JP3095748B1 - Cement solidifying material for boric acid, cement solidifying method of boric acid, and cement solidified body - Google Patents
Cement solidifying material for boric acid, cement solidifying method of boric acid, and cement solidified bodyInfo
- Publication number
- JP3095748B1 JP3095748B1 JP27964899A JP27964899A JP3095748B1 JP 3095748 B1 JP3095748 B1 JP 3095748B1 JP 27964899 A JP27964899 A JP 27964899A JP 27964899 A JP27964899 A JP 27964899A JP 3095748 B1 JP3095748 B1 JP 3095748B1
- Authority
- JP
- Japan
- Prior art keywords
- boric acid
- cement
- solidifying
- lithium hydroxide
- solidifying material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00862—Uses not provided for elsewhere in C04B2111/00 for nuclear applications, e.g. ray-absorbing concrete
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
【要約】
【課題】 多量のほう酸を混入しても固化することを可
能としたほう酸用セメント固化材、ほう酸のセメント固
化方法及び固化体を提供する。
【解決手段】 セメントにアルミン酸ナトリウムを配合
した。さらに、助材として水酸化リチウムを用いた。An object of the present invention is to provide a cement solidifying material for boric acid, a method of solidifying boric acid cement, and a solidified body, which can solidify even if a large amount of boric acid is mixed. SOLUTION: Sodium aluminate is added to cement. Further, lithium hydroxide was used as an auxiliary material.
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、ほう酸用セメント
固化材、ほう酸のセメント固化方法及びセメント固化体
に関する。The present invention relates to a cement solidifying material for boric acid, a method of solidifying boric acid cement, and a cement solidified body.
【０００２】[0002]
【従来の技術】従来、加圧水型軽水炉（ＰＷＲ）では、
炉心で加熱された一次冷却（減速）水を蒸気発生器内の
細管内に供給し、この蒸気発生器で二次冷却水を加熱す
ることにより発生させた蒸気でタービン発電機を稼動さ
せることとしている。一次冷却水には、中性子吸収能の
高いほう酸が原子炉の反応・制御に利用する目的で添加
されている。使用済みの一次冷却水中のほう酸は、セメ
ントによって固化処理されている。ここで、ほう酸は、
セメントの固化を阻害するため、多量に混入させること
ができない。そこで、従来、予めカルシウム（Ｃａ）塩
として不溶化するかあるいは縮合リン酸を用いて固化す
ることが試みられている。しかし、カルシウム塩とする
と、不溶性のほう酸カルシウムが配管その他へスケーリ
ングする可能性があった。また、縮合リン酸を用いる方
法では、環境汚染となるリン酸を用いることが現実的で
はない等の問題があった。2. Description of the Related Art Conventionally, in a pressurized water reactor (PWR),
The primary cooling (deceleration) water heated in the reactor core is supplied into the narrow tube in the steam generator, and the steam generated by heating the secondary cooling water with this steam generator is used to operate the turbine generator. I have. Boric acid with high neutron absorption capacity is added to the primary cooling water for the purpose of using it for the reaction and control of the reactor. Boric acid in the used primary cooling water has been solidified by cement. Here, boric acid is
Since it inhibits the solidification of cement, it cannot be mixed in large amounts. Therefore, conventionally, attempts have been made to insolubilize in advance as a calcium (Ca) salt or to solidify using a condensed phosphoric acid. However, when calcium salts were used, insoluble calcium borate could be scaled to piping and the like. In addition, the method using condensed phosphoric acid has a problem that it is not practical to use phosphoric acid which causes environmental pollution.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記事情に
対してなされたものであり、多量のほう酸を混入しても
固化することを可能としたほう酸用セメント固化材、ほ
う酸のセメント固化方法及び固化体を提供することを目
的とする。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a cement solidifying material for boric acid and a method of cementing boric acid, which can solidify even if a large amount of boric acid is mixed therein. And a solidified body.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するた
め、本発明は、ほう酸用セメント固化材であって、セメ
ントに固化促進材としてアルミン酸ナトリウムを配合し
たことを特徴とする。セメントとしては、高炉セメン
ト、ポルトランドセメントを一般的に用いることができ
る。また、さらに放射能固定材として、例えば、粉末ゼ
オライトを配合することもできる。本発明は、このよう
なほう酸用セメント固化材に対して、助材として水酸化
リチウムを添加することも含む。水酸化リチウムを助材
として添加することにより、固化速度を調整することが
できる。In order to achieve the above-mentioned object, the present invention provides a cement solidifying material for boric acid, characterized in that sodium aluminate is added to cement as a solidifying accelerator. As the cement, blast furnace cement and Portland cement can be generally used. Further, as the radioactivity fixing material, for example, powdered zeolite can be blended. The present invention also includes the addition of lithium hydroxide as an auxiliary to such cement hardened material for boric acid. The solidification rate can be adjusted by adding lithium hydroxide as an auxiliary material.
