JP4580326B2 - Method for producing waste ion exchange resin aggregates - Google Patents

Method for producing waste ion exchange resin aggregates Download PDF

Info

Publication number
JP4580326B2
JP4580326B2 JP2005329857A JP2005329857A JP4580326B2 JP 4580326 B2 JP4580326 B2 JP 4580326B2 JP 2005329857 A JP2005329857 A JP 2005329857A JP 2005329857 A JP2005329857 A JP 2005329857A JP 4580326 B2 JP4580326 B2 JP 4580326B2
Authority
JP
Japan
Prior art keywords
exchange resin
ion exchange
water
waste ion
mass
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.)
Active
Application number
JP2005329857A
Other languages
Japanese (ja)
Other versions
JP2007136274A (en
Inventor
孝 大津
丈志 出水
正弘 萩原
正治 辻田
光彦 能見
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ebara Corp
Original Assignee
Ebara Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ebara Corp filed Critical Ebara Corp
Priority to JP2005329857A priority Critical patent/JP4580326B2/en
Publication of JP2007136274A publication Critical patent/JP2007136274A/en
Application granted granted Critical
Publication of JP4580326B2 publication Critical patent/JP4580326B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Landscapes

  • Processing Of Solid Wastes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Description

発明の属する技術分野TECHNICAL FIELD OF THE INVENTION

本発明は、細粒状廃イオン交換樹脂の処理技術に関し、特に、含水率が高く焼却し難い細粒状廃イオン交換樹脂を焼却処理する処理技術に関する。   The present invention relates to a processing technique for fine granular waste ion exchange resin, and particularly to a processing technique for incinerating fine granular waste ion exchange resin that has a high water content and is difficult to incinerate.

本発明は、含水率が高い細粒状廃イオン交換樹脂を固化体に成形し、燃料として再利用する処理技術に関し、汽力発電施設、特に原子力発電施設で発生する放射性イオン交換樹脂の焼却処理技術として有用である。   The present invention relates to a processing technology in which a fine granular waste ion exchange resin having a high water content is formed into a solidified body and reused as a fuel, and as an incineration processing technology for radioactive ion exchange resin generated in a steam power generation facility, particularly in a nuclear power generation facility. Useful.

従来の技術Conventional technology

汽力発電施設、特に原子力発電施設などでは、発電施設の運転において発生する放射能を有する液体の処理に、粒状又は粉末状のイオン交換樹脂を使用して放射能の除去を行っている。これらイオン交換樹脂は、再生して繰り返し使用するか、あるいは再生せずに放射性廃棄物として廃棄処理されることになっている。しかし、これら使用済みの放射性イオン交換樹脂（廃イオン交換樹脂）は、粒径が０．４〜１．０mm程度の粒状又は数１０μm程度の粉末状の細粒状物質であるため飛散し易い。通常は、原子力発電施設の放射能汚染などの問題を防止するために、水を張った槽内で保管し、容器に入れて搬送するか又は水スラリーとして配管を経由して移送するなどして取り扱われている。そのため、使用済みの放射性イオン交換樹脂は多量の水分を含み、燃焼しにくい、という問題がある。また、粒度が細かすぎて、通常、発電施設などに既設されている焼却炉では、燃焼室に留まることなく通過してしまい未焼却のまま残ってしまうので焼却処理が難しい、という問題がある。そのため、廃イオン交換樹脂は、処理されずに、発電施設内の廃棄物貯留槽に保管されたままになっており、その貯蔵量は増加の一途を辿っている。   In steam power generation facilities, particularly nuclear power generation facilities, the removal of radioactivity is performed by using granular or powdered ion exchange resins for the treatment of radioactive liquids generated during operation of power generation facilities. These ion exchange resins are to be regenerated and used repeatedly or disposed of as radioactive waste without being regenerated. However, since these used radioactive ion exchange resins (waste ion exchange resins) are granular materials having a particle size of about 0.4 to 1.0 mm or powders of about several tens of μm, they are easily scattered. Normally, in order to prevent problems such as radioactive contamination of nuclear power generation facilities, store in a tank filled with water and transport it in a container or transport it as water slurry via a pipe. It is handled. Therefore, the used radioactive ion exchange resin has a problem that it contains a large amount of moisture and is difficult to burn. Moreover, since the particle size is too fine, an incinerator that is usually installed in a power generation facility or the like has a problem that it is difficult to incinerate because it passes through the combustion chamber and remains unincinerated. For this reason, the waste ion exchange resin is not treated but is kept in the waste storage tank in the power generation facility, and the storage amount thereof is steadily increasing.

これまで、廃イオン交換樹脂の処理方法として、化学処理方式、熱分解方式、スチーム方式、溶融処理方式、直接処理方式などが提案されているが、これまで提案されている種々の方式では、装置が複雑で制御が困難であること、処理コストがかかり過ぎること、安定した運転ができないこと、故障が多いこと、材料上に問題があること、などの種々の理由によって実用化されていないか、または実用化されていても問題が多いのが現状である。   Up to now, chemical treatment methods, thermal decomposition methods, steam methods, melt treatment methods, direct treatment methods, etc. have been proposed as treatment methods for waste ion exchange resins. Is not practical because of various reasons such as complicated and difficult to control, excessive processing costs, inability to operate stably, many failures, problems on materials, etc. Or, even if it is put into practical use, there are many problems at present.

廃イオン交換樹脂を簡易に処理する方法として、本発明者らは可燃性結合材と廃イオン交換樹脂を混合、若しくは更にカルシウム塩を加えてブレンドして集合固化体を製造する方法を提唱した（特許文献１）。この製造方法は、廃イオン交換樹脂の水分を粗切りし、これに石油系ワックスなどの可燃性結合材を混合して、混錬成形機にて加熱成形するものである。この製造方法によれば、カルシウム塩を添加することで廃イオン交換樹脂の焼却時に発生するＳＯｘの量を低減することができるが、加圧時に液状化しやすく、混練式固化体製造装置内部に水分が溜まることで装置の運転が不安定になり、安定して連続的に高収率で固化体を製造することが難しいという問題が残る。
特開2005-31060号公報 As a method for easily treating the waste ion exchange resin, the present inventors proposed a method for producing a solidified aggregate by mixing a combustible binder and a waste ion exchange resin, or further blending by adding a calcium salt ( Patent Document 1). In this production method, the water of the waste ion exchange resin is roughly cut, and a combustible binder such as petroleum wax is mixed therewith, followed by heat molding with a kneading molding machine. According to this production method, the amount of SO x generated during incineration of the waste ion exchange resin can be reduced by adding a calcium salt, but it is liable to be liquefied at the time of pressurization. The accumulation of moisture makes the operation of the apparatus unstable, and there remains a problem that it is difficult to stably and continuously produce a solidified body with a high yield.
JP 2005-31060

本発明の目的は、低コストで効率的、且つ安定的な焼却処理を可能にする廃イオン交換樹脂集合固化体の製造方法、特に連続製造方法、製造装置及び廃イオン交換樹脂集合固化体を提供することにある。なお、「集合固化体」とは、可燃性結合材をバインダとして、細粒状の廃イオン交換樹脂を結合させてなる集合体を固形化したもの全般を意味する。   An object of the present invention is to provide a method for producing a solidified waste ion exchange resin, particularly a continuous production method, a production apparatus and a waste solidified ion exchange resin solidified body, which enables efficient and stable incineration at low cost. There is to do. The “aggregated solidified body” means all the solidified aggregates formed by binding fine granular waste ion exchange resin using a combustible binder as a binder.

上記課題を解決するため、本発明者らは鋭意研究した結果、細粒状の廃イオン交換樹脂と、石油ワックスや植物性ワックスなどの比較的低融点で且つ常温で固体である可燃性結合材と、廃イオン交換樹脂中に含まれる水分を吸収する吸水材とを混合し、さらに場合によってはカルシウム塩を添加混合し、加熱しながら混練し、球状、円柱状、角柱状など所望の形状に成形し、冷却することによって、既設の焼却炉に容易に装荷して焼却処理できる廃イオン交換樹脂の固化体を製造できることを知見した。   In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, a fine-grained waste ion exchange resin and a combustible binder having a relatively low melting point such as petroleum wax and vegetable wax and solid at room temperature. , Mixed with a water-absorbing material that absorbs moisture contained in the waste ion exchange resin, and optionally added and mixed with calcium salt, kneaded while heating, and molded into a desired shape such as spherical, cylindrical, prismatic, etc. Then, by cooling, it was found that a solidified body of a waste ion exchange resin that can be easily loaded into an existing incinerator and incinerated can be produced.

本発明によれば、廃イオン交換樹脂から樹脂表面水を除去する粗水切り工程と、粗水切りした後の廃イオン交換樹脂と、吸水材とを混合して、該吸水材に該廃イオン交換樹脂の残留水分を吸水させる吸水工程と、吸水後の廃イオン交換樹脂と吸水材とに、粉末又は粒状の可燃性結合材を添加し混合する可燃性結合材添加工程と、吸水後の廃イオン交換樹脂と吸水材と可燃性結合材との混合物を混練成形機に供給する工程と、吸水後の廃イオン交換樹脂と吸水材と該可燃性結合材とを可燃性結合材の軟化点以上で溶融点に至らない温度に維持しながら混練して成形体に成形する混練成形工程と、該成形体を冷却し固体化する冷却固化工程と、を含む、廃イオン交換樹脂の集合固化体の製造方法が提供される。   According to the present invention, the rough water draining step for removing the resin surface water from the waste ion exchange resin, the waste ion exchange resin after the rough water drain and the water absorbing material are mixed, and the waste ion exchange resin is mixed with the water absorbent material. A water absorption process for absorbing residual water, a combustible binder addition process for adding a powder or granular combustible binder to the waste ion exchange resin and water absorbent after mixing, and a waste ion exchange after water absorption The step of supplying a mixture of resin, water absorbent and combustible binder to a kneading machine, and melting the waste ion exchange resin after absorbing water, the water absorbent and the combustible binder above the softening point of the combustible binder. A method for producing a solidified body of waste ion exchange resin, comprising: a kneading and molding step of kneading and molding into a molded body while maintaining a temperature not reaching the point; and a cooling and solidifying step of cooling and solidifying the molded body Is provided.

本発明において、前記吸水工程の後、前記混練成形工程の前に、カルシウム塩を添加するカルシウム塩添加工程をさらに含むことが好ましい。特に、可燃性結合材添加工程の後で混練成形工程の前に、カルシウム塩を添加することが好ましい。   In the present invention, it is preferable to further include a calcium salt addition step of adding a calcium salt after the water absorption step and before the kneading and forming step. In particular, it is preferable to add the calcium salt after the combustible binder addition step and before the kneading and forming step.

