JPS6136199B2 - - Google Patents
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- Publication number
- JPS6136199B2 JPS6136199B2 JP8506378A JP8506378A JPS6136199B2 JP S6136199 B2 JPS6136199 B2 JP S6136199B2 JP 8506378 A JP8506378 A JP 8506378A JP 8506378 A JP8506378 A JP 8506378A JP S6136199 B2 JPS6136199 B2 JP S6136199B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- radioactive waste
- oxides
- terms
- compound
- 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
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- 239000002901 radioactive waste Substances 0.000 claims description 65
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 26
- 150000003377 silicon compounds Chemical class 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- -1 aluminum compound Chemical class 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 150000001553 barium compounds Chemical class 0.000 claims 6
- 229940043430 calcium compound Drugs 0.000 claims 5
- 150000001674 calcium compounds Chemical class 0.000 claims 5
- 150000003438 strontium compounds Chemical class 0.000 claims 5
- 229940125904 compound 1 Drugs 0.000 claims 4
- 239000004615 ingredient Substances 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 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
- 238000001816 cooling Methods 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
- 238000002386 leaching Methods 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- 239000002699 waste material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 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
- 239000007788 liquid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000941 radioactive substance Substances 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012857 radioactive material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002915 spent fuel radioactive waste Substances 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 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
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910015999 BaAl Inorganic materials 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
- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 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
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 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
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 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
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011361 granulated particle 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
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 230000002265 prevention Effects 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
- 239000002910 solid waste 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
- 238000012360 testing method Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000010457 zeolite Substances 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アルミニウムおよびケイ
素の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、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てることができる。
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」と言う）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じて開発された。
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
放熱性が悪く、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、強度的にはすぐれ易いこと、
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体化を得
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％及びその他の元素の酸
化物を含有する放射性廃棄物のか焼体に、酸化物
に換算してアルミニウム化合物とケイ素化合物と
を、重量比でAl2O3／SiO2が0.5〜1.67の範囲で、
各々15重量％以上合計40重量％以上配合し、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
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
よつて生ずる沈澱スラツジ等の各種の固体廃棄物
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、本発明で使用するアルミニウム化合物は、
酸化アルミニウム（Al2O3）又は溶融もしくは焼
結処理によりAl2O3に変化する化合物であればよ
い。溶融・焼結によりAl2O3に変化するアルミニ
ウム化合物としては、例えばダイアスポア
（AlOOH）、窒化アルミニウム（AlN）等があげ
られる。同様に、ケイ素化合物としては、SiO2
又は溶融もしくは焼結処理によりSiO2に変化す
る物質、例えば窒化ケイ素（Si3N4）、シリコン樹
脂、炭化ケイ素（SiO）等を使用することができ
る。更に、アルミニウムおよびケイ素、場合によ
つては更らに後述のニツケル、カルシウム等のう
ち２種以上の金属を含む化合物、例えばカオリン
（Al4Si4O10（OH）8）、モンモリロナイト
（Al4Si4O10（OH）2・nH2O）のような粘土類、
種々の沸石類（例えばCaAl2S5〜7O12〜18・５〜
7H2O、BaAl2Si6O16・6H2O等）等も使用でき
る。
か焼体に配合するアルミニウム化合物とケイ素
化合物とは、Al2O3、SiO2に換算して、Al2O3／
SiO2の比が0.5〜1.67の範囲で、各々15重量％以
上、合計40重量％以上の配合量が必要である。ア
ルミニウム化合物もしくはケイ素化合物が15重量
％未満の場合、又はそれらの合計量が40重量％未
満の場合には、Mo単体、Na2O・MoO3、K2O・
MoO3、Cs2O・MoO3等が析出し易く、固化体の
耐浸出性が著しく低下するからである。また、
Al2O3／SiO2の比が0.50〜1.67の範囲外にある場
合にも、固化体の耐浸出性は劣化する。
アルミニウム化合物およびケイ素化合物を、こ
のような重量比で、か焼体中に配合し、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60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
廃棄物のか焼体にアルミニウム化合物およびケイ
素化合物を40重量％以上（Al2O3、SiO2として）
と、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。NiOを、10重量％を越え
て配合させると固化体の耐浸出性の劣下をもたら
し１重量％未満を配合させては、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、例えば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アルミニウム化合物およびケ
イ素化合物を40重量％以上（Al2O3、SiO2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
化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10〜１
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％未満で
は、その効果があらわれないからである。これら
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
廃棄物のか焼体にアルミニウム化合物およびケイ
素化合物を40重量％以上（Al2O3、SiO2として）
と、ニツケル化合物に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）を配合し、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
述のアルミニウム化合物およびケイ素化合物を所
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1700〜2300℃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800〜1400℃
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、窒素アルミニウム（AlN）、窒
化シリコン（Si3N4）、シリコン樹脂、炭化シリコ
ン（SiC）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Al2O3、SiO2、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。
本発明の固化体は常圧、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、Al2O3および
SiO2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
Al2O3、SiO2、NiO、CaO等とともに熱的に安
定な相を形成するため、固化体は1400℃まで安
定な耐熱性を有している。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) 本発明の固化体中には、放射性廃棄物のか焼
体を最高60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 to a solidified ceramic body containing calcined radioactive waste (referred to as "calcined body"), and a compound of aluminum and silicon in the calcined body powder. The present invention relates to a method for producing the solidified ceramic body by mixing and then 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.