【０００５】本発明に係るほう酸用セメント固化材は、
ほう酸のセメント固化材に固化促進材としてアルミン酸
ナトリウムの他、助材として用いる水酸化リチウムを予
め含むこともできる。すなわち、「アルミン酸ナトリウ
ムを配合する」とは、水酸化リチウムを併せて配合する
ことも含む。本発明に係るほう酸用セメント固化材は、
固化材中にアルミン酸ナトリウムを固化材全体の重量に
対し、少なくとも１５ｗｔ％含む。これ以下であると、
セメント固化体の十分な強度を得ることが困難である。
そして、このような強度面からは、好適には２０ｗｔ％
以上含むことが好適である。理論的には、アルミン酸ナ
トリウムと必要な量の水酸化リチウムのみから成る固化
材も可能であるが、アルミン酸ナトリウムの量が多すぎ
ると過度に固化しやすくなって混錬しにくくなる。そこ
で、固化材中に少なくとも５１ｗｔ％のセメントを含む
ことが好適である。このようなことを考慮して、アルミ
ン酸ナトリウムの好適な配合範囲は、固化材のうち２０
〜４０ｗｔ％である。水酸化リチウム（結合水１分子を
含む、本明細書中では全て結合水を含めて考慮する）
は、アルミン酸ナトリウムとの重量比で１０％以上であ
って１００％以下、さらに好適には、１４〜２０％の範
囲で用いる。ここで用いるとは、固化材とは異なる助材
として用いることも、予め固化材の一部として用いるこ
とも含む。The cement solidifying material for boric acid according to the present invention comprises:
In addition to sodium aluminate as a solidification accelerating material, lithium hydroxide used as an auxiliary material can be previously contained in the boric acid cement solidifying material. That is, “compounding sodium aluminate” also includes compounding lithium hydroxide. The cement solidifying material for boric acid according to the present invention,
The solidified material contains at least 15% by weight of sodium aluminate based on the total weight of the solidified material. Below this,
It is difficult to obtain sufficient strength of the solidified cement.
And from such a strength aspect, preferably 20 wt%
It is preferable to include the above. Theoretically, a solidifying material consisting only of sodium aluminate and the required amount of lithium hydroxide is possible, but if the amount of sodium aluminate is too large, it tends to be excessively solidified and difficult to knead. Therefore, it is preferable to include at least 51 wt% of cement in the solidified material. In view of the above, the preferred range of sodium aluminate is 20% of the solidified material.
４０40 wt%. Lithium hydroxide (including one molecule of bound water, all in this specification including bound water)
Is used in a range of 10% or more and 100% or less, more preferably 14 to 20% by weight with respect to sodium aluminate. The term “used” as used herein includes the use as an auxiliary material different from the solidified material and the use as a part of the solidified material in advance.
【０００６】本発明は、別の側面としてほう酸のセメン
ト固化方法であり、上記ほう酸用セメント固化材をほう
酸溶液と混合すること、又は上記ほう酸用セメント固化
材をほう酸粉末と混合し、加水することを含む。本発明
は、さらに上記したほう酸のセメント固化方法によっ
て、ほう酸、水、セメント、放射能固定材、アルミン酸
ナトリウム、水酸化リチウムを混合して固化した固化体
であって、３ｗｔ-Ｂ％以上のほう酸を含む。Another aspect of the present invention is a method for solidifying boric acid cement, in which the cement solidifying material for boric acid is mixed with a boric acid solution, or the cement solidifying material for boric acid is mixed with boric acid powder and watered. including. The present invention further provides a solidified product obtained by mixing boric acid, water, cement, a radioactive fixing material, sodium aluminate, and lithium hydroxide by the above-described boric acid cement solidifying method, wherein the solidified material has a content of 3 wt-B% or more. Contains boric acid.