すなわち、本発明の廃イオン交換樹脂集合固化体の製造方法は、粗水切りした廃イオン交換樹脂を可燃性結合材と混合させる前に、予め吸水材と混合させて残留水分を吸水させてしまうことを特徴とする。残留水分を吸水した後の吸水材は、加圧しても吸水した水分を放出することがほとんどなく、残留水分が吸水された後の廃イオン交換樹脂に対してカルシウム塩を添加することによって、カルシウム塩が廃イオン交換樹脂中の残留水分を吸出すことを防止することができる。このように、カルシウム塩が水分とほとんど接触することが無くなり、その後の混練成形工程での混錬加圧成形時において液状化することがないため、安定的に集合固化体を製造することができる。   That is, in the method for producing a solidified waste ion exchange resin according to the present invention, before the waste ion exchange resin drained from coarse water is mixed with the combustible binder, the residual water is absorbed in advance by mixing with the water absorbing material. It is characterized by. The water-absorbing material after absorbing residual moisture hardly releases the absorbed water even when pressurized, and by adding calcium salt to the waste ion exchange resin after residual moisture is absorbed, It is possible to prevent the salt from sucking out residual moisture in the waste ion exchange resin. In this way, the calcium salt is hardly in contact with moisture, and is not liquefied at the time of kneading pressure molding in the subsequent kneading molding step, so that the aggregated solidified body can be produced stably. .

本発明において処理することができる廃イオン交換樹脂としては、汽力発電施設、特に原子力発電施設などで発生する廃イオン交換樹脂を挙げることができる。しかし、これらに限定されず、およそ焼却処理が必要な廃イオン交換樹脂全般に適用することができる。   Examples of the waste ion exchange resin that can be treated in the present invention include waste ion exchange resins generated in steam power generation facilities, particularly nuclear power generation facilities. However, the present invention is not limited to these, and can be applied to all waste ion exchange resins that generally require incineration.

本発明において処理することができる廃イオン交換樹脂の種類は特に限定されるものではなく、陰イオン交換樹脂と陽イオン交換樹脂とを含む混合廃イオン交換樹脂、実質的に陰イオン交換樹脂のみを含む廃陰イオン交換樹脂、実質的に陽イオン交換樹脂のみを含む廃陽イオン交換樹脂などを対象とすることができる。具体的には、強酸性陽イオン交換樹脂、強塩基性陰イオン交換樹脂、弱酸性陽イオン交換樹脂、弱塩基性陰イオン交換樹脂、キレート樹脂などに適用可能である。強酸性陽イオン交換樹脂としては、ダイヤイオンSKN-1、SKN-3、PK228G、SK1BN（以上、三菱化学製）、アンバーライト200C、IR120B、アンバージェット1600（以上、ローム＆ハース製）、ダウエックスHCR-W2-H、HGR-H、MS650C（以上、ダウケミカル製）を好ましく挙げることができる。強塩基性陰イオン交換樹脂としては、ダイヤイオンSAN-1、SMN-1、SMN-3、PA312L、PA316L（以上、三菱化学製）、アンバーライトIRA900、IRA400T（以上、ローム＆ハース製）、ダウエックスSBR-OH、SBR-P-C-OH、MS550A（以上、ダウケミカル）を好ましく挙げることができる。弱酸性陽イオン交換樹脂としては、WK10、WK11、WK20（以上、三菱化学製）、MAC3（ダウケミカル製）を好ましく挙げることができる。弱塩基性陰イオン交換樹脂としては、WA10、WA11、WA20、WBA-2（以上、三菱化学製）を好ましく挙げることができる。キレート樹脂としては、ユニセレック（ユニチカ製）を好ましく挙げることができる。   The kind of the waste ion exchange resin that can be treated in the present invention is not particularly limited, and a mixed waste ion exchange resin containing an anion exchange resin and a cation exchange resin, substantially only an anion exchange resin. The waste anion exchange resin containing, the waste cation exchange resin substantially containing only the cation exchange resin can be targeted. Specifically, the present invention can be applied to strong acid cation exchange resins, strong base anion exchange resins, weak acid cation exchange resins, weak base anion exchange resins, chelate resins, and the like. Strongly acidic cation exchange resins include Diaion SKN-1, SKN-3, PK228G, SK1BN (Mitsubishi Chemical), Amberlite 200C, IR120B, Amberjet 1600 (Rohm & Haas), Dowex Preferred examples include HCR-W2-H, HGR-H, and MS650C (above, manufactured by Dow Chemical). Strongly basic anion exchange resins include Diaion SAN-1, SMN-1, SMN-3, PA312L, PA316L (Mitsubishi Chemical), Amberlite IRA900, IRA400T (Rohm & Haas), Dow X SBR-OH, SBR-PC-OH, MS550A (above, Dow Chemical) can be preferably mentioned. Preferable examples of weakly acidic cation exchange resins include WK10, WK11, WK20 (above, manufactured by Mitsubishi Chemical) and MAC3 (manufactured by Dow Chemical). Preferred examples of the weakly basic anion exchange resin include WA10, WA11, WA20, and WBA-2 (above, manufactured by Mitsubishi Chemical). As the chelate resin, Uniselec (manufactured by Unitika) can be preferably mentioned.

これら廃イオン交換樹脂の粒径は特に限定されるものではないが、一般的な焼却炉では焼却処理が不充分であるような細粒状の廃イオン交換樹脂である場合に本発明が特に効果的であるので、好ましい。典型的には、平均粒径が０．４〜１．０mm程度の粒状、又は平均粒径が数１０μm程度の粉末状の廃イオン交換樹脂が好ましい。なお、粉末樹脂としては、エピコール社のPD1、PD3、グレーバー社のパウデックスなどを挙げることができる。さらに、本発明において処理することができる廃イオン交換樹脂は、乾燥形態でも湿潤形態でもよい。しかし、従来技術では湿潤状態の廃イオン交換樹脂の焼却処理が困難であった点を考慮すれば、湿潤状態の廃イオン交換樹脂を本発明により処理することで、より一層の効果がもたらされるので、好ましい。   The particle size of these waste ion exchange resins is not particularly limited, but the present invention is particularly effective when the waste ion exchange resins are fine granular materials that are not sufficiently incinerated in a general incinerator. Therefore, it is preferable. Typically, a granular waste ion exchange particle having an average particle diameter of about 0.4 to 1.0 mm or a powdery waste ion exchange resin having an average particle diameter of about several tens of μm is preferable. Examples of the powder resin include Epicol PD1, PD3, and Graber's Powdex. Furthermore, the waste ion exchange resin that can be treated in the present invention may be in a dry or wet form. However, in view of the fact that it is difficult to incinerate the waste state ion exchange resin in the wet state in the prior art, the treatment of the waste state ion exchange resin in the wet state according to the present invention provides a further effect. ,preferable.

本発明で使用する吸水材としては、ポリアクリル酸、ポリアクリル酸のアルカリ金属塩、ポリアクリル酸のアルカリ土類金属塩、グアガム誘導体、ポリアルキレンオキサイド及びセルロース系繊維などを好ましく挙げることができ、特に架橋型ポリアクリル酸ナトリウム、架橋型ポリアクリル酸カルシウムが好ましい。   Preferred examples of the water-absorbing material used in the present invention include polyacrylic acid, alkali metal salts of polyacrylic acid, alkaline earth metal salts of polyacrylic acid, guar gum derivatives, polyalkylene oxides and cellulosic fibers. In particular, crosslinked sodium polyacrylate and crosslinked calcium polyacrylate are preferred.

吸水材の含有量は前記廃イオン交換樹脂100質量部に対して20質量部以下であることが好ましく、10質量部以下であることがより好ましく、特に5質量部以下であることが好ましい。一般に使用されているポリアクリル酸などの吸水性ポリマーは、自重の10倍以上の水分を吸収が可能であるため、少量の使用でも廃イオン交換樹脂中の残留水分を十分に吸水することができる。吸水材の含有量が多すぎると、可燃性結合剤が廃イオン交換樹脂粒子間に行き渡らず、結合力が低下して固化体の強度も低下し、固化できない場合もある。これを避けるためには、可燃性結合材を増量する必要が生じ、経済的にも好ましくない。   The content of the water-absorbing material is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less with respect to 100 parts by mass of the waste ion exchange resin. Commonly used water-absorbing polymers such as polyacrylic acid can absorb water more than 10 times its own weight, so even if it is used in a small amount, it can absorb water remaining in the waste ion exchange resin sufficiently. . If the content of the water-absorbing material is too large, the combustible binder does not spread between the waste ion-exchange resin particles, the binding force is reduced, the strength of the solidified body is lowered, and solidification may not be achieved. In order to avoid this, it is necessary to increase the amount of the combustible binder, which is not preferable economically.

本発明で用いることができる可燃性結合材は、軟化点が水の沸点以下で且つ常温で固体である物質であることが好ましく、石油ワックス、植物性ワックス、木蝋、白蝋などを好ましく挙げることができる。石油ワックスとしては、軟化温度範囲が45〜55℃のパラフィンワックス、例えばＪＩＳＫ２２３５に規定されている１２５Ｐ、１３０Ｐ、１３５Ｐ、１４０Ｐ、１４５Ｐ、１５０Ｐ、１５５Ｐなどを好ましく用いることができる。本発明において可燃性結合材を加熱成形する場合には、可燃性結合材を融点に至らない温度での軟化した状態で用いることが好ましい。融点を超えると可燃性結合材の液状化現象が起こり、収量が極端に低下するので好ましくない。可燃性結合材を粉末又は粒状で用いる場合には、１５５Ｐ（粒状、顆粒状、紛状）や１４０Ｐ（顆粒状）が好ましい。なお、パラフィンワックスについて「融点」とは、溶融した試料を既定の条件で放冷したとき、試料の温度降下速度が規定の速度以下となったときの温度である（ＪＩＳＫ２２３５）。   The combustible binder that can be used in the present invention is preferably a substance that has a softening point below the boiling point of water and is solid at room temperature, and preferably includes petroleum wax, vegetable wax, wood wax, white wax, and the like. Can do. As the petroleum wax, a paraffin wax having a softening temperature range of 45 to 55 ° C., for example, 125P, 130P, 135P, 140P, 145P, 150P, 155P, etc. defined in JISK2235 can be preferably used. In the present invention, when the combustible binder is thermoformed, the combustible binder is preferably used in a softened state at a temperature that does not reach the melting point. Exceeding the melting point is not preferable because a liquefaction phenomenon of the combustible binder occurs and the yield is extremely reduced. When the combustible binder is used in powder or granular form, 155P (granular, granular, powdery) or 140P (granular) is preferred. Note that the “melting point” of paraffin wax is the temperature at which the temperature drop rate of the sample falls below a prescribed rate when the molten sample is allowed to cool under predetermined conditions (JISK2235).

