words, the content rate is significantly improved compared to conventional vitrified materials, and as a result, radioactive waste can be packed in high density into storage containers (canisters), and the number of canisters can be reduced. can. (5) The solidified product may be stored as is in a storage container, but by controlling the radiation dose by, for example, providing an appropriate container or shield, food can be irradiated with radiation to prevent spoilage, insect damage, and damage during transportation and storage. Suitable for purposes such as preventing germination, extending storage period, etc. Next, examples and comparative examples of the present invention will be described. Incidentally, as the radioactive waste calcined bodies used in Examples and Comparative Examples, Nos. 1 to 3 were used to simulate the composition of the remaining radioactive waste calcined bodies from which U and Pu were recovered after processing spent nuclear fuel. Three types of powders having the compositions shown in the table were prepared (hereinafter referred to as "simulated calcined bodies").
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
実施例および比較例で得られた固化体につい
て、機械的強度、浸出率、熱伝導率を測定し、更
にＸ線回折により固化体中にモリブデン単体、
Na2O・MoO3、Cs2O・MoO3、K2O・MoO3の相
が生成しているか否かを調べた。なお、機械的強
度の測定は固化体により測定用試験片（３×３×
30mmの角柱）を作製し、三点曲げ法によつて機械
的強度（ただし、スパン長さ20mm印加速度0.5
cm／分）を測定した。
浸出率の測定法は（JIS−R3502）の方法に従
つて測定した。また、熱伝導率は室温でレーザフ
ラツシユ法に従つて測定した。
実施例１〜11比較例１〜10
各実施例および各比較例に係る模擬か焼体と金
属化合物の配合物を、第４表に示す配合比で調整
した。金属化合物の粉末は、平均粒径２μｍ以下
のものを用いた。調整した配合物20ｇを圧縮成形
し、30mmφのペレツトとし、次に焼結させ固化体
とした。圧縮成形、焼結の条件および、得られた
固化体についての測定結果を、第４表に併せ示し
た。[Table] The mechanical strength, leaching rate, and thermal conductivity of the solidified bodies obtained in Examples and Comparative Examples were measured, and X-ray diffraction analysis revealed that molybdenum alone,
It was investigated whether phases of Na 2 O.MoO 3 , Cs 2 O.MoO 3 , and K 2 O.MoO 3 were generated. In addition, the mechanical strength was measured using a test piece (3 x 3 x
A 30mm rectangular column) was manufactured using the three-point bending method to achieve mechanical strength (span length 20mm, applied acceleration 0.5).
cm/min) was measured. The leaching rate was measured according to the method of (JIS-R3502). Further, the thermal conductivity was measured at room temperature according to the laser flash method. Examples 1 to 11 Comparative Examples 1 to 10 Blends of the simulated calcined bodies and metal compounds according to each of the Examples and Comparative Examples were adjusted at the blending ratios shown in Table 4. The metal compound powder used had an average particle size of 2 μm or less. 20 g of the prepared mixture was compression molded to form pellets of 30 mm in diameter, and then sintered to form a solidified body. Table 4 also shows the compression molding and sintering conditions and the measurement results for the obtained solidified product.
【表】【table】
【表】
実施例12〜22比較例11〜20
各実施例および各比較例に係る模擬か焼体と金
属化合物の配合物を、第５表に示す配合比で調整
した。金属化合物の粉末は、平均粒径２μｍ以下
のものを用いた。調整した配合物100ｇをカーボ
ン容器の中に充填し、この配合物の中へカーボン
電極を挿入した。アーク放電により2300℃で配合
物を溶融させた後、冷却して固化体とした。溶融
条件、得られた固化体についての測定結果を、第
５表に併せ示した。[Table] Examples 12 to 22 Comparative Examples 11 to 20 Blends of the simulated calcined bodies and metal compounds according to each of the Examples and Comparative Examples were adjusted at the blending ratios shown in Table 5. The metal compound powder used had an average particle size of 2 μm or less. 100 g of the prepared blend was filled into a carbon container, and a carbon electrode was inserted into the blend. The compound was melted at 2300°C by arc discharge, and then cooled to form a solidified product. The melting conditions and measurement results for the obtained solidified product are also shown in Table 5.