【０００７】[0007]
【発明の実施の形態】次に、本発明に係るほう酸用セメ
ント固化材、ほう酸のセメント固化方法及びセメント固
化体の実施の形態についてさらに詳細に説明する。本発
明に係るほう酸用セメント固化材は、セメントにアルミ
ン酸ナトリウムを配合している。セメントのみ配合する
と、ほう酸を多量に含有させた場合に、セメント固化反
応を阻害してしまう。しかし、固化促進材としてアルミ
ン酸ナトリウムを配合すると固化が阻害されることがな
い。本発明は、このような利点を発揮するように実施さ
れるべきである。まず、本発明に係るほう酸用セメント
固化材の配合成分に関する好適な実施の形態について、
試験研究結果を参照しつつ説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the cement solidifying material for boric acid, the method for solidifying boric acid cement and the cement solidified body according to the present invention will be described in further detail. The cement solidifying material for boric acid according to the present invention contains sodium aluminate in the cement. When only cement is blended, when a large amount of boric acid is contained, the cement solidification reaction is inhibited. However, when sodium aluminate is blended as a solidification accelerator, solidification is not hindered. The present invention should be implemented to provide such advantages. First, regarding a preferred embodiment relating to the compounding component of the cement solidifying material for boric acid according to the present invention,
Explanation will be given with reference to the test and research results.
【０００８】図１に廃液中のほう酸濃度と、一軸圧縮強
度の関係を示す。図１のグラフは、以下の条件におい
て、固化材に助材（水酸化リチウム）を加え、これらに
ほう酸溶液を加え、セメント固化反応を行わせてセメン
ト固化体を得た。なお、図１の試験を含めて、本明細書
中においてｗｔ％は、重量％を示す。 固化条件 固化材：アルミン酸ナトリウム３５ｗｔ％（固化材中） Ｂ種高炉セメント：バランス（残余全て） 粉末ゼオライト：５ｗｔ％（放射能固定材） ＬｉＯＨ・Ｈ2Ｏ：７ｗｔ％ 給液 Ｎａ／Ｂモル比＝０．２５、１０ｗｔ-Ｂ／ｖ％
（ホウ素換算重量として） 液固化材比率＝１．０７ｍ3-液／ｔｏｎ-固化材FIG. 1 shows the relationship between the concentration of boric acid in the waste liquid and the uniaxial compressive strength. In the graph of FIG. 1, under the following conditions, an auxiliary material (lithium hydroxide) was added to the solidified material, a boric acid solution was added thereto, and a cement solidification reaction was performed to obtain a solidified cement. In addition, including the test of FIG. 1, wt% in this specification indicates wt%. Solidifying conditions solidifying material: sodium aluminate 35 wt% (in consolidated materials) B species blast-furnace slag cement: balance (remainder all) powder Zeolite: 5 wt% (radioactivity fixing material) LiOH · H 2 O: 7wt % Dispense Na / B molar Ratio = 0.25, 10wt-B / v%
(As boron equivalent weight) Liquid solidified material ratio = 1.07 m 3 -liquid / ton-solidified material
【０００９】図１に示すように、アルミン酸ナトリウム
を配合することにより、６〜１２ｗｔ-Ｂ／ｖ％（ホウ
素換算ｗ／ｖ％、溶液の単位体積あたりのホウ素重量と
して算出した百分率）の濃度範囲で十分な一軸圧縮強度
（１００ｋｇ／ｃｍ2を得ることができる。一軸圧縮強
度としては、１５ｋｇ／ｃｍ2あれば、一般的な基準を
満たす。なお、図１において、この条件のもと、混錬不
可能の範囲があるのは、ある程度のほう酸濃度以下で
は、セメントの固化が早く進行してしまうことを示して
いる。As shown in FIG. 1, by adding sodium aluminate, the concentration of 6 to 12 wt-B / v% (w / v% in terms of boron, percentage calculated as the weight of boron per unit volume of the solution) is obtained. A sufficient uniaxial compressive strength (100 kg / cm 2 ) can be obtained within the range. A uniaxial compressive strength of 15 kg / cm 2 satisfies a general standard. The fact that there is a range in which kneading is not possible indicates that the solidification of the cement progresses rapidly below a certain concentration of boric acid.