可燃性結合材の含有量は、細粒状廃イオン交換樹脂100質量部に対して33質量部〜200質量部の範囲であることが好ましく、60質量部〜80質量部の範囲であることがより好ましい。この範囲であれば、廃イオン交換樹脂と可燃性結合材の混合体は、安定した形状を保つことが可能であり、その上、可燃性結合材の使用量を減少させることができるので経済的観点からも有利である。   The content of the combustible binder is preferably in the range of 33 parts by mass to 200 parts by mass, more preferably in the range of 60 parts by mass to 80 parts by mass with respect to 100 parts by mass of the fine granular waste ion exchange resin. preferable. Within this range, the mixture of the waste ion exchange resin and the combustible binder can maintain a stable shape, and furthermore, the amount of combustible binder used can be reduced, which is economical. It is also advantageous from the viewpoint.

本発明において用いることができるカルシウム塩としては、硝酸カルシウム、水酸化カルシウム、酢酸カルシウム、酸化カルシウム、炭酸カルシウム及び炭酸水素カルシウムなどを好ましく挙げることができる。カルシウム塩は、イオン交換樹脂、特に陽イオン交換樹脂中の硫酸イオンと反応して、硫酸カルシウムとして析出させるため、ＳＯｘの排出を抑止する。特に、硝酸カルシウムを用いる場合には、燃焼効率を高めることもでき、燃焼残渣を著しく削減できる。   Preferred examples of the calcium salt that can be used in the present invention include calcium nitrate, calcium hydroxide, calcium acetate, calcium oxide, calcium carbonate, and calcium hydrogen carbonate. The calcium salt reacts with the sulfate ion in the ion exchange resin, particularly the cation exchange resin, and precipitates as calcium sulfate, so that the emission of SOx is suppressed. In particular, when calcium nitrate is used, combustion efficiency can be increased and combustion residues can be significantly reduced.

本発明において用いることができるカルシウム塩の量は、イオン交換樹脂中に含まれる硫黄（Ｓ）の量に応じて変動する。典型的には、イオン交換樹脂中の硫黄に対して、1〜5wt％、好ましくは1〜2wt％の範囲となるように添加することが好ましく、一般的には、廃イオン交換樹脂100質量部に対して3.5質量部以上20質量部以下であることが好ましく、より好ましくは7質量部以上10質量部以下である。カルシウム塩を多量に用いることは、燃焼効率の向上及び燃焼残渣の低減には資するが、廃イオン交換樹脂の焼却処理の運転コストが高くなってしまうので好ましくない。一般的には、陽イオン交換樹脂1g中約15wt％の硫黄が含まれている。廃イオン交換樹脂が陽イオン交換樹脂と陰イオン交換樹脂とを１：１で含む場合、カルシウム塩の添加量を硫黄分に対して10wt％とすると、例えば硝酸カルシウムとして添加することができるカルシウム塩の量は、イオン交換樹脂１リットル当たり17.4gとなる。陽イオン交換樹脂中に含まれる硫黄に対して、その約0.4当量〜約0.8当量の水酸化カルシウムを添加することができる。   The amount of calcium salt that can be used in the present invention varies depending on the amount of sulfur (S) contained in the ion exchange resin. Typically, it is preferably added so as to be in the range of 1 to 5 wt%, preferably 1 to 2 wt% with respect to sulfur in the ion exchange resin, and generally 100 parts by mass of the waste ion exchange resin. Is preferably 3.5 parts by weight or more and 20 parts by weight or less, more preferably 7 parts by weight or more and 10 parts by weight or less. Use of a large amount of calcium salt contributes to improvement of combustion efficiency and reduction of combustion residues, but is not preferable because the operation cost of incineration treatment of waste ion exchange resin is increased. Generally, about 15 wt% sulfur is contained in 1 g of cation exchange resin. When the waste ion exchange resin contains a cation exchange resin and an anion exchange resin at a ratio of 1: 1, if the addition amount of calcium salt is 10 wt% with respect to the sulfur content, for example, calcium salt that can be added as calcium nitrate Is 17.4 g per liter of ion exchange resin. About 0.4 equivalents to about 0.8 equivalents of calcium hydroxide can be added to sulfur contained in the cation exchange resin.

したがって、本発明によれば、廃イオン交換樹脂と、可燃性結合材と、吸水材と、場合によってはカルシウム塩とを含む廃イオン交換樹脂の集合固化体が提供される。本発明による廃イオン交換樹脂の集合固化体の形状、寸法は、特に限定されるものではないが、汽力発電施設などが保有する通常の焼却設備で焼却処理可能な形状、寸法であることが好ましい。焼却炉の投入口を通過する大きさであれば、焼却処理は可能であるが、人による運搬を考慮し20kg以下が好ましい。さらに、本発明の廃イオン交換樹脂の集合固化体は、一般的な原子力発電所が保有する焼却設備で焼却することができるような強度を有することが好ましい。集合固化体は、焼却設備に投入する際に大部分が粉砕しない程度の強度、積載時の荷重や、運搬時の重機を使った衝撃に耐える程度の強度を持つことが好ましい。   Therefore, according to this invention, the aggregate solidification body of the waste ion exchange resin containing a waste ion exchange resin, a combustible binder, a water absorbing material, and the calcium salt depending on the case is provided. The shape and dimensions of the solidified solid body of the waste ion exchange resin according to the present invention are not particularly limited, but are preferably shapes and dimensions that can be incinerated by ordinary incineration facilities possessed by a power generation facility or the like. . Incineration is possible if it is large enough to pass through the inlet of the incinerator, but 20 kg or less is preferable in consideration of transportation by humans. Furthermore, it is preferable that the aggregated solidified body of the waste ion exchange resin of the present invention has such strength that it can be incinerated with an incineration facility owned by a general nuclear power plant. The aggregated solid body preferably has a strength that does not pulverize most when it is put into an incineration facility, a strength that can withstand a load during loading, and an impact using a heavy machine during transportation.

また、本発明によれば、本発明の廃イオン交換樹脂の集合固化体の製造方法を実施する製造装置が提供される。本発明の廃イオン交換樹脂集合固化体の製造装置は、廃イオン交換樹脂貯槽と、可燃性結合材貯槽と、吸水材貯槽と、該廃イオン交換樹脂貯槽からの廃イオン交換樹脂、該可燃性結合材貯槽からの可燃性結合材及び吸水材貯槽からの吸水材を計量する計量機構と、該計量機構により計量された廃イオン交換樹脂、可燃性結合材及び吸水材を受け入れ、混合する混合槽と、加熱手段を具備し、混合物を加熱しながら混練し、所望形状に成形する混練成形装置と、成形体を冷却する冷却手段と、を具備する。
［好ましい実施形態］
本方法の一実施形態として、原子力発電施設から排出される廃イオン交換樹脂を例にして、図面を参照しながら詳細に説明する。 Moreover, according to this invention, the manufacturing apparatus which enforces the manufacturing method of the aggregate solidification body of the waste ion exchange resin of this invention is provided. The apparatus for producing a solidified solid body of waste ion exchange resin according to the present invention includes a waste ion exchange resin storage tank, a combustible binder storage tank, a water absorbent storage tank, a waste ion exchange resin from the waste ion exchange resin storage tank, and a combustible substance. A metering mechanism for measuring the combustible binder from the binder storage tank and the water absorbent from the water absorbent storage tank, and a mixing tank for receiving and mixing waste ion exchange resin, combustible binder and water absorbent measured by the metering mechanism And a heating unit, kneading and molding the mixture while heating, and forming a desired shape, and a cooling unit for cooling the molded body.
[Preferred embodiment]
As an embodiment of this method, a waste ion exchange resin discharged from a nuclear power generation facility will be described as an example with reference to the drawings.

図１は、本発明の廃イオン交換樹脂集合固化体の製造装置による製造方法の工程を示す概略フロー図である。   FIG. 1 is a schematic flow diagram showing the steps of a production method using a production apparatus for a waste ion exchange resin aggregate solidified body of the present invention.

図１に示すように、本発明の製造装置は、廃イオン交換樹脂貯槽１０と、可燃性結合材貯槽２０と、吸水材貯槽３０と、廃イオン交換樹脂貯槽１０からの廃イオン交換樹脂、可燃性結合材貯槽２０からの可燃性結合材及び吸水材貯槽３０からの吸水材を計量する計量機構６０と、計量機構６０により計量された廃イオン交換樹脂、可燃性結合材及び吸水材を受け入れ、混合する混合槽７０と、加熱手段を具備し、混合物７２を加熱しながら混練して成形体８４に成形する混練成形装置８０と、成形体を冷却する冷却手段と、を具備する。図１に示すように、さらに、カルシウム塩貯槽４０及び予備貯槽５０を具備することが好ましい。予備貯槽５０は、必要に応じて、混合槽７０又は混練成形装置８０に供給するための任意の添加剤を貯蔵することができる。本発明の製造装置は、さらに、混練成形装置８０の出口に切断手段９０を具備し、切断手段９０により所望寸法に切断された集合固化体８６を貯蔵する固化体貯槽１００を具備し、該固化体貯槽１００は冷却手段としても作用する構成であることが好ましい。また、固化体貯槽１００は、焼却炉（図示せず）に集合固化体８６を投入する投入手段１１０を具備するものでもよい。   As shown in FIG. 1, the production apparatus of the present invention includes a waste ion exchange resin storage tank 10, a combustible binder storage tank 20, a water absorbent storage tank 30, a waste ion exchange resin from the waste ion exchange resin storage tank 10, and a combustible material. A measuring mechanism 60 for measuring the combustible binder from the water-soluble binder storage tank 20 and the water-absorbing material from the water-absorbing material storage tank 30, and receiving the waste ion exchange resin, combustible binder and water-absorbing material measured by the measuring mechanism 60; A mixing tank 70 for mixing, a heating unit, a kneading and forming apparatus 80 for kneading the mixture 72 while heating to form a molded body 84, and a cooling unit for cooling the molded body are provided. As shown in FIG. 1, it is preferable to further include a calcium salt storage tank 40 and a preliminary storage tank 50. The preliminary storage tank 50 can store any additive to be supplied to the mixing tank 70 or the kneading and forming apparatus 80 as necessary. The production apparatus of the present invention further includes a cutting means 90 at the outlet of the kneading and forming apparatus 80, and further includes a solidified body storage tank 100 for storing the aggregate solidified body 86 cut to a desired size by the cutting means 90. It is preferable that the body storage tank 100 has a configuration that also functions as a cooling means. Further, the solidified body storage tank 100 may include a charging unit 110 for charging the aggregate solidified body 86 into an incinerator (not shown).