【表】【table】
Claims (1)
Fe2O35〜20重量％、MoO35〜15重量％、ZrO25〜
15重量％、CeO22〜10重量％、Cs2O2〜10重量
％、BaO1〜５重量％、SrO1〜５重量％、
Rb2O0.2〜２重量％、Y2O30.2〜２重量％、
NiO0.2〜２重量％、希土類酸化物５〜20重量
％、Cr2O30.2〜２重量％を含有する放射性廃棄物
のか焼体に、ジルコニウム化合物を30重量％以上
（ZrO2として）配合し、熱処理を施し固化して成
り、モリブデン単体、Na2O・MoO3、K2O・
MoO3およびCs2O・MoO3を構成相として含まな
いことを特徴とする放射性廃棄物のセラミツク固
化体。 ２ 酸化物に換算してNa2O5〜40重量％、
Fe2O35〜20重量％、MoO35〜15重量％、ZrO25〜
15重量％、CeO22〜10重量％、Cs2O2〜10重量
％、BaO1〜５重量％、SrO1〜５重量％、
Rb2O0.2〜２重量％、Y2O30.2〜２重量％、
NiO0.2〜２重量％、希土類酸化物５〜20重量
％、Cr2O30.2〜２重量％を含有する放射性廃棄物
のか焼体に、ジルコニウム化合物を30重量％以上
（ZrO2として）と、ニツケル化合物１〜10重量％
（NiOとして）を配合し、熱処理を施し固化して
成り、モリブデン単量体、Na2O・MoO3、K2O・
MoO3およびCs2O・MoO3を構成相として含まな
いことを特徴とする放射性廃棄物のセラミツク固
化体。 ３ 酸化物に換算してNa2O5〜40重量％、
Fe2O35〜20重量％、MoO35〜15重量％、ZrO25〜
15重量％、CeO22〜10重量％、Cs2O2〜10重量
％、BaO1〜５重量％、SrO1〜５重量％、
Rb2O0.2〜２重量％、Y2O30.2〜２重量％、
NiO0.2〜２重量％、希土類酸化物５〜20重量
％、Cr2O30.2〜２重量％を含有する放射性廃棄物
のか焼体に、ジルコニウム化合物を30重量％以上
（ZrO2として）と、カルシウム化合物、ストロン
チウム化合物およびバリウム化合物の少なくとも
１種を１〜10重量％（CaO、SrO、BaOとして）
を配合し、熱処理を施し固化して成り、モリブデ
ン単体、Na2O・MoO3、K2O・MoO3および
Cs2O・MoO3を構成相として含まないことを特徴
とする放射性廃棄物のセラミツク固化体。 ４ 酸化物に換算してNa2O5〜40重量％、
Fe2O35〜20重量％、MoO35〜15重量％、ZrO25〜
15重量％、CeO22〜10重量％、Cs2O2〜10重量
％、BaO1〜５重量％、SrO1〜５重量％、
Rb2O0.2〜２重量％、Y2O30.2〜２重量％、
NiO0.2〜２重量％、希土類酸化物５〜20重量
％、Cr2O30.2〜２重量％を含有する放射性廃棄物
のか焼体に、ジルコニウム化合物を30重量％以上
（ZrO2として）と、ニツケル化合物１〜10重量％
（NiOとして）と、カルシウム化合物、ストロン
チウム化合物およびバリウム化合物の少なくとも
１種を１〜10重量％（CaO、SrO、BaOとして）
を配合し、熱処理を施し固化して成り、モリブデ
ン単体、Na2O・MoO3、K2O・MoO3および
Os2O・MoO3を構成相として含まないことを特徴
とする放射性廃棄物のセラミツク固化体。 ５ 放射性廃棄物のか焼体に、ジルコニウム化合
物を30重量％以上（ZrO2として）配合し、圧縮
成型後焼結することを特徴とする、放射性廃棄物
のセラミツク固化体の製造法。 ６ 放射性廃棄物のか焼体に、ジルコニウム化合
物を30重量％以上（ZrO2として）と、ニツケル
化合物１〜10重量％（NiOとして）を配合し、圧
縮成型後焼結する、特許請求の範囲第５項記載の
放射性廃棄物のセラミツク固化体の製造法。 ７ 放射性廃棄物のか焼体に、ジルコニウム化合
物を30重量％以上（ZrO2として）と、カルシウ
ム化合物、ストロンチウム化合物およびバリウム
化合物の少なくとも１種を１〜10重量％（CaO、
SrO、BaOとして）を配合し、圧縮成型後焼結す
る、特許請求の範囲第５項記載の放射性廃棄物の
セラミツク固化体の製造法。 ８ 放射性廃棄物のか焼体に、ジルコニウム化合
物を30重量％以上（ZrO2として）と、ニツケル
化合物１〜10重量％（NiOとして）と、カルシウ
ム化合物、ストロンチウム化合物およびバリウム
化合物の少なくとも１種を１〜10重量％（CaO、
SrO、BaOとして）を配合し、焼結する、特許請
求の範囲第５項記載の放射性廃棄物のセラミツク
固化体の製造法。 ９ 放射性廃棄物のか焼体に、ジルコニウム化合
物を30重量％以上（ZrO2として）配合し、溶融
後冷却することを特徴とする、放射性廃棄物のセ
ラミツク固化体の製造法。 １０ 放射性廃棄物のか焼体に、ジルコニウム化
合物を30重量％以上（ZrO2として）と、ニツケ
ル化合物１〜10重量％（NiOとして）を配合し、
溶融後冷却する、特許請求の範囲第９項記載の放
射性廃棄物のセラミツク固化体の製造法。 １１ 放射性廃棄物のか焼体に、ジルコニウム化
合物を30重量％以上（ZrO2として）と、カルシ
ウム化合物、ストロンチウム化合物およびバリウ
ム化合物の少なくとも１種を１〜10重量％
（CaO、SrO、BaOとして）を配合し、溶融後冷
却する、特許請求の範囲第９項記載の放射性廃棄
物のセラミツク固化体の製造法。 １２ 放射性廃棄物のか焼体に、ジルコニウム化
合物を30重量％以上（ZrO2として）と、ニツケ
ル化合物１〜10重量％（NiOとして）と、カルシ
ウム化合物、ストロンチウム化合物およびバリウ
ム化合物の少なくとも１種を１〜10重量％
（CaO、SrO、BaOとして）を配合し、溶融後冷
却する、特許請求の範囲第９項記載の放射性廃棄
物のセラミツク固化体の製造法。 １３ 酸化物に換算してNa2O5〜40重量％、
Fe2O35〜20重量％、MoO35〜15重量％、ZrO25〜
15重量％、CeO22〜10重量％、Cs2O2〜10重量
％、BaO1〜５重量％、SrO1〜５重量％、
Rb2O0.2〜２重量％、Y2O30.2〜２重量％、
NiO0.2〜２重量％、希土類酸化物５〜20重量
％、Cr2O30.2〜２重量％並びにTc2O7、RuO2、