【００１０】図２に、アルミン酸ナトリウムの添加率と
一軸圧縮強度との関係を調べた結果を示す。上記したよ
うに、一軸圧縮強度としては、１５ｋｇ／ｃｍ2あれ
ば、一般的な基準を満たす。図２の結果で見ると、固化
材中にアルミン酸ナトリウムを固化材全体の重量に対
し、少なくとも１５ｗｔ％含むことが必要であることが
了解される。好適には２０ｗｔ％以上であることが了解
される。アルミン酸ナトリウムの量が多すぎる、固化反
応が過度に進んで混錬しにくくなる。そこで、固化材中
に少なくとも５１ｗｔ％のセメントを含むことが好適で
ある。このようなことを考慮して、アルミン酸ナトリウ
ムの好適な配合範囲は、固化材のうち２０〜４０ｗｔ％
である。なお、この際の固化条件を以下に示す。なお、
固化方法は、図１と同様である。 固化条件 固化材：アルミン酸ナトリウム 図に示すｗｔ％で変化
させた。 Ｂ種高炉セメント：バランス（残余全て） 粉末ゼオライト：５ｗｔ％（放射能固定材） ＬｉＯＨ・Ｈ2Ｏ：５ｗｔ％と７ｗｔ％（固化材の一部
として配合割合を算出） 給液 Ｎａ／Ｂモル比＝０．２５、１０ｗｔ-Ｂ／ｖ％
（ホウ素換算重量として） 液固化材比率＝１．０７ｍ3-液／ｔｏｎ-固化材FIG. 2 shows the result of examining the relationship between the addition rate of sodium aluminate and the uniaxial compressive strength. As described above, if the uniaxial compressive strength is 15 kg / cm 2 , a general standard is satisfied. From the results shown in FIG. 2, it is understood that it is necessary that the solidified material contains at least 15 wt% of sodium aluminate based on the total weight of the solidified material. It is understood that it is preferably at least 20 wt%. If the amount of sodium aluminate is too large, the solidification reaction proceeds excessively, making kneading difficult. Therefore, it is preferable to include at least 51 wt% of cement in the solidified material. In consideration of the above, the preferable compounding range of sodium aluminate is 20 to 40% by weight of the solidified material.
It is. The solidification conditions at this time are shown below. In addition,
The solidification method is the same as in FIG. Solidification conditions Solidification material: sodium aluminate It was changed at the wt% shown in the figure. Class B blast-furnace slag cement: balance (remainder all) powder Zeolite: 5 wt% (radioactivity fixing material) LiOH · H 2 O: 5wt % and 7 wt% (calculated blending ratio as part of the solidified material) supply fluid Na / B molar Ratio = 0.25, 10wt-B / v%
(As boron equivalent weight) Liquid solidified material ratio = 1.07 m 3 -liquid / ton-solidified material
【００１１】本発明では、ほう酸用セメント固化材に対
して、助材として水酸化リチウムを添加することが好適
である。水酸化リチウムを助材として添加することによ
り、固化速度を抑えることができる。すなわち、アルミ
ン酸ナトリウムは、セメントの固化を早めすぎるおそれ
があるが、水酸化リチウムの添加によってそれを調整す
ることができる。図２の試験の場合、７ｗｔ％配合した
場合のほうが、５ｗｔ％配合した場合よりも混合が容易
であった。水酸化リチウムは、混合量が多いほど効果が
高い。しかし、図２の試験を行う経過において、アルミ
ン酸ナトリウムとの重量比で１０％以上であって、１０
０％以下までの量であり、コストを考慮して１４〜２０
％の範囲で用いることが実用的である。In the present invention, it is preferable to add lithium hydroxide as an auxiliary agent to the solidified cement for boric acid. The solidification rate can be suppressed by adding lithium hydroxide as an auxiliary material. In other words, sodium aluminate may prematurely solidify the cement, which can be adjusted by adding lithium hydroxide. In the case of the test of FIG. 2, mixing was easier when 7 wt% was blended than when 5 wt% was blended. The effect of lithium hydroxide is higher as the mixing amount is larger. However, in the course of performing the test of FIG. 2, the weight ratio with respect to sodium aluminate was 10% or more and 10% or more.