次に、図１に示すフローに従って本発明の廃イオン交換樹脂集合固化体の製造方法を説明する。   Next, the manufacturing method of the waste ion exchange resin aggregate solidified body of this invention is demonstrated according to the flow shown in FIG.

一般的に、原子力発電施設からの廃イオン交換樹脂は放射性物質を吸着しているので、細粒状の廃イオン交換樹脂を廃棄物貯留槽（図示せず）に移送し水中保管している。廃棄物貯留槽（図示せず）に水中保管されていた廃イオン交換樹脂をメッシュスクリーン（図示せず）などを通過させて、樹脂表面水を粗く水切りする。粗水切りした廃イオン交換樹脂を、廃イオン交換樹脂貯槽１０に受入れ、計量機構６０に供給して計量した後、混合槽７０に投入する。次に、吸水材貯槽３０から吸水材を計量機構６０に供給して計量した後、廃イオン交換樹脂が投入されている混合槽７０に投入し、廃イオン交換樹脂と吸水材とを混合させて、廃イオン交換樹脂の残留水分を吸水材に吸水させる。次いで、可燃性結合材貯槽２０から可燃性結合材を計量機構６０に供給して計量した後、混合槽７０に投入し、脱水後の廃イオン交換樹脂と吸水後の吸水材との混合物に混合させる。このとき、カルシウム塩貯槽４０からカルシウム塩を計量機構６０で計量してから混合槽７０に投入して、可燃性結合材と一緒に廃イオン交換樹脂と吸水材との混合物に混合させてもよい。また全ての材料を混合機に投入してから混合しても良い。廃イオン交換樹脂と可燃性結合材とが均一に混合されるまで混合槽７０内で撹拌混合させる。   Generally, since waste ion exchange resin from nuclear power generation facilities adsorbs radioactive substances, fine granular waste ion exchange resin is transferred to a waste storage tank (not shown) and stored in water. The waste ion exchange resin stored in water in a waste storage tank (not shown) is passed through a mesh screen (not shown) or the like to roughly drain the resin surface water. The waste ion exchange resin from which the rough water has been drained is received in the waste ion exchange resin storage tank 10, supplied to the measuring mechanism 60, weighed, and then charged into the mixing tank 70. Next, after supplying the water absorbing material from the water absorbing material storage tank 30 to the measuring mechanism 60 and measuring it, the water absorbing material is added to the mixing tank 70 in which the waste ion exchange resin is charged, and the waste ion exchange resin and the water absorbing material are mixed. Then, the residual water of the waste ion exchange resin is absorbed by the water absorbing material. Next, after the combustible binder is supplied from the combustible binder storage tank 20 to the measuring mechanism 60 and weighed, it is put into the mixing tank 70 and mixed with the mixture of the dehydrated waste ion exchange resin and the water absorbent after water absorption. Let At this time, the calcium salt from the calcium salt storage tank 40 may be measured by the measuring mechanism 60 and then charged into the mixing tank 70, and may be mixed with the mixture of the waste ion exchange resin and the water absorbing material together with the combustible binder. . Further, all the materials may be mixed after being charged into the mixer. The waste ion exchange resin and the combustible binder are stirred and mixed in the mixing tank 70 until they are uniformly mixed.

次いで、混合槽７０で得られた混合物７２を材料供給機７８に一括または分割で投入し、さらに混合させた後、混合物８２を混練成形装置８０に定量供給し、可燃性結合材の軟化点以上で溶融点に至らない温度に維持しながら混練して、脱水後の廃イオン交換樹脂を可燃性結合材によって結合させて成形体８４とする。この成形体８４には、廃イオン交換樹脂の残留水分を吸水した吸水材と、廃イオン交換樹脂のスルホン酸などの硫黄分と結合させるためのカルシウム塩も含まれている。   Next, the mixture 72 obtained in the mixing tank 70 is added to the material supply machine 78 in a lump or dividedly and further mixed, and then the mixture 82 is quantitatively supplied to the kneading and forming apparatus 80 so as to exceed the softening point of the combustible binder. Then, the mixture is kneaded while maintaining the temperature not reaching the melting point, and the dehydrated waste ion exchange resin is bonded with a combustible binder to form a molded body 84. The molded body 84 also contains a water absorbing material that absorbs residual moisture of the waste ion exchange resin and a calcium salt for binding to a sulfur content such as sulfonic acid of the waste ion exchange resin.

混練成形装置（押出成形機）８０の出口に設けた回転ブレードなどの切断手段９０によって所望寸法に切断された成形体８４を袋１０２などに受入れて、固化体貯槽１００内に導入する。固化体貯槽１００内で放冷しながら貯蔵して、集合固化体８６とする。集合固化体８６は、焼却処理に供されるまで固化体貯槽１００内で保管される。固化体貯槽１００には、反転機構１１０などの投入手段が設けられていて、集合固化体８６を焼却装置に容易に投入できるようになされていることが好ましい。焼却処理は、汽力発電施設などが保有する通常の焼却装置にて焼却することが好ましい。   A molded body 84 cut to a desired size by a cutting means 90 such as a rotary blade provided at the outlet of a kneading molding apparatus (extrusion molding machine) 80 is received in a bag 102 or the like and introduced into the solidified body storage tank 100. The solidified body 86 is stored in the solidified body storage tank 100 while being allowed to cool to obtain a solidified body 86. The aggregate solidified body 86 is stored in the solidified body storage tank 100 until it is subjected to an incineration process. The solidified body storage tank 100 is preferably provided with charging means such as a reversing mechanism 110 so that the aggregate solidified body 86 can be easily charged into the incinerator. The incineration process is preferably incinerated with a normal incinerator owned by a steam power generation facility or the like.

本発明は上記実施形態に限定されるものではなく、種々の設計変更が可能であることは当業者には容易に理解されよう。以下、代表的な変更例を説明する。   The present invention is not limited to the above embodiment, and those skilled in the art will readily understand that various design changes are possible. Hereinafter, typical examples of changes will be described.

本発明の製造方法及び装置において、廃イオン交換樹脂を廃イオン交換樹脂貯槽１０内に貯蔵保管する前段階として、原子力発電設備などの廃イオン交換樹脂発生源から廃イオン交換樹脂を採取して、廃イオン交換樹脂貯槽１０に受入れる工程及び設備を含めることができる。廃イオン交換樹脂受入工程に用いることができる供給手段としては、台車などの人力による供給、又は動力揚重機、コンベア、リフター、フォークリフト、リーチフォークリフト、気送装置、ニーダー等の搬送装置を介しての動力による供給を挙げることができる。また、上記の搬送装置に、材料容器の開封装置、反転装置、掻き取り装置等を組み合わせてもよい。さらに、上述の供給手段は、手動により操作しても、自動制御してもよい。   In the production method and apparatus of the present invention, as a step before storing and storing the waste ion exchange resin in the waste ion exchange resin storage tank 10, the waste ion exchange resin is collected from a waste ion exchange resin generation source such as a nuclear power generation facility, A process and equipment to be received in the waste ion exchange resin storage tank 10 can be included. Supply means that can be used in the waste ion exchange resin receiving process include supply by human power such as a cart, or via a transport device such as a power lifting machine, conveyor, lifter, forklift, reach forklift, air feeding device, kneader, etc. Mention may be made of power supply. In addition, a material container opening device, a reversing device, a scraping device, or the like may be combined with the transport device. Furthermore, the above-described supply means may be operated manually or automatically.

本発明の廃イオン交換樹脂貯槽１０、可燃性結合材貯槽２０、吸水材貯槽３０、カルシウム塩貯槽４０及び予備貯槽５０としては、１バッチ若しくは数バッチの材料を保管し、固化体の製造に備える貯槽であればよく、例えば下記のような貯槽が考えられる。なお、材質は特に限定しない。（１）上面の全部又は一部及び／又は側面の一部が開放であり、材料投入が可能な投入口と排出口を有する容器。（２）人力または動力で開閉可能な蓋・扉を有する貯槽。（３）投入口にホッパを有する貯槽。（４）人力または動力で開閉可能な蓋・扉を有するホッパを具備する貯槽。（５）手動又は自動の材料容器の開封装置、反転装置、掻き取り装置を具備する貯槽。（６）覗き窓や体積計量目盛り等の目視計量手段を具備する貯槽。（７）材料を平滑に調整するノッカー、ショッカー、バイブレータ等の加震機を具備する貯槽。（８）赤外線・超音波等のレベル計、重量計又は重量センサなどの計量手段を具備する貯槽。（９）計量値を電気信号に変換して発信する信号発信装置を有する貯槽。（１０）規定量を作業者に告知する告知手段を有する貯槽。（１１）貯槽自体が移動・反転等できる構造であり、人力又は動力で、移送容器または混合槽に投入できる貯槽。（１２）水切り機構、ドレン回収機構、空気押出機構、負圧吸引機構を具備する貯槽。（１３）除湿、乾燥手段を具備する貯槽。   As the waste ion exchange resin storage tank 10, the combustible binder storage tank 20, the water absorbing material storage tank 30, the calcium salt storage tank 40, and the reserve storage tank 50 of the present invention, one batch or several batches of materials are stored to prepare for the production of a solidified body. Any storage tank may be used. For example, the following storage tanks are conceivable. The material is not particularly limited. (1) A container having an input port and a discharge port in which all or a part of the upper surface and / or a part of the side surface are open and materials can be input. (2) A storage tank with a lid and door that can be opened and closed by human power or power. (3) A storage tank having a hopper at the inlet. (4) A storage tank having a hopper having a lid / door that can be opened and closed by human power or power. (5) A storage tank having a manual or automatic material container opening device, a reversing device, and a scraping device. (6) A storage tank having visual weighing means such as a viewing window and a volumetric scale. (7) A storage tank equipped with a shaker such as a knocker, shocker or vibrator that adjusts the material smoothly. (8) A storage tank having measuring means such as a level meter such as infrared rays and ultrasonic waves, a weight meter, or a weight sensor. (9) A storage tank having a signal transmission device that converts a measured value into an electric signal and transmits the electric signal. (10) A storage tank having a notification means for notifying the operator of the specified amount. (11) A storage tank having a structure in which the storage tank itself can be moved and reversed, and can be charged into a transfer container or a mixing tank by human power or power. (12) A storage tank having a draining mechanism, a drain recovery mechanism, an air extrusion mechanism, and a negative pressure suction mechanism. (13) A storage tank having dehumidification and drying means.