Rh2O3、PdO、Ag2O、CdO、SnO、SeO2、TeO2
およびアクチニド元素酸化物の少なくとも一種を
含有する放射性廃棄物のか焼体に、ジルコニウム
化合物を30重量％以上（ZrO2として）以上配合
し、熱処理を施し固化して成り、モリブデン単
体、Na2O・MoO3、K2O・MoO3およびCs2O・
MoO3を構成相として含まないことを特徴とする
放射性廃棄物のセラミツク固化体。[Claims] 1. 5 to 40% by weight of Na 2 O in terms of oxide,
Fe2O3 5 ~20wt%, MoO3 5~15wt%, ZrO2 5 ~
15% by weight, CeO2 2-10% by weight, Cs2O2-10 % by weight, BaO1-5% by weight, SrO1-5% by weight,
Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight,
Adding 30% by weight or more of a zirconium compound (as ZrO 2 ) to the calcined body of radioactive waste containing 0.2 to 2% by weight of NiO , 5 to 20% by weight of rare earth oxides, and 0.2 to 2% by weight of Cr 2 O 3 It is then heat treated and solidified to form molybdenum alone, Na 2 O・MoO 3 , K 2 O・
A ceramic solidified body of radioactive waste characterized by not containing MoO 3 and Cs 2 O・MoO 3 as constituent phases. 2 Na 2 O 5 to 40% by weight in terms of oxides,
Fe2O3 5 ~20wt%, MoO3 5~15wt%, ZrO2 5 ~
15% by weight, CeO2 2-10% by weight, Cs2O2-10 % by weight, BaO1-5% by weight, SrO1-5% by weight,
Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight,
At least 30% by weight of a zirconium compound (as ZrO 2 ) is added to the calcined body of radioactive waste containing 0.2 to 2% by weight of NiO , 5 to 20% by weight of rare earth oxides, and 0.2 to 2% by weight of Cr 2 O 3 . , nickel compound 1-10% by weight
(as NiO) and heat-treated to solidify it.Molybdenum monomer, Na 2 O・MoO 3 , K 2 O・
A ceramic solidified body of radioactive waste characterized by not containing MoO 3 and Cs 2 O・MoO 3 as constituent phases. 3 Na 2 O 5 to 40% by weight in terms of oxides,
Fe2O3 5 ~20wt%, MoO3 5~15wt%, ZrO2 5 ~
15% by weight, CeO2 2-10% by weight, Cs2O2-10 % by weight, BaO1-5% by weight, SrO1-5% by weight,
Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight,
At least 30% by weight of a zirconium compound (as ZrO 2 ) is added to the calcined body of radioactive waste containing 0.2 to 2% by weight of NiO , 5 to 20% by weight of rare earth oxides, and 0.2 to 2% by weight of Cr 2 O 3 . , 1 to 10% by weight of at least one of calcium compounds, strontium compounds, and barium compounds (as CaO, SrO, BaO)
It is made by blending and solidifying by heat treatment, and it is made of molybdenum alone, Na 2 O・MoO 3 , K 2 O・MoO 3 and
A ceramic solidified body of radioactive waste characterized by not containing Cs 2 O/MoO 3 as a constituent phase. 4 5 to 40% by weight of Na 2 O in terms of oxides,
Fe2O3 5 ~20wt%, MoO3 5~15wt%, ZrO2 5 ~
15% by weight, CeO2 2-10% by weight, Cs2O2-10 % by weight, BaO1-5% by weight, SrO1-5% by weight,
Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight,