In addition, this solidified material can be used to irradiate food by controlling the radiation dose by, for example, adding a suitable barrier or barrier to prevent spoilage, insect damage, germination, etc. during transportation and storage, and to extend shelf life. be able to. 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 is a problem not only in terms of safety and management, but also in terms of quantity and volume, so there is a strong need for the establishment of 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 into the surrounding area 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. Furthermore, since the amount of radioactive waste is expected to increase in the future,
For efficient storage, it is desirable that the ratio of the weight of waste to the total weight of waste and additives (hereinafter referred to as "content ratio") 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 oxide 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 dissipation property of the heat generated by the collapse of the container is poor, and as a result, the temperature tends to rise during storage.Furthermore, the storage container is likely to be damaged due to this temperature rise, and its strength is likely to be poor.
etc. 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 with phosphoric acid or borosilicate glass, etc., and 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 glass solidified body with a stable structure, the upper limit of the amount of calcined body powder added is 25 to 30% by weight. was. Therefore, a solidified body that has high thermal conductivity, has good heat dissipation properties, is resistant to the decay heat of radioactive materials, and can be filled and solidified with radioactive waste at a higher density, and a method for producing the same. development 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 Adding aluminum compounds and silicon compounds in terms of oxides to the calcined body of radioactive waste containing oxides of other elements, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67,
It is made by blending 15% by weight or more of each and a total of 40% by weight or more, and solidifying it by heat treatment of melting or sintering, and contains elemental molybdenum, Na 2 O・MoO 3 , K 2 O・MoO 3 and
It is characterized by being a ceramic that does not contain Cs 2 O/MoO 3 as a constituent phase. Other oxides contained in the calcined body include Tc 2 O 7 , RuO 2 , Rh 2 O 3 ,
Examples include PdO, Ag 2 O, CdO, SnO, SeO 2 , TeO 2 and actinide element oxides. The calcined body of radioactive waste in the present invention includes, for example, radioactive waste remaining after processing spent nuclear fuel and recovering U and Pu, concentrated liquid of recycled waste liquid from a mixed-bed desalination machine, and waste generated from buildings. Various waste liquids containing radioactive materials such as concentrated waste liquid from floor drains and equipment drains, reactor purification systems, fuel pool systems, condensate systems, etc.
High concentration or medium-low concentration obtained by calcining various solid 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 aluminum compound used in the present invention is
It may be aluminum oxide (Al 2 O 3 ) or a compound that changes to Al 2 O 3 by melting or sintering. Examples of aluminum compounds that change into Al 2 O 3 by melting and sintering include Diaspore (AlOOH) and aluminum nitride (AlN). Similarly, as a silicon compound, SiO 2
Alternatively, it is possible to use a substance that changes into SiO 2 by melting or sintering, such as silicon nitride (Si 3 N 4 ), silicone resin, silicon carbide (SiO), and the like. Furthermore, compounds containing aluminum and silicon, and in some cases, two or more metals such as nickel and calcium as described below, such as kaolin (Al 4 Si 4 O 10 (OH) 8 ), montmorillonite (Al 4 clays such as Si 4 O 10 (OH) 2・nH 2 O),
Various zeolites (e.g. CaAl 2 S 5~7 O 12~18・5~
7H 2 O, BaAl 2 Si 6 O 16・6H 2 O, etc.) can also be used. The aluminum compound and silicon compound blended into the calcined body are Al 2 O 3 /SiO 2 in terms of Al 2 O 3 and SiO 2 .