また、廃イオン交換樹脂貯槽から廃イオン交換樹脂を計量機構６０又は混合槽７０に投入するために、以下のような排出機構をさらに具備していてもよい。（１）手動又は自動の弁手段を具備する排出機構。（２）覗き窓や計量部に体積計量目盛り等を有する目視計量手段を具備する排出機構。（３）材料を平滑に調整できる加震機等を具備する排出機構。（４）赤外線・超音波等のレベル計、重量計又は重量センサなどの計量機構を具備する排出機構。（５）計量値を電気信号に変換して発信する電気信号発信装置を有する排出機構。（６）規定量を作業者に告知できる告知手段を有する排出機構。（７）フィーダー、ニーダー、シリンダー等の定量供給機を具備する排出機構。（８）材料の詰まりを解消できるノッカー、ショッカー、バイブレータ等の加震機や内部攪拌装置等を具備する排出機構。   Further, in order to put the waste ion exchange resin from the waste ion exchange resin storage tank into the metering mechanism 60 or the mixing tank 70, the following discharge mechanism may be further provided. (1) A discharge mechanism having manual or automatic valve means. (2) A discharge mechanism provided with visual weighing means having a volumetric graduation or the like in a viewing window or weighing section. (3) A discharge mechanism equipped with a shaker or the like that can adjust the material smoothly. (4) A discharge mechanism equipped with a measuring mechanism such as a level meter such as infrared rays and ultrasonic waves, a weight meter or a weight sensor. (5) A discharge mechanism having an electrical signal transmission device that converts a measured value into an electrical signal and transmits the electrical signal. (6) A discharge mechanism having a notification means capable of notifying the operator of the specified amount. (7) A discharge mechanism including a quantitative feeder such as a feeder, a kneader, or a cylinder. (8) A discharge mechanism including a shaker such as a knocker, shocker, or vibrator that can eliminate clogging of materials, an internal stirring device, or the like.

また、計量機構６０としては、以下のような装置を利用することができる。（１）手動又は自動の材料容器の開封装置、反転装置、掻き取り装置を具備する計量槽。（２）覗き窓や計量部に体積計量目盛り等を付けた目視計量手段を具備する計量槽。（３）材料を平滑に調整できる加震機等を具備する計量槽。（４）赤外線・超音波等のレベル計、重量計又は重量センサなどの計量手段を有する計量槽。（５）計量値を電気信号に変換して、発信できる信号発信装置を有する計量槽。（６）規定量を作業者に告知できる告知手段を有する計量槽。（７）移送容器または混合機に投入するために計量槽自体を手動又は自動で移動・反転できる構造を具備する計量槽。（８）体積計量容器・重量計量器。   Moreover, as the measuring mechanism 60, the following devices can be used. (1) A measuring tank having a manual or automatic material container opening device, a reversing device, and a scraping device. (2) A measuring tank having a visual measuring means with a volumetric scale or the like attached to a viewing window or a measuring section. (3) A measuring tank equipped with a shaker or the like that can adjust the material smoothly. (4) A measuring tank having measuring means such as a level meter such as infrared rays and ultrasonic waves, a weight meter, or a weight sensor. (5) A measuring tank having a signal transmission device capable of converting a measurement value into an electric signal and transmitting the electric signal. (6) A measuring tank having a notification means capable of notifying the operator of the specified amount. (7) A measuring tank having a structure in which the measuring tank itself can be moved / reversed manually or automatically for feeding into a transfer container or a mixer. (8) Volume measuring container / weight measuring instrument.

また、混合槽７０としては、以下のような装置を利用することができる。（１）バケツや袋などの容器（手動又は撹拌機構により混合を行う）。（２）手動又は自動の材料容器の開封装置、反転装置、掻き取り装置を具備する混合槽。（３）覗き窓や計量部に体積計量目盛り等の目視計量手段を具備する混合槽。（４）材料を平滑に調整する加震機等を具備する混合槽。（５）赤外線・超音波等のレベル計、重量計又は重量センサなどの計量手段を具備する混合槽。（６）計量値を電気信号に変換して発信する信号発信手段を具備する混合槽。（８）規定量を作業者に告知できる告知手段を有する混合槽。（９）移送機器または成形機に投入するために混合機自体を手動又は自動で移動・反転できる構造を具備する混合槽。   Moreover, as the mixing tank 70, the following apparatuses can be utilized. (1) Containers such as buckets and bags (mixing is performed manually or by a stirring mechanism). (2) A mixing tank comprising a manual or automatic material container opening device, a reversing device, and a scraping device. (3) A mixing tank provided with a visual measuring means such as a volumetric scale on the viewing window or measuring section. (4) A mixing tank equipped with a shaker or the like for adjusting the material smoothly. (5) A mixing tank provided with measuring means such as a level meter such as infrared rays and ultrasonic waves, a weight meter, or a weight sensor. (6) A mixing tank provided with signal transmission means for converting a measured value into an electric signal and transmitting the electric signal. (8) A mixing tank having a notification means capable of notifying the operator of the specified amount. (9) A mixing tank having a structure in which the mixer itself can be moved or reversed manually or automatically for feeding into a transfer device or a molding machine.

また、混合槽７０から混練成形装置８０に混合物を供給するための材料供給機７８には、以下のような供給手段をさらに具備していてもよい。（１）台車、動力揚重機、コンベア、リフター、フォークリフト、リーチフォークリフト、気送装置、ニーダー等の手動又は自動の搬送装置。（２）材料の詰まりを防止するノッカー、ショッカー、バイブレータ等の加震機を具備する材料供給装置。（３）必要に応じ材料を加熱・冷却・真空乾燥が可能な機構又は装置を有する供給装置。（４）混練槽の材料過不足信号に対応し、供給速度を変速可能な装置を有する供給機。   Moreover, the material supply machine 78 for supplying the mixture from the mixing tank 70 to the kneading and forming apparatus 80 may further include supply means as described below. (1) Manual or automatic transfer devices such as carts, power hoists, conveyors, lifters, forklifts, reach forklifts, air feeding devices, kneaders. (2) A material supply apparatus including a shaker such as a knocker, shocker or vibrator that prevents clogging of the material. (3) A supply device having a mechanism or device capable of heating, cooling, and vacuum drying a material as necessary. (4) A feeder having a device capable of changing the feeding speed in response to the material excess / shortage signal of the kneading tank.

また、混練成形装置８０としては、以下のような装置を利用することができる。（１）人力で圧縮成形する成形機。（２）可燃性結合材の軟化温度範囲に温度制御する温度制御機構付き成形型枠を利用する加圧成形機。（３）可燃性結合材の軟化温度範囲に温度制御する温度制御機構付き成形型枠を利用し、手動又は自動で重量付加用液体を入れる液体利用加圧成形機。（４）可燃性結合材の軟化温度範囲に温度制御が可能である温度制御機構を具備する成形機。（５）加圧部直前の材料接触部又は成形機全体の冷却が可能な冷却手段を具備する成形機。（６）ブリケット、タブレット、ペレット等の造粒成形機。（７）スクリュー、シリンダ等の押出成形機（８）プレス、ホットプレス等の圧縮成形機等。（９）製造速度可変機構を具備する成形機。（１０）成形圧力検出・制御機構を具備する成形機。（１１）圧力変動に速度を追従できる圧力変動追従型製造速度可変機構を有する成形機。（１２）製造速度の変動を供給装置に追従信号として発信が可能な装置を有する成形機。（１３）過電流検出自動制御機構を具備する成形機。（１４）温度検出自動制御機構を具備する成形機。（１５）材料の真空乾燥が可能である真空乾燥装置を有する成形機。（１６）内部で材料の導電率等を測定し、水分の蓄積が有った場合に装置を停止したり警報等の発信が可能な水分検出自動制御機構を具備する成形機。（１７）成形機動力を利用して固化体を切断する切断機構を有する成形機。（１８）製造速度変動追従型切断速度制御機構を具備する成形機。   Further, as the kneading and forming apparatus 80, the following apparatuses can be used. (1) A molding machine that performs compression molding manually. (2) A pressure molding machine using a molding mold with a temperature control mechanism for controlling the temperature within the softening temperature range of the combustible binder. (3) A liquid-based pressure molding machine that uses a molding frame with a temperature control mechanism that controls the temperature within the softening temperature range of the combustible binder, and that manually or automatically puts a liquid for weight addition. (4) A molding machine including a temperature control mechanism capable of controlling the temperature within the softening temperature range of the combustible binder. (5) A molding machine provided with a cooling means capable of cooling the material contact part immediately before the pressurizing part or the entire molding machine. (6) A granulating machine for briquettes, tablets, pellets and the like. (7) Extruders such as screws and cylinders (8) Compression molding machines such as presses and hot presses. (9) A molding machine provided with a variable manufacturing speed mechanism. (10) A molding machine having a molding pressure detection / control mechanism. (11) A molding machine having a pressure fluctuation tracking type manufacturing speed variable mechanism capable of following the speed to the pressure fluctuation. (12) A molding machine having a device capable of transmitting a fluctuation in manufacturing speed as a follow-up signal to a supply device. (13) A molding machine provided with an overcurrent detection automatic control mechanism. (14) A molding machine equipped with a temperature detection automatic control mechanism. (15) A molding machine having a vacuum drying device capable of vacuum drying of materials. (16) A molding machine provided with a moisture detection automatic control mechanism capable of measuring the electrical conductivity of a material inside and stopping the apparatus or transmitting an alarm or the like when moisture has accumulated. (17) A molding machine having a cutting mechanism for cutting the solidified body using the power of the molding machine. (18) A molding machine provided with a manufacturing speed variation following type cutting speed control mechanism.