The amount is up to 0% or less.
It is practical to use in the range of%.
【００１２】図３に、減容比と、一軸圧縮強度との関係
を調べた結果を示す。このグラフにおいて、横軸は、ド
ラム缶１単位にホウ素換算値で２．１ｋｇを含むものを
１単位として示した比率である。一軸圧縮強度は、減容
比に逆比例する。本発明の場合、減容比の実用的上限
は、１１．５である。固化条件は、以下の通りであり、
固化材と水酸化リチウムの混合の後、ほう酸を粉末とし
て加え、これを混合容器で混合攪拌し、最後に水を加え
ることとした。そして、セメント固化反応によって固化
体を得た。 固化条件 固化材：アルミン酸ナトリウム ３５ｗｔ％ Ｂ種高炉セメント：バランス（残余全て） 粉末ゼオライト：５ｗｔ％（放射能固定材） ＬｉＯＨ・Ｈ2Ｏ：５ｗｔ％（固化材の一部として配合
割合を算出） 水１００ｇ、乾燥ほう酸粉体６０〜１１０ｇで変化させ
た。 給液 Ｎａ／Ｂモル比＝０．２５ 固化体形状：５０φ×１００Ｈ 材令：４週間FIG. 3 shows the result of examining the relationship between the volume reduction ratio and the uniaxial compressive strength. In this graph, the abscissa axis represents the ratio of one drum unit containing 2.1 kg in terms of boron as one unit. Uniaxial compressive strength is inversely proportional to the volume reduction ratio. In the case of the present invention, the practical upper limit of the volume reduction ratio is 11.5. The solidification conditions are as follows,
After mixing of the solidifying material and lithium hydroxide, boric acid was added as a powder, and this was mixed and stirred in a mixing vessel, and finally water was added. Then, a solid was obtained by a cement solidification reaction. Solidifying conditions solidifying material: sodium 35 wt% B species blast aluminate cement: balance (remainder all) powder Zeolite: 5 wt% (radioactivity fixing material) LiOH · H 2 O: calculated blending ratio as part of a 5 wt% (consolidated materials ) The amount was changed with 100 g of water and 60 to 110 g of dry boric acid powder. Liquid supply Na / B molar ratio = 0.25 Solidified form: 50φ × 100H Material age: 4 weeks
【００１３】図４に、給液／固化材混合比と一軸圧縮強
度の関係を示す。この関係から、給液／固化材混合比
は、１付近から１．２付近までの間であれば、得られる
固化体について問題がないことが了解される。固化条件
は、以下の通りである。固化方法は、図１、図２と同様
とした。 固化条件 固化材：アルミン酸ナトリウム ３５ｗｔ％ Ｂ種高炉セメント：バランス（残余全て） 粉末ゼオライト：５ｗｔ％（放射能固定材） ＬｉＯＨ・Ｈ2Ｏ：７ｗｔ％（固化材の一部として配合
割合を算出） 給液 Ｎａ／Ｂモル比＝０．２５、１０ｗｔ-Ｂ／ｖ％
（ホウ素換算重量として）FIG. 4 shows the relationship between the liquid feed / solidification material mixture ratio and the uniaxial compressive strength. From this relationship, it can be understood that there is no problem with the obtained solidified body as long as the liquid / solidification material mixture ratio is between about 1 and about 1.2. The solidification conditions are as follows. The solidification method was the same as in FIGS. Solidifying conditions solidifying material: sodium 35 wt% B species blast aluminate cement: balance (remainder all) powder Zeolite: 5 wt% (radioactivity fixing material) LiOH · H 2 O: calculated blending ratio as part of a 7 wt% (consolidated materials ) Feed Na / B molar ratio = 0.25, 10wt-B / v%
(As boron equivalent weight)
【００１４】以上の図１〜図４の結果にもとづいて、本
発明のほう酸用セメント固化材の配合割合として好適な
実施の形態としては以下のものを挙げることができる。
予め水酸化リチウムを配合しない場合： セメント ５１〜７１重量部 放射能固定材 ５〜１０重量部 アルミン酸ナトリウム ４０〜２０重量部 助材として用いる水酸化リチウム ８〜４重量部 予め水酸化リチウムを配合する場合には、全体をこのよ
うな重量比で当初より配合しておく。本発明に係るほう
酸のセメント固化方法を実施することにより、３ｗｔ-
Ｂ％以上のほう酸を含むセメント固化体を得ることがで
きる。Based on the results shown in FIGS. 1 to 4, preferred embodiments of the compounding ratio of the cement solidifying material for boric acid according to the present invention include the following.