It is necessary that the SiO 2 ratio be in the range of 0.5 to 1.67, with a blending amount of 15% by weight or more for each, and a total of 40% by weight or more. When the aluminum compound or silicon compound is less than 15% by weight, or when the total amount thereof is less than 40% by weight, Mo alone, Na 2 O・MoO 3 , K 2 O・
This is because MoO 3 , Cs 2 O・MoO 3 , etc. are likely to precipitate, and the leaching resistance of the solidified material is significantly reduced. Also,
The leaching resistance of the solidified body also deteriorates when the ratio of Al 2 O 3 /SiO 2 is outside the range of 0.50 to 1.67. A ceramic solidified body produced by blending an aluminum compound and a silicon compound in such a weight ratio into a calcined body and melting or sintering is heated at 1000°C.
It is extremely stable even at the above-mentioned high temperatures, and is extremely superior in terms of leaching resistance, thermal conductivity, and mechanical strength compared to a calcined body sintered alone. Furthermore, the content can be increased to a maximum of 60% by weight without sacrificing these excellent properties. The second invention regarding the solidified body of the present invention is to add 40% by weight or more of aluminum compounds and silicon compounds (as Al 2 O 3 , SiO 2 ) to the calcined body of radioactive waste.
and 1-10% by weight of nickel compound (as NiO)
It is characterized by being blended with and solidified. 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. This is because if NiO is added in an amount exceeding 10% by weight, the leaching resistance of the solidified product deteriorates, and if it is added in an amount less than 1% by weight, the effect will not be achieved. As a nickel compound,
NiO or compounds that become NiO by melting or sintering, such as 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 to add 40% by weight or more of an aluminum compound and a silicon compound (as Al 2 O 3 and SiO 2 ) and at least one of calcium, strontium, and barium to the calcined body of radioactive waste. of metal compounds from 1 to 10
% by weight (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,
When combined (as SrO, BaO), the leaching resistance of the solidified material can be further improved. Mixing ratio 10-1
The reason why the amount is limited to 10% by weight is because if it exceeds 10% by weight, the leaching resistance of the solidified product deteriorates, and if it is less than 1% by weight, the effect will not be exhibited. These compounds such as calcium can also 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 regarding the solidified body of the present invention is to add 40% by weight or more of an aluminum compound and a silicon compound (as Al 2 O 3 , SiO 2 ) to the calcined body of radioactive waste.
and 1 to 10% by weight (as NiO) of a nickel compound, and 1 to 10% of a metal compound of at least one of calcium, strontium, and barium.
% by weight (as CaO, SrO, BaO) and solidified. 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 aluminum compound and silicon compound are added to the calcined body of radioactive waste, and if necessary, a predetermined amount of a nickel compound and/or at least one metal compound among Ca, Sr, and Ba is added to the calcined body of radioactive waste. Mix. The method of mixing radioactive waste and metal compounds is to form a film on the surface of the metal compound powder to be mixed, in addition to the usual powder mixing method.For example, water is added to this powder, kneaded to form a slurry, and then sieved. The radioactive waste may be sprayed onto the surface of the particles at a temperature of about 600°C, for example, using the granulated particles as a fluidized bed. A ceramic solidified body can be obtained by charging this blend into a container, melting it at about 1700 to 2300°C, and then solidifying it into an ingot of a certain shape. Alternatively, the compound can be compressed at 800-1400°C.
It can also be made into a solidified ceramic body by sintering it. To facilitate compression molding,
Binding agents such as water, paraffin, polyvinyl alcohol, etc. can be added to the formulation. When the metal compound to be blended is aluminum nitrogen (AlN), silicon nitride (Si 3 N 4 ), silicone resin, silicon carbide (SiC), etc., it is finalized in a solidified ceramic body by sintering or melting treatment. It is necessary to perform sintering or melting in an oxidizing atmosphere such as air so that the material changes into oxides (eg, Al 2 O 3 , SiO 2 , NiO, CaO, etc.). The solidified body of the present invention can be produced by an existing sintering method, whether under normal pressure or pressurization, or by an existing melting method, whether by 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, Al 2 O 3 and
Because of SiO 2 , a dense and strong ceramic solidified body can be obtained. 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
Since it forms a thermally stable phase with Al 2 O 3 , SiO 2 , NiO, CaO, etc., the solidified material has stable heat resistance up to 1400°C. 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 60% by weight of calcined radioactive waste.