また、混練成形装置８０により得られた成形体はそのまま貯蔵しても良いが、集合固化体を所望の寸法とするために混練成形装置８０の出口で成形体を切断することが望ましく、以下のような方法及び切断機を利用してもよい。（１）手動により成形体を折るか、刃物等の道具を用いて切断する。（２）連続又は間欠で圧縮空気を成形体に吹き付けて、成形体を折る。（３）成形機出口に邪魔板等を設置し、成形体を衝突させて折る。（４）邪魔板等を単独又は複数取り付けた折り曲げ部を、人力又は動力により往復・回転運動させ成形体を折る。（５）動力で作動する刃物を用いて、成形体を切断する。（６）混練成形装置の製造速度信号に追従して切断速度を変速させて、成形体を切断する。（７）位置検出センサを用いて成形体の位置を検出して切断機を作動させ、成形体を切断する。（８）ローラコンベア等で成形体を受けて直線的に長く成形し、位置センサを用いて、所望の寸法、例えば固化体貯槽の内寸法に併せて切断する。   Further, the molded body obtained by the kneading and molding apparatus 80 may be stored as it is, but it is desirable to cut the molded body at the outlet of the kneading and molding apparatus 80 in order to make the aggregate solidified body have a desired size. Such a method and a cutting machine may be used. (1) The molded body is folded manually or cut using a tool such as a blade. (2) The compressed body is blown by blowing compressed air continuously or intermittently onto the molded body. (3) A baffle plate or the like is installed at the exit of the molding machine, and the molded body is collided and folded. (4) Folding the molded body by reciprocating / rotating the bent portion with one or more baffle plates or the like by human power or power. (5) The molded body is cut using a blade that operates with power. (6) The cutting speed is changed following the manufacturing speed signal of the kneading molding apparatus, and the molded body is cut. (7) The position of the molded body is detected using the position detection sensor, the cutting machine is operated, and the molded body is cut. (8) A molded body is received by a roller conveyor or the like, and is linearly elongated. Using a position sensor, the molded body is cut according to a desired dimension, for example, the inner dimension of the solidified body storage tank.

また、冷却手段としては固化体貯槽１００内で保管中に自然放冷する態様でもよいが、周囲温度が高温である場合には成形体同士が接着することを回避するために以下のような冷却方法を利用することができる。（１）人力又は動力により送風し、風冷する。（２）施設の換気空調の給気・排気を利用し風冷する。（３）成形体を液体に浸すか又は液体を噴霧して冷却する。（４）成形体を仮受け容器に受けて、放冷又は風冷、液体冷却した後に、固化体貯槽、袋、容器などに固化体を人力又は動力で投入する。   In addition, as a cooling means, a mode of naturally cooling during storage in the solidified body storage tank 100 may be used, but in order to avoid that the molded bodies adhere to each other when the ambient temperature is high, the following cooling is performed. The method can be used. (1) The air is blown and cooled by human power or power. (2) Use facility air supply / exhaust air cooling to cool the air. (3) The molded body is immersed in a liquid or sprayed with a liquid and cooled. (4) The molded body is received in a temporary receiving container and allowed to cool, wind, or liquid, and then the solidified body is charged into a solidified body storage tank, bag, container, etc. by human power or power.

本発明の集合固化体又は集合固化体の前駆体である成形体を固化体貯槽１００内に保管する場合には、焼却装置への投入の便を考慮して、袋１０２又は容器等に小分けして保管することが好ましい。袋は封をせずに開放したままでも、袋自体で縛ったり、紐、粘着テープ、ポリシーラ等を利用して封をしてもよい。固化体貯槽１００としては、ドラム缶等の硬質材料で、固化体の変形や飛散を防止できるように蓋をした場合に密封性が高く、輸送等に耐える強度を持ち、運搬性が良く重量測定が容易で、焼却炉に投入する際には反転装置等に容易に取付可能であるなどの特性を有する貯槽であることが好ましい。   When storing the aggregated solid body or the molded body precursor of the aggregated solid body of the present invention in the solidified body storage tank 100, it is subdivided into bags 102 or containers in consideration of the convenience of charging into the incinerator. It is preferable to store them. Even if the bag is left unopened without being sealed, it may be tied with the bag itself, or sealed with a string, an adhesive tape, a policyr or the like. The solidified body storage tank 100 is made of a hard material such as a drum can, and has a high sealing property when it is covered so as to prevent deformation and scattering of the solidified body. It is preferable that the storage tank has characteristics such that it can be easily attached to an inversion device or the like when being put into an incinerator.

また、本発明の廃イオン交換樹脂集合固化体を焼却装置へ投入する際には、台車、人力又は動力揚重機、コンベア、リフター、フォークリフト、リーチフォークリフト等の搬送装置を介し焼却炉の投入口付近まで貯槽を運搬した後に、以下のような投入方法を用いることができる。（１）人力で固化体又は袋詰めの固化体を投入する。（２）人力又は動力で貯槽を吊上げ、反転等を行い省力化できる装置を利用して投入する。（３）固化体貯槽１００から固化体単品又は袋詰めの固化体を、動力揚重機、コンベア、リフター、フォークリフト、リーチフォークリフト等の搬送装置を介し、焼却炉の投入口に投入する。（４）掻き取り装置を用いて投入する。   In addition, when the waste ion exchange resin aggregate solidified body of the present invention is thrown into the incinerator, the vicinity of the inlet of the incinerator through a conveying device such as a cart, manpower or power lifting machine, conveyor, lifter, forklift, reach forklift The following charging method can be used after transporting the storage tank to the bottom. (1) A solid or bag-packed solid is put in manually. (2) The storage tank is lifted by human power or power, and it is thrown in using a device that can invert and save labor. (3) A solidified product or a solidified product packed in a bag is charged from the solidified material storage tank 100 to a charging port of an incinerator through a conveying device such as a power lifting machine, a conveyor, a lifter, a forklift, and a reach forklift. (4) Use a scraping device.

本方法により得られた集合固化体は、目視確認により、廃イオン交換樹脂と可燃性結合材とが均一に混合しており、大きな割れ、引け巣がなく、既存の焼却設備に投入しても粉砕せずに必要な寸法を維持できるので、充分に焼却処理可能である。   The aggregate solidified body obtained by this method has been confirmed by visual confirmation that the waste ion exchange resin and the flammable binder are uniformly mixed, and there are no large cracks or shrinkage cavities. Since necessary dimensions can be maintained without crushing, incineration can be sufficiently performed.

また、本方法によれば、従来、スクリーンなどを内蔵した水切り容器に廃イオン交換樹脂を供給して、樹脂粒間水までを除去し、さらに乾燥機により樹脂粒間水を除去しなければ焼却処理できなかった廃イオン交換樹脂を、粗い水切りで樹脂表面に付着している水分だけを除去するだけでよいので、特殊な水切り及び乾燥設備が不要で非常に簡便である。   In addition, according to the present method, conventionally, waste ion exchange resin is supplied to a draining container having a built-in screen or the like to remove the water between the resin particles, and incineration unless the resin intergranular water is removed by a dryer. Since the waste ion exchange resin that could not be treated only needs to remove the water adhering to the resin surface by rough draining, special draining and drying equipment are not required, which is very simple.

さらに、特に陽イオン交換樹脂中に含まれる硫黄分からのSOx発生の問題を回避するために利用するカルシウム塩の添加を、吸水材により廃イオン交換樹脂の残留水分を除去した後に行うので、廃イオン交換樹脂の加圧時の液状化を防止することができ、集合固化体の安定連続製造が可能である。 In addition, the calcium salt used to avoid the problem of SO x generation from sulfur contained in the cation exchange resin is added after the residual moisture of the waste ion exchange resin is removed by the water absorbing material. It is possible to prevent liquefaction of the ion exchange resin during pressurization, and stable and continuous production of the aggregated solidified body is possible.

また、可燃性結合材とブレンドした後の集合固化体の成形も、単に放冷するだけで行うことができるので、非常に簡便である。   In addition, since the aggregated solid body after blending with the combustible binder can be formed simply by cooling, it is very simple.

以下、実施例を参照しながら本発明を説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated referring an Example, this invention is not limited to these.

図１に示す製造装置を用いて、表１に示す重量比率で廃イオン交換樹脂（陽イオン交換樹脂と陰イオン交換樹脂）に吸水材（ポリアクリル酸ナトリウム又はポリアクリル酸カルシウム）を計量添加して混合し、次に可燃性結合材（石油ワックス：日本製蝋（株）社製 顆粒状ワックス：PF-155；適性軟化温度範囲45〜55℃）を計量添加して混合し、最後にカルシウム塩（水酸化カルシウム）を計量添加して混合して混合物を形成させ、混合物をノズル部を約５５℃に加熱した連続式混練押出し成形装置（本田鐵工（株）社製 横軸スクリュー型押出成形機：HDE-３D）に供給し、加熱しながら混練・成形して成形体を形成し、連続式混練押出し成形機出口にて約100mmに切断して、本発明の廃イオン交換樹脂集合固化体を製造した。なお、実施例２で用いたポリアクリル酸カルシウムは、吸水材としての作用とカルシウム塩としての作用を兼備するため、実施例１で用いた吸水材（ポリアクリル酸ナトリウム）とカルシウム塩（水酸化カルシウム）の合計量（１７質量部）よりも少量（１５質量部）とした。   1. Using the manufacturing apparatus shown in FIG. 1, weigh and add a water-absorbing material (sodium polyacrylate or calcium polyacrylate) to waste ion exchange resin (cation exchange resin and anion exchange resin) at the weight ratio shown in Table 1. Next, weigh and add a flammable binder (petroleum wax: Nippon Wax Co., Ltd., granular wax: PF-155; suitable softening temperature range 45-55 ° C), and finally mix calcium Salt (calcium hydroxide) is metered in and mixed to form a mixture, and the mixture is continuously kneaded and extruded with a nozzle heated to about 55 ° C (Honda Seiko Co., Ltd. horizontal axis screw type extrusion) Molding machine: HDE-3D), kneaded and molded with heating to form a molded body, cut to about 100mm at the outlet of continuous kneading extrusion molding machine, solidified waste ion exchange resin of the present invention The body was manufactured. In addition, since the polycalcium acrylate used in Example 2 has the effect | action as a water absorbing material and the effect | action as a calcium salt, the water absorbing material (polyacrylic acid sodium) used in Example 1 and calcium salt (hydroxylation) A smaller amount (15 parts by mass) than the total amount (17 parts by mass) of calcium.

吸水材を使用しなかった以外は上述の方法と同様にして、対照の廃イオン交換樹脂集合固化体を製造した。   A control waste ion-exchange resin aggregate was produced in the same manner as described above except that no water-absorbing material was used.

本発明の装置による連続製造性及び焼却装置での焼却状態を目視により確認した。結果を表１に示す。   The continuous productivity by the apparatus of the present invention and the incineration state in the incinerator were confirmed visually. The results are shown in Table 1.

Figure 0004580326
Figure 0004580326

連続製造性に関して、対照では運転開始直後は１０ｋｇ／ｈ程度の処理が可能であったが、水分の圧搾蓄積により収量が徐々に低下し、運転開始３０分後には収量はほとんどゼロとなった。一方、吸水材としてポリアクリル酸塩を添加した実施例１及び２では６０ｋｇ／ｈの収量が常時達成可能であった。   Regarding the continuous productivity, in the control, a treatment of about 10 kg / h was possible immediately after the start of operation, but the yield gradually decreased due to the accumulation of moisture by pressing, and the yield became almost zero after 30 minutes from the start of operation. On the other hand, in Examples 1 and 2 in which polyacrylate was added as a water absorbing material, a yield of 60 kg / h could always be achieved.