When lithium hydroxide is not previously compounded: Cement 51 to 71 parts by weight Radioactive material 5 to 10 parts by weight Sodium aluminate 40 to 20 parts by weight Lithium hydroxide used as an auxiliary agent 8 to 4 parts by weight Lithium hydroxide is previously compounded In this case, the entirety is blended in such a weight ratio from the beginning. By carrying out the method for solidifying boric acid cement according to the present invention, 3 wt-
A cement solid containing B% or more of boric acid can be obtained.
【００１５】本発明の別の側面であるほう酸のセメント
固化方法に関する実施の形態を次に説明する。図５、図
６は、上記ほう酸用セメント固化材をほう酸溶液と混合
することにより固化する実施の形態を示す。図７〜図９
は、上記ほう酸用セメント固化材をほう酸粉末と混合
し、加水することにより固化する実施の形態を示す。以
下各々について説明する。An embodiment of a method for solidifying boric acid cement as another aspect of the present invention will be described below. FIGS. 5 and 6 show an embodiment in which the cement solidifying material for boric acid is solidified by mixing with a boric acid solution. 7 to 9
Shows an embodiment in which the cement solidifying material for boric acid is mixed with boric acid powder and solidified by adding water. Hereinafter, each will be described.
【００１６】まず、図５の実施の形態について説明す
る。この実施の形態では、まず、本発明に係る固化材を
助材である水酸化リチウムと混合する。これらの原料の
配合割合は、上記したところによる。そして、これらを
混合容器内で混合する。混合物にほう酸溶液を加える。
加えるべきほう酸溶液の濃度は、前記したように６〜１
２ｗｔ-Ｂ／ｖ％の範囲が好適である。ほう酸溶液を加
えた後、攪拌を継続し、セメント固化反応によって固化
が完了した後、セメント固化体を得ることができる。な
お、本発明の固化材を用いることにより、型内に導入す
るためのタイミング的な余裕は確保される。この実施の
形態は、固化材とリチウムの混合物を予め準備しておく
ことができるので、発電所における作業が簡略化すると
いう利点がある。先の図１、２、４に関する試験におい
ては、この実施の形態に係るセメント固化方法を実施し
た。First, the embodiment shown in FIG. 5 will be described. In this embodiment, first, the solidified material according to the present invention is mixed with lithium hydroxide as an auxiliary material. The mixing ratio of these raw materials is as described above. And these are mixed in a mixing container. Add the boric acid solution to the mixture.
The concentration of the boric acid solution to be added is 6 to 1 as described above.
A range of 2 wt-B / v% is preferred. After adding the boric acid solution, stirring is continued, and after solidification is completed by the cement solidification reaction, a solidified cement body can be obtained. Note that by using the solidifying material of the present invention, a timing margin for introduction into the mold is secured. This embodiment has an advantage that the operation in the power plant is simplified because a mixture of the solidifying material and lithium can be prepared in advance. In the test relating to FIGS. 1, 2, and 4, the cement solidification method according to this embodiment was performed.