At least 30% by weight of a zirconium compound (as ZrO 2 ) is added to the calcined body of radioactive waste containing 0.2 to 2% by weight of NiO , 5 to 20% by weight of rare earth oxides, and 0.2 to 2% by weight of Cr 2 O 3 . , nickel compound 1-10% by weight
(as NiO) and 1 to 10% by weight of at least one of a calcium compound, a strontium compound, and a barium compound (as CaO, SrO, BaO)
It is made by blending and solidifying by heat treatment, and it is made of molybdenum alone, Na 2 O・MoO 3 , K 2 O・MoO 3 and
A ceramic solidified body of radioactive waste characterized by not containing Os 2 O/MoO 3 as a constituent phase. 5. A method for producing a ceramic solidified body of radioactive waste, which comprises blending 30% by weight or more of a zirconium compound (as ZrO 2 ) into a calcined body of radioactive waste, and sintering the mixture after compression molding. 6. Claim No. 6, in which 30% by weight or more of a zirconium compound (as ZrO 2 ) and 1 to 10% by weight of a nickel compound (as NiO) are mixed into a calcined body of radioactive waste, and the mixture is compressed and then sintered. A method for producing a ceramic solidified body of radioactive waste according to item 5. 7 The calcined body of radioactive waste is injected with 30% by weight or more of a zirconium compound (as ZrO 2 ) and 1 to 10% by weight of at least one of a calcium compound, a strontium compound, and a barium compound (CaO,
A method for producing a ceramic solidified body of radioactive waste according to claim 5, which comprises blending SrO, BaO), compression molding, and sintering. 8 Add 30% by weight or more of a zirconium compound (as ZrO 2 ), 1 to 10% by weight of a nickel compound (as NiO), and at least one of a calcium compound, a strontium compound, and a barium compound to the calcined body of radioactive waste. ~10 wt% (CaO,
A method for producing a ceramic solidified body of radioactive waste according to claim 5, which comprises blending and sintering SrO, BaO). 9. A method for producing a ceramic solidified body of radioactive waste, which comprises blending 30% by weight or more of a zirconium compound (as ZrO 2 ) into a calcined body of radioactive waste, and cooling it after melting. 10 Adding 30% by weight or more of a zirconium compound (as ZrO 2 ) and 1 to 10% by weight of a nickel compound (as NiO) to the calcined body of radioactive waste,
A method for producing a ceramic solidified body of radioactive waste according to claim 9, which comprises cooling after melting. 11 Add 30% by weight or more of a zirconium compound (as ZrO 2 ) and 1 to 10% by weight of at least one of a calcium compound, a strontium compound, and a barium compound to the calcined body of radioactive waste.