得られた集合固化体の外観や形状を目視により、有意な割れなどがないことを確認した。更に、集合固化体を３メートルの高さからコンクリートの平坦な床に自由落下させて、有意な変形やひび割れが生じないことを確認した。また、加熱空気を連続して供給できる常圧の小型焼却炉を700℃に予熱し、集合固化体を数百グラム投入したところ、短時間で着火して良好な燃焼状態を示した。また、間欠的に集合固化体を追加投入したところ、良好な燃焼状態を継続して維持できることが確認された。さらに、燃焼空気を分析したところ、主な有害成分と考えられるSOｘの濃度は1ppm以下と良好であることを確認した。 It was confirmed by visual observation of the appearance and shape of the obtained solidified body that there were no significant cracks. Furthermore, the aggregate solidified body was allowed to fall freely from a height of 3 meters onto a flat concrete floor, and it was confirmed that no significant deformation or cracking occurred. In addition, when a small-sized incinerator with normal pressure capable of continuously supplying heated air was preheated to 700 ° C and charged with several hundred grams of aggregated solid, it ignited in a short time and showed a good combustion state. Moreover, when the aggregate solidified body was additionally added intermittently, it was confirmed that a good combustion state could be continuously maintained. Furthermore, when the combustion air was analyzed, it was confirmed that the concentration of SO x considered to be a major harmful component was as good as 1 ppm or less.

本発明によれば、細粒状の廃イオン交換樹脂を既設の焼却設備で焼却処理可能な形態とした集合固化体及びその成形方法及び焼却処理方法が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the aggregate solidified body made into the form which can be incinerated with the existing incineration equipment, and its shaping | molding method and incineration processing method are provided.

本発明の集合固化体は、従来提案されているイオン交換樹脂の処理方法の問題点、すなわち乾燥処理によりイオン交換樹脂の粒内水を除去する前処理工程が必要であること；廃イオン交換樹脂が細粒状であり、樹脂移送が煩雑であること；など焼却処理の困難さなどをすべて解決し、低コストで効率的、且つ安定的な焼却処理を可能にする。   The aggregate solidified body of the present invention requires a pretreatment process for removing the intragranular water of the ion exchange resin by a drying process, that is, a problem of the conventionally proposed ion exchange resin treatment method; waste ion exchange resin It is fine-grained and the resin transfer is complicated; all the difficulties of incineration such as are solved, and efficient and stable incineration is possible at low cost.

そして、廃イオン交換樹脂と吸水材とを混合させて、吸収材に廃イオン交換樹脂の残留水分を吸水させた後に、カルシウム塩を添加することにより、安定的に集合固化体を製造すると共に、陽イオン交換樹脂焼却時に発生するＳＯｘを抑制することができ、焼却炉の腐食問題及び環境中へのＳＯｘ排気問題を解決することができる。   And, after mixing the waste ion exchange resin and the water absorbing material, and absorbing the residual moisture of the waste ion exchange resin to the absorbent material, by adding calcium salt, stably producing the aggregate solidified body, SOx generated at the time of cation exchange resin incineration can be suppressed, and the problem of corrosion of the incinerator and the problem of exhausting SOx into the environment can be solved.

また、本発明によれば、原子力発電施設などにおいて、これまで適切な処理方法がないため大量に保管され、今後も増加することが予測されている放射性廃棄物としての廃イオン交換樹脂を可燃性結合材と一緒に集合固化体として成形することにより、各原子力発電施設などが保有している既設の焼却設備を用いて容易に焼却処理可能にする。よって、新規な処理設備又は既設の処理設備を改良するなどの設備投資を伴わずに、大量に保管されている廃イオン交換樹脂を従来の雑固体を焼却する態様で容易に且つ効率的に、低コストで焼却処理可能とする。   Further, according to the present invention, in a nuclear power generation facility or the like, waste ion exchange resin as a radioactive waste that has been stored in large quantities because there is no appropriate treatment method so far and is expected to increase in the future is combustible. By forming it as a solidified body together with the binder, it is possible to easily incinerate using existing incineration facilities owned by each nuclear power generation facility. Therefore, it is easy and efficient to incinerate conventional miscellaneous solids of waste ion exchange resin stored in large quantities without capital investment such as improvement of new processing equipment or existing processing equipment, Incineration is possible at low cost.

さらに、本発明は、原子力発電施設からの廃イオン交換樹脂のみならず、火力発電所その他の設備からの廃イオン交換樹脂にも適用可能である。よって、近年、特に問題となっている産業廃棄物の減容化及び焼却処理の一助となる。   Furthermore, the present invention is applicable not only to waste ion exchange resins from nuclear power generation facilities, but also to waste ion exchange resins from thermal power plants and other facilities. Therefore, in recent years, it is helpful for volume reduction and incineration of industrial waste, which has become a particular problem.

図１は、本発明の連続製造方法及び装置の工程フローを示す概略図である。FIG. 1 is a schematic view showing a process flow of the continuous production method and apparatus of the present invention.

符号の説明Explanation of symbols

１０：廃イオン交換樹脂貯槽
２０：可燃性結合材貯槽
３０：吸水材貯槽
４０：カルシウム塩貯槽
６０：計量機構
７０：混合槽
７８：材料供給機
８０：混練成形装置
９０：切断手段
１００：固化体貯槽 10: Waste ion exchange resin storage tank 20: Combustible binder storage tank 30: Water absorbing material storage tank 40: Calcium salt storage tank 60: Metering mechanism 70: Mixing tank 78: Material feeder 80: Kneading molding apparatus 90: Cutting means 100: Solidified body Storage tank

Claims (12)