In other words, compared to conventional vitrification, the content rate has been significantly improved, and as a result, radioactive waste can be
The storage container (canister) can be densely packed, and the number of canisters can be reduced. (5) The solidified product may be stored as is in a storage container, but food can be irradiated by irradiating the food by controlling the radiation dose by, for example, placing an appropriate container or shield to prevent spoilage, insect damage, and germination during transportation and storage. Suitable for purposes such as prevention of such problems and extension of storage period. 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
度の測定は固化体より測定用試験片（３×３×30
mm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0.5cm／
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ーフラツシユ法
に従つて測定した。
実施例１〜13、比較例１〜８
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
Molybdenum alone was found in the solidified material by line diffraction.
It was investigated whether phases of Na 2 O.MoO 3 , Cs 2 O.MoO 3 , and K 2 O.MoO 3 were generated. The mechanical strength was measured using test pieces (3 x 3 x 30
mm square prism) and mechanically strengthened by three-point bending method (span length 20mm, applied acceleration 0.5cm/
The minutes were 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 13, Comparative Examples 1 to 8 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14〜26、比較例９〜17
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2000℃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 14 to 26, Comparative Examples 9 to 17 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. After melting the compound at 2000°C by arc discharge, it was cooled to form a solidified body. 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、酸化物に換算してアルミニウム化合
物とケイ素化合物とを、重量比でAl2O3／SiO2が
0.5〜1.67の範囲で、各々15重量％以上合計40重
量％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。 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量％、Cs2O2〜10重量％、
BaO1〜５重量％、SrO1〜５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、酸化物
に換算してアルミニウム化合物とケイ素化合物と
を、重量比でAl2O3／SiO2が0.5〜1.67の範囲で、
各々15重量％以上合計40重量％以上と、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、酸化物に換算してアルミニウム化合
物とケイ素化合物とを、重量比でAl2O3／SiO2が
0.5〜1.67の範囲で、各々15重量％以上合計40重
量％以上と、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、酸化物に換算してアルミニウム化合
物とケイ素化合物とを、重量比でAl2O3／SiO2が
0.5〜1.67の範囲で、各々15重量％以上合計40重
量％以上と、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、酸化物に換算して
アルミニウム化合物とケイ素化合物とを、重量比
でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重量
％以上合計40重量％以上配合し、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
ク固化体の製造方法。 ６ 放射性廃棄物のか焼体に、酸化物に換算して
アルミニウム化合物とケイ素化合物とを、重量比
でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重量
％以上合計40重量％以上と、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方法。 ７ 放射性廃棄物のか焼体に、酸化物に換算して
アルミニウム化合物とケイ素化合物とを、重量比
でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重量
％以上合計40重量％以上と、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
固化体の製造方法。 ８ 放射性廃棄物のか焼体に、酸化物に換算して
アルミニウム化合物とケイ素化合物とを、重量比
でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重量
％以上合計40重量％以上と、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
造方法。 ９ 放射性廃棄物のか焼体に、酸化物に換算して
アルミニウム化合物とケイ素化合物とを、重量比
でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重量
％以上合計40重量％以上配合し、溶融冷却するこ
とを特徴とする、放射性廃棄物のセラミツク固化
体の製造方法。 １０ 放射性廃棄物のか焼体に、酸化物に換算し
てアルミニウム化合物とケイ素化合物とを、重量
比でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重
量％以上合計40重量％以上と、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方法。 １１ 放射性廃棄物のか焼体に、酸化物に換算し
てアルミニウム化合物とケイ素化合物とを、重量
比でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重
量％以上合計40重量％以上と、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
固化体の製造方法。 １２ 放射性廃棄物のか焼体に、酸化物に換算し
てアルミニウム化合物とケイ素化合物とを、重量
比でAl2O3／SiO2が0.5〜1.67の範囲で、各々15重
量％以上合計40重量％以上と、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
固化体の製造方法。 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、酸化物に換算
してアルミニウム化合物とケイ素化合物とを、重
量比でAl2O3／SiO2が0.5〜1.67の範囲で、各々15
重量％以上合計40重量％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,
Calcined 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 is added with aluminum compounds and silicon compounds in terms of oxides. , the weight ratio of Al 2 O 3 /SiO 2 is
In the range of 0.5 to 1.67, 15% by weight or more each , 40% by weight or more in total, and heat - treated to solidify it. A ceramic solidified body of radioactive waste characterized by not containing 3 as a constituent phase. 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 O0.2~2
% by weight, 0.2-2% by weight of Y 2 O 3 , 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 , An aluminum compound and a silicon compound in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67,
It is made by blending 15% by weight or more of each with a total of 40% by weight or more and 1 to 10% by weight of a nickel compound (as NiO) and solidifying it by heat treatment.