【００１７】次に、図６の実施の形態について説明す
る。この実施の形態では、予め、水酸化リチウムとほう
酸溶液を混合し、それに本発明に係る固化材を加える。
他の操作は、図５の実施の形態と異なるところはない。
固化材の配合割合、水酸化リチウムの添加量は、上記し
たところによる。ほう酸溶液の濃度は、前記したように
６〜１２ｗｔ-Ｂ／ｖ％の範囲が好適である。この実施
の形態は、混合が一回で済むので、処理が早いという利
点がある。Next, the embodiment of FIG. 6 will be described. In this embodiment, lithium hydroxide and boric acid solution are mixed in advance, and the solidifying material according to the present invention is added thereto.
Other operations are not different from the embodiment of FIG.
The mixing ratio of the solidifying material and the amount of lithium hydroxide added are as described above. As described above, the concentration of the boric acid solution is preferably in the range of 6 to 12 wt-B / v%. This embodiment has the advantage that the processing is quick because only one mixing is required.
【００１８】次に、図７の実施の形態について説明す
る。この実施の形態では、図５の実施の形態と異なり、
固化材と水酸化リチウムの混合の後、被処理物であるほ
う酸を粉末として加え、これを混合容器で混合攪拌し、
最後に水を加えることとしている。そして、セメント固
化反応によって固化体を得ることとしている。この実施
の形態では、加える水にほう酸粉末を直接加えた場合に
得られる溶液の濃度が、６〜１２ｗｔ-Ｂ／ｖ％の範囲
となるように設定する。固化材の配合割合、水酸化リチ
ウムの添加量は、上記したところによる。なお、本発明
の固化材を用いることにより、型内に導入するためのタ
イミング的な余裕は確保される。この実施の形態は、固
化材とリチウムの混合物を予め準備しておくことができ
るので、発電所における作業が簡略化するという利点が
ある。先の図３に関する試験においては、この実施の形
態に係るセメント固化方法を実施した。Next, the embodiment shown in FIG. 7 will be described. In this embodiment, unlike the embodiment of FIG.
After mixing the solidifying material and lithium hydroxide, boric acid, which is an object to be treated, is added as a powder, and this is mixed and stirred in a mixing vessel,
Finally, add water. Then, a solidified body is obtained by a cement solidification reaction. In this embodiment, the concentration of the solution obtained when boric acid powder is directly added to the water to be added is set to be in the range of 6 to 12 wt-B / v%. The mixing ratio of the solidifying material and the amount of lithium hydroxide added are as described above. Note that by using the solidifying material of the present invention, a timing margin for introduction into the mold is secured. This embodiment has an advantage that the operation in the power plant is simplified because a mixture of the solidifying material and lithium can be prepared in advance. In the test related to FIG. 3 described above, the cement solidification method according to this embodiment was performed.
【００１９】次に、図８の実施の形態について説明す
る。この実施の形態では、図７の実施の形態と異なり、
ほう酸粉末に予め水酸化リチウムを配合し、そして、配
合物を固化材と混合攪拌している。固化材の配合割合、
水酸化リチウムの添加量は、上記したところによる。そ
の他は、図７の実施の形態と異なるところはない。セメ
ント固化反応によって固化体を得ることとしている。こ
の実施の形態は、混合が一回で済むので、処理が早いと
いう利点がある。Next, the embodiment shown in FIG. 8 will be described. This embodiment differs from the embodiment of FIG.
Lithium hydroxide is previously blended with boric acid powder, and the blend is mixed with a solidifying material and stirred. Mixing ratio of solidified material,
The amount of lithium hydroxide added is as described above. Other than that, there is no difference from the embodiment of FIG. A solidified body is to be obtained by a cement solidification reaction. This embodiment has the advantage that the processing is quick because only one mixing is required.
【００２０】最後に、図９の実施の形態について説明す
る。この実施の形態では、ほう酸粉末に予め水を加え
て、６〜１２ｗｔ-Ｂ／ｖ％の範囲のほう酸溶液を作成
し、これに水酸化リチウムを添加し、攪拌混合する。次
いで、固化材を加えることとしている。そして、セメン
ト固化反応によって固化体を得ることとしている。固化
材の配合割合、水酸化リチウムの添加量は、上記したと
ころによる。本発明の固化材を用いることにより、型内
に導入するためのタイミング的な余裕は確保される。こ
の実施の形態は、混合が一回で済むので、処理が早いと
いう利点がある。Finally, the embodiment shown in FIG. 9 will be described. In this embodiment, water is added to boric acid powder in advance to prepare a boric acid solution in a range of 6 to 12 wt-B / v%, lithium hydroxide is added thereto, and the mixture is stirred and mixed. Next, a solidifying material is added. Then, a solidified body is obtained by a cement solidification reaction. The mixing ratio of the solidifying material and the amount of lithium hydroxide added are as described above. By using the solidifying material of the present invention, a timing margin for introduction into the mold is secured. This embodiment has the advantage that the processing is quick because only one mixing is required.