A method for producing a ceramic solidified body of radioactive waste according to claim 9, which comprises blending (as CaO, SrO, BaO), melting and cooling. 12 Add 30% by weight or more of a zirconium compound (as ZrO 2 ), 1 to 10% by weight of a nickel compound (as NiO), and at least one of a calcium compound, a strontium compound, and a barium compound to the calcined body of radioactive waste. ~10% by weight
A method for producing a ceramic solidified body of radioactive waste according to claim 9, which comprises blending (as CaO, SrO, and BaO), melting, and then cooling. 13 5 to 40% by weight of Na 2 O in terms of oxides,
Fe2O3 5 ~20wt%, MoO3 5~15wt%, ZrO2 5 ~
15% by weight, CeO2 2-10% by weight, Cs2O2-10 % by weight, BaO1-5% by weight, SrO1-5% by weight,
Rb 2 O 0.2-2% by weight, Y 2 O 3 0.2-2% by weight,
0.2-2% by weight of NiO, 5-20% by weight of rare earth oxides, 0.2-2% by weight of Cr 2 O 3 and Tc 2 O 7 , RuO 2 ,
Rh2O3 , PdO, Ag2O , CdO, SnO, SeO2 , TeO2
The calcined body of radioactive waste containing at least one type of actinide element oxide is blended with 30% by weight or more of a zirconium compound (as ZrO 2 ), and heat-treated to solidify it. MoO 3 , K 2 O・MoO 3 and Cs 2 O・
A ceramic solidified body of radioactive waste characterized by not containing MoO 3 as a constituent phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8506478A JPS5512448A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8506478A JPS5512448A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5512448A JPS5512448A (en) | 1980-01-29 |
| JPS6136200B2 true JPS6136200B2 (en) | 1986-08-16 |
Family
ID=13848193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8506478A Granted JPS5512448A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5512448A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146898A (en) * | 1982-02-24 | 1983-09-01 | 株式会社東芝 | Method of processing radioactive waste |
| JPS58160899A (en) * | 1982-03-18 | 1983-09-24 | 株式会社東芝 | Method of processing radioactive waste |
| JPS58218696A (en) * | 1982-06-15 | 1983-12-19 | 株式会社東芝 | Method of processing radioactive waste |
| JPS60198498A (en) * | 1984-03-21 | 1985-10-07 | 動力炉・核燃料開発事業団 | Method of treating spent fuel coated tube, etc. |
| AU3183797A (en) * | 1996-07-04 | 1998-02-02 | British Nuclear Fuels Plc | Encapsulation of waste |
-
1978
- 1978-07-14 JP JP8506478A patent/JPS5512448A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5512448A (en) | 1980-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4097401A (en) | Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes | |
| McCarthy | High-level waste ceramics: materials considerations, process simulation, and product characterization | |
| US4514329A (en) | Process for vitrifying liquid radioactive waste | |
| CN1033113C (en) | Nuclear fuel elements comprising trap for fission products based on oxide | |
| US4094809A (en) | Process for solidifying high-level nuclear waste | |
| BUYKX et al. | Titanate ceramics for the immobilization of sodium‐bearing high‐level nuclear waste | |
| US9922741B2 (en) | Method for the pre-calcining treatment of an aqueous nitric solution comprising at least one radionuclide and optionally ruthenium | |
| US6320091B1 (en) | Process for making a ceramic composition for immobilization of actinides | |
| JP4690623B2 (en) | Ceramic medium for waste immobilization and method for immobilizing waste from reprocessed nuclear fuel assemblies | |
| JPS6136200B2 (en) | ||
| CN116239379B (en) | Ce-Cr-Fe co-doped perovskite zircon ceramic solidified body and preparation method and application thereof | |
| CN1033669C (en) | Radioactive absorbent for fission products produced on nuclear fuel elements | |
| US3117372A (en) | Stabilized rare earth oxides for a control rod and method of preparation | |
| JPS6231319B2 (en) | ||
| JPS6136199B2 (en) | ||
| JPS6231318B2 (en) | ||
| JPS631559B2 (en) | ||
| JPS631560B2 (en) | ||
| Mukerjee et al. | Fabrication technologies for ThO2-based fuel | |
| Burghartz et al. | X-ray diffraction analysis and data interpretation of stabilized zirconia inert matrix fuel doped with plutonium | |
| US7148394B2 (en) | Ceramic for packaging of radioactive cesium | |
| Pratheep Kumar et al. | Encapsulation of heterovalent ions of two simulated high-level nuclear wastes and crystallization into single-phase NZP-based wasteforms | |
| RU2380775C1 (en) | Methods of inclusion of high active concentrate of trans-plutonium and rare earth elements into ceramics | |
| Oversby | Properties of SYNROC C nuclear-waste form: a state-of-the-art review | |
| DE60022535T2 (en) | BORATING MATERIAL BASED ON BOR FOR THE STORAGE OR TRANSMUTATION OF DURABLE RADIOACTIVE ELEMENTS |