Na 2 O・MoO 3 , K 2 O・MoO 3 and Cs 2 O・MoO 3
A ceramic solidified body of radioactive waste characterized by not containing as a constituent phase. 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,
Calcined 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 is added with aluminum compounds and silicon compounds in terms of oxides. , the weight ratio of Al 2 O 3 /SiO 2 is
In the range of 0.5 to 1.67, 15% by weight or more and 40% by weight or more in total, and 1 to 10% by weight (as CaO, SrO, BaO) of at least one of a calcium compound, a strontium compound, and a barium compound are blended and heat treated. It is made of molybdenum alone, Na 2 O・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. 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,
Calcined 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 is added with aluminum compounds and silicon compounds in terms of oxides. , the weight ratio of Al 2 O 3 /SiO 2 is
In the range of 0.5 to 1.67, 15% by weight or more each and 40% by weight or more in total, and 1 to 10% by weight of nickel compound (NiO
It is made by blending 1 to 10% by weight (as CaO, SrO, BaO) of at least one of calcium compound, strontium compound, and barium compound (as CaO, SrO, BaO) and solidifying it by heat treatment. 3 , K 2 O・MoO 3 and Os 2 O・
A ceramic solidified body of radioactive waste characterized by not containing MoO 3 as a constituent phase. 5 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. A method for producing a ceramic solidified body of radioactive waste, which comprises blending the above ingredients, compression molding, and then sintering. 6 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. Above, nickel compound 1~
5. The method for producing a ceramic solidified body of radioactive waste according to claim 5, wherein 10% by weight (as NiO) is blended, compression molded, and then sintered. 7 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. Above, calcium compounds,
1 to 10% by weight of at least one of a strontium compound and a barium compound (CaO, SrO, BaO
6. A method for producing a ceramic solidified body of radioactive waste according to claim 5, wherein the ceramic solidified body of radioactive waste is blended with the following: 8 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. Above, nickel compound 1~
10% by weight (as NiO) and calcium compounds,
1 to 10% by weight of at least one of a strontium compound and a barium compound (CaO, SrO, BaO
A method for producing a ceramic solidified body of radioactive waste according to claim 5, which comprises blending and sintering a ceramic solidified body of radioactive waste. 9 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. A method for producing a ceramic solidified body of radioactive waste, which comprises blending the above ingredients and melting and cooling the mixture. 10 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. Above, nickel compound 1
10. The method for producing a ceramic solidified body of radioactive waste according to claim 9, wherein the ceramic solidified body of radioactive waste is blended with ~10% by weight (as NiO) and cooled after melting. 11 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. In addition to the above, 1 to 10% by weight of at least one of calcium compounds, strontium compounds, and barium compounds (CaO, SrO,
10. The method for producing a ceramic solidified body of radioactive waste according to claim 9, wherein the ceramic solidified body of radioactive waste is blended with BaO), melted, and then cooled. 12 Add aluminum compounds and silicon compounds to the calcined body of radioactive waste in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67, each at 15% by weight or more and a total of 40% by weight. Above, nickel compound 1
~10% by weight (as NiO) and 1 to 10% by weight of at least one of calcium, strontium and barium compounds (CaO, SrO,
10. The method for producing a ceramic solidified body of radioactive waste according to claim 9, wherein the ceramic solidified body of radioactive waste is blended with BaO), melted, and then cooled. 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
and a calcined body of radioactive waste containing at least one type of actinide element oxide, an aluminum compound and a silicon compound in terms of oxides, with a weight ratio of Al 2 O 3 /SiO 2 in the range of 0.5 to 1.67. , 15 each
It is made by blending a total of 40% or more by weight and solidifying it by heat treatment, and contains molybdenum alone, Na2O ,
A ceramic solidified body of radioactive waste characterized by not containing MoO 3 , K 2 O・MoO 3 and Cs 2 O・MoO 3 as constituent phases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8506378A JPS5512447A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8506378A JPS5512447A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5512447A JPS5512447A (en) | 1980-01-29 |
| JPS6136199B2 true JPS6136199B2 (en) | 1986-08-16 |
Family
ID=13848166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8506378A Granted JPS5512447A (en) | 1978-07-14 | 1978-07-14 | Ceramiccsolidified radioactive waste* and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5512447A (en) |
Families Citing this family (3)
| 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 |
-
1978
- 1978-07-14 JP JP8506378A patent/JPS5512447A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5512447A (en) | 1980-01-29 |
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