廃イオン交換樹脂から樹脂表面水を除去する粗水切り工程と、
粗水切りした後の廃イオン交換樹脂と、ポリアクリル酸、ポリアクリル酸アルカリ金属塩、ポリアクリル酸アルカリ土類金属塩及びセルロース系繊維から選択される吸水材とを前記廃イオン交換樹脂１００質量部に対して２０質量部以下の比率で混合して、該吸水材に該廃イオン交換樹脂の残留水分を吸水させる吸水工程と、
吸水後の廃イオン交換樹脂と吸水材とに、軟化点が水の沸点以下で且つ常温で固体である石油ワックス、植物性ワックス、木蝋、白蝋から選択される粉末又は粒状の可燃性結合材を、前記廃イオン交換樹脂１００質量部に対して３３質量部〜２００質量部の範囲の比率で添加し混合する可燃性結合材添加工程と、
吸水後の廃イオン交換樹脂と吸水材と可燃性結合材との混合物を混錬成形機に供給する工程と、
吸水後の廃イオン交換樹脂と吸水材と該可燃性結合材とを可燃性結合材の軟化点以上で溶融点に至らない温度に維持しながら混練して、所望の形状の成形体に成形する混練成形工程と、
該成形体を冷却し固体化する冷却固化工程と、
を含む、廃イオン交換樹脂の集合固化体の製造方法。 A rough draining process for removing water on the resin surface from the waste ion exchange resin;
100 parts by mass of the waste ion-exchange resin after draining the coarse ion and the water-absorbing material selected from polyacrylic acid, alkali metal polyacrylate, alkaline earth metal polyacrylate, and cellulosic fiber A water absorption step of mixing at a ratio of 20 parts by mass or less with respect to the water absorption material to absorb the residual moisture of the waste ion exchange resin,
A powder or granular flammable binder selected from petroleum wax, vegetable wax, wood wax, and white wax whose softening point is below the boiling point of water and is solid at room temperature, after waste water absorption resin and water absorbing material A combustible binder addition step of adding and mixing at a ratio in the range of 33 parts by mass to 200 parts by mass with respect to 100 parts by mass of the waste ion exchange resin ,
Supplying a mixture of the waste ion exchange resin after absorbing water, the water absorbing material and the combustible binder to the kneading molding machine;
The waste ion exchange resin after absorbing water, the water absorbing material, and the flammable binder are kneaded while maintaining the temperature above the softening point of the flammable binder and not reaching the melting point to form a molded body having a desired shape. A kneading and molding process;
A cooling and solidifying step of cooling and solidifying the molded body;
The manufacturing method of the aggregate solidification body of waste ion exchange resin containing this. 前記吸水材を前記廃イオン交換樹脂１００質量部に対して１０質量部以下の比率で混合する、請求項１に記載の製造方法。The manufacturing method of Claim 1 which mixes the said water absorbing material in the ratio of 10 mass parts or less with respect to 100 mass parts of said waste ion exchange resins. 前記吸水材を前記廃イオン交換樹脂１００質量部に対して５質量部以下の比率で混合する、請求項１に記載の製造方法。The manufacturing method of Claim 1 which mixes the said water absorbing material in the ratio of 5 mass parts or less with respect to 100 mass parts of said waste ion exchange resins. 前記吸水材は、ポリアクリル酸カルシウムである、請求項１に記載の製造方法。 The manufacturing method according to claim 1, wherein the water absorbing material is calcium polyacrylate . 前記吸水材は、ポリアクリル酸ナトリウムである、請求項１に記載の製造方法。 The manufacturing method according to claim 1, wherein the water absorbing material is sodium polyacrylate . 前記ポリアクリル酸ナトリウムを前記廃イオン交換樹脂１００質量部に対して５質量部以下の比率で混合する、請求項５に記載の製造方法。 The manufacturing method of Claim 5 which mixes the said sodium polyacrylate with the ratio of 5 mass parts or less with respect to 100 mass parts of said waste ion exchange resins. 廃イオン交換樹脂から樹脂表面水を除去する粗水切り工程と、
粗水切りした後の廃イオン交換樹脂と、ポリアクリル酸、ポリアクリル酸アルカリ金属塩、ポリアクリル酸アルカリ土類金属塩及びセルロース系繊維から選択される吸水材とを前記廃イオン交換樹脂１００質量部に対して２０質量部以下の比率で混合して、該吸水材に該廃イオン交換樹脂の残留水分を吸水させる吸水工程と、
吸水後の廃イオン交換樹脂と吸水材とに、軟化点が水の沸点以下で且つ常温で固体である石油ワックス、植物性ワックス、木蝋、白蝋から選択される粉末又は粒状の可燃性結合材を、前記廃イオン交換樹脂１００質量部に対して３３質量部〜２００質量部の範囲の比率で添加し混合する可燃性結合材添加工程と、
吸水後の廃イオン交換樹脂と吸水材と可燃性結合材とに、カルシウム塩を前記廃イオン交換樹脂１００質量部に対して３．５質量部以上２０質量部以下の範囲で添加するカルシウム塩添加工程と、
吸水後の廃イオン交換樹脂と吸水材と可燃性結合材とカルシウム塩との混合物を混錬成形機に供給する工程と、
吸水後の廃イオン交換樹脂と吸水材と該可燃性結合材とカルシウム塩とを可燃性結合材の軟化点以上で溶融点に至らない温度に維持しながら混練して、所望の形状の成形体に成形する混練成形工程と、
該成形体を冷却し固体化する冷却固化工程と、
を含む、廃イオン交換樹脂の集合固化体の製造方法。 A rough draining process for removing water on the resin surface from the waste ion exchange resin;
100 parts by mass of the waste ion-exchange resin after draining the coarse ion and the water-absorbing material selected from polyacrylic acid, alkali metal polyacrylate, alkaline earth metal polyacrylate, and cellulosic fiber A water absorption step of mixing at a ratio of 20 parts by mass or less with respect to the water absorption material to absorb the residual moisture of the waste ion exchange resin,
A powder or granular flammable binder selected from petroleum wax, vegetable wax, wood wax, and white wax whose softening point is below the boiling point of water and is solid at room temperature, after waste water absorption resin and water absorbing material A combustible binder addition step of adding and mixing at a ratio in the range of 33 parts by mass to 200 parts by mass with respect to 100 parts by mass of the waste ion exchange resin,
Calcium salt addition in which calcium salt is added in a range of 3.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the waste ion exchange resin to the waste ion exchange resin, the water absorbing material, and the combustible binder after water absorption. Process,
Supplying a mixture of waste ion exchange resin, water absorbing material, flammable binder and calcium salt after water absorption to a kneading molding machine;
A molded product having a desired shape by kneading the waste ion exchange resin after absorbing water, the water absorbing material, the combustible binder, and the calcium salt while maintaining the temperature not lower than the softening point of the combustible binder and reaching the melting point. A kneading and molding step to form into,
A cooling and solidifying step of cooling and solidifying the molded body ;
The manufacturing method of the aggregate solidification body of waste ion exchange resin containing this. 前記カルシウム塩添加工程において、吸水後の廃イオン交換樹脂と吸水材と可燃性結合材とに、カルシウム塩を前記廃イオン交換樹脂１００質量部に対して７質量部以上１０質量部以下の範囲で添加する、請求項７に記載の製造方法。In the calcium salt addition step, the calcium salt is added to the waste ion exchange resin, the water absorbing material, and the combustible binder after water absorption in a range of 7 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the waste ion exchange resin. The manufacturing method of Claim 7 added. 廃イオン交換樹脂の貯槽と、
軟化点が水の沸点以下で且つ常温で固体である石油ワックス、植物性ワックス、木蝋、白蝋から選択される可燃性結合材の貯槽と、
ポリアクリル酸、ポリアクリル酸アルカリ金属塩、ポリアクリル酸アルカリ土類金属塩及びセルロース系繊維から選択される吸水材の貯槽と、
該廃イオン交換樹脂の貯槽からの廃イオン交換樹脂、該可燃性結合材の貯槽からの可燃性結合材及び吸水材の貯槽からの吸水材を計量する計量機構と、
該計量機構により計量された廃イオン交換樹脂、可燃性結合材及び吸水材を受け入れ、混合する混合槽と、
加熱手段を具備し、混合物を加熱混練しながら所望形状の成形体に成形する混練成形装置と、
成形体を冷却する冷却手段と、
を具備する、廃イオン交換樹脂の集合固化体の製造装置。 A storage tank of waste ion exchange resin;
A tank of combustible binder selected from petroleum wax, vegetable wax, wood wax, white wax having a softening point below the boiling point of water and solid at room temperature ;
Polyacrylic acid, a storage tank of water absorbent material is selected from polyacrylic acid alkali metal salt, polyacrylic acid alkaline earth metal salt and cellulosic fibers,
A metering mechanism for metering the waste ion-exchange resin from the reservoir of the waste ion-exchange resin, the water absorbent material from the reservoir of combustible binder and the water-absorbing material from the reservoir of the combustible binder,
A mixing tank that receives and mixes the waste ion exchange resin, the combustible binder, and the water absorbing material measured by the measuring mechanism;
A kneading and forming apparatus comprising a heating means and forming the mixture into a molded body having a desired shape while heating and kneading the mixture;
A cooling means for cooling the molded body;
An apparatus for producing an aggregate solidified body of waste ion exchange resin. さらに、カルシウム塩の貯槽を具備する、請求項９に記載の製造装置。 Further comprises a reservoir of calcium salt manufacturing apparatus according to claim 9. さらに、前記成形装置の出口に成形体を切断する切断手段を具備する、請求項９又は１０に記載の製造装置。 Furthermore, the manufacturing apparatus of Claim 9 or 10 provided with the cutting means which cut | disconnects a molded object at the exit of the said shaping | molding apparatus. 前記冷却手段は、固化体の貯槽である、請求項９〜１１のいずれか１項に記載の製造装置。 The said cooling means is a manufacturing apparatus of any one of Claims 9-11 which is a storage tank of a solidified body.
JP2005329857A 2005-11-15 2005-11-15 Method for producing waste ion exchange resin aggregates Active JP4580326B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005329857A JP4580326B2 (en) 2005-11-15 2005-11-15 Method for producing waste ion exchange resin aggregates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005329857A JP4580326B2 (en) 2005-11-15 2005-11-15 Method for producing waste ion exchange resin aggregates

Publications (2)

Publication Number Publication Date
JP2007136274A JP2007136274A (en) 2007-06-07
JP4580326B2 true JP4580326B2 (en) 2010-11-10

Family

ID=38199769

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005329857A Active JP4580326B2 (en) 2005-11-15 2005-11-15 Method for producing waste ion exchange resin aggregates

Country Status (1)

Country Link
JP (1) JP4580326B2 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011069753A (en) * 2009-09-28 2011-04-07 Hitachi-Ge Nuclear Energy Ltd System and method solidification treatment of used resin
JP5795242B2 (en) * 2011-10-28 2015-10-14 株式会社荏原製作所 Method for producing a solidified body of radioactive waste and a solidified body
JP5961046B2 (en) * 2012-06-12 2016-08-02 株式会社荏原製作所 Production method and production apparatus for radioactive waste ion-exchange resin aggregates
JP6596208B2 (en) * 2015-02-27 2019-10-23 株式会社荏原製作所 Method and apparatus for producing waste oil solidified body
KR101674345B1 (en) * 2016-03-31 2016-11-10 세안기술 주식회사 A pelletizing method of the concentrated waste solidified by paraffin and equipment thereof
KR101676274B1 (en) 2016-05-24 2016-11-29 세안기술 주식회사 A pelletizing system of the concentrated waste solidified by paraffin and controll method thereof
JP6983843B2 (en) * 2019-09-05 2021-12-17 株式会社小熊鉄工所 Waste dehydration and solidification equipment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000266896A (en) * 1999-03-17 2000-09-29 Ngk Insulators Ltd Processing method for waste ion exchange resin
JP2005031060A (en) * 2003-06-16 2005-02-03 Ebara Corp Molding and incineration method of solidified aggregate

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0666999B2 (en) * 1984-11-08 1994-08-24 日通工株式会社 Visible display method in button telephone device
JPS61128197A (en) * 1984-11-28 1986-06-16 株式会社日立製作所 Method of treating radioactive spent ion exchange resin
JPS61139356A (en) * 1984-12-11 1986-06-26 Takai Seisakusho:Kk Preparation of fried bean curd having strong fried skin
JPS61213797A (en) * 1985-03-20 1986-09-22 三井造船株式会社 Incineration treatment method of radioactive contaminated waste ion exchange resin
JPS62214400A (en) * 1986-03-17 1987-09-21 三菱重工業株式会社 Method of processing waste resin from nuclear power plant
JPS63229400A (en) * 1987-03-18 1988-09-26 株式会社日立製作所 Processing method of radioactive waste
JPS6324199A (en) * 1987-06-26 1988-02-01 株式会社日立製作所 Method of processing radioactive waste
JPH05150095A (en) * 1991-11-27 1993-06-18 Hitachi Ltd Solidifying method for used ion exchange resin
JPH1066866A (en) * 1996-08-28 1998-03-10 Nippon Soda Co Ltd Evacuation treatment agent for nursing
JP3806214B2 (en) * 1997-01-24 2006-08-09 Ｔｄｋ株式会社 Writable plastic label and method for manufacturing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000266896A (en) * 1999-03-17 2000-09-29 Ngk Insulators Ltd Processing method for waste ion exchange resin
JP2005031060A (en) * 2003-06-16 2005-02-03 Ebara Corp Molding and incineration method of solidified aggregate

Also Published As

Publication number Publication date
JP2007136274A (en) 2007-06-07

Similar Documents

Publication Publication Date Title
JP4580326B2 (en) Method for producing waste ion exchange resin aggregates
CN104874587A (en) System for treatment of fly ash from waste incineration
CA2708501A1 (en) Manufactured aggregate material and method
CN213557402U (en) Carbon black powder granulation system
JP5961046B2 (en) Production method and production apparatus for radioactive waste ion-exchange resin aggregates
CN205269646U (en) Waste incineration fly ash treatment system
CN115155365A (en) Glass kiln smoke dust recycling system and method
CN214288134U (en) Automatic system for preparing nano energy-absorbing material
CN209577720U (en) A kind of granular curing system of asphalt waste
CN207287538U (en) A kind of Concrete multifunctional corrosion remover production system
CN209178345U (en) A kind of waste emulsified mixture sludge treatment equipment
CN112642092A (en) Mobile household garbage incineration fly ash emergency curing and stabilizing equipment
CN208527662U (en) A kind of solid waste stabilization processes device
CN210145941U (en) Chemical fertilizer agitating unit for farming
JP3015237B2 (en) Radioactive waste solidification equipment
CN113694792A (en) Automatic mixing system and mixing method for drilling fluid
CN209502540U (en) A kind of flyash curing chelating device
CN108311527A (en) A kind of solid waste stabilization processes device
CN109385321A (en) A kind of waste emulsified mixture oil-sludge treatment method
CN219169202U (en) Closed automatic pretreatment and solidification treatment system for mercury-containing waste
JPH1190205A (en) Granulating machine
CN215463475U (en) Improvement type flying dust chelate dosing unit
JP2011240319A (en) Method for disposing waste residues and waste residues granulator
CN214266154U (en) Mortar production line is with storehouse of weighing
CN212892859U (en) Ton bag breaking measurement pneumatic conveying system

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20071219

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100215

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100303

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20100427

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20100804

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20100827

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130903

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Ref document number: 4580326

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250