【００２１】[0021]
【実施例】上記図５から図９の各実施の形態について、
ほう酸溶液、又はほう酸粉末を固化させた。 実施例１ 図５の実施の形態を実施した。以下の表１に示す配合割
合の固化材を、助材である水酸化リチウムと混合した。
水酸化リチウムの配合割合は、表１に示す割合とした。
これらを混合容器内で混合した。混合物にほう酸溶液を
加えた。加えたほう酸溶液の濃度は、１０ｗｔ-Ｂ／ｖ
％であった。これを表１に示す比率で固化材に加えた。
ほう酸溶液を加えた後、攪拌を継続し、セメント固化反
応によって固化が完了し、セメント固化体を得た。固化
材中のほう素含有量は、表１に示した通りであった。ま
た、一軸圧縮強度は、２６０ｋｇ／ｃｍ2であり十分な
強度を得ることができた。この実施例１では、固化材と
リチウムの混合物を予め準備しておくことができたの
で、作業が簡略であった。DESCRIPTION OF THE PREFERRED EMBODIMENTS Regarding each of the embodiments shown in FIGS.
The boric acid solution or boric acid powder was solidified. Example 1 The embodiment of FIG. 5 was implemented. The solidifying materials having the compounding ratios shown in Table 1 below were mixed with lithium hydroxide as an auxiliary material.
The mixing ratio of lithium hydroxide was as shown in Table 1.
These were mixed in a mixing vessel. A boric acid solution was added to the mixture. The concentration of the added boric acid solution is 10 wt-B / v
%Met. This was added to the solidified material at the ratio shown in Table 1.
After the boric acid solution was added, the stirring was continued, and the solidification was completed by the cement solidification reaction to obtain a solidified cement. The boron content in the solidified material was as shown in Table 1. Further, the uniaxial compressive strength was 260 kg / cm 2 , and sufficient strength could be obtained. In Example 1, the operation was simplified because a mixture of the solidifying material and lithium could be prepared in advance.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例２ 図６の実施の形態を実施した。この実施例では、予め、
水酸化リチウムとほう酸溶液を混合し、固化材を加え
た。固化材の配合割合、水酸化リチウムの添加量は、先
の表１に示す通りであり、実施例１と同様であった。ほ
う酸溶液の濃度は、１０ｗｔ-Ｂ／ｖ％であった。セメ
ント固化反応によって固化が完了し、セメント固化体を
得た。固化材中のほう素含有量は、表１に示した通りで
あった。また、一軸圧縮強度は、２５０ｋｇ／ｃｍ2で
あり十分な強度を得ることができた。この実施の形態
は、混合が一回で済むので、処理が早かった。Example 2 The embodiment of FIG. 6 was implemented. In this embodiment,
Lithium hydroxide and boric acid solution were mixed, and a solidifying material was added. The mixing ratio of the solidifying material and the amount of lithium hydroxide added were as shown in Table 1 above, and were the same as in Example 1. The concentration of the boric acid solution was 10 wt-B / v%. The solidification was completed by the cement solidification reaction, and a solidified cement was obtained. The boron content in the solidified material was as shown in Table 1. Further, the uniaxial compressive strength was 250 kg / cm 2 , and sufficient strength could be obtained. In this embodiment, the processing is quick because only one mixing is required.
【００２４】実施例３ 図７の実施の形態を実施した。固化材と水酸化リチウム
の混合の後、被処理物であるほう酸を粉末として加え、
これを混合容器で混合攪拌し、最後に水を加えた。固化
材の配合割合は、以下の表２に示す通りとし、水酸化リ
チウム及びほう酸粉末の混合割合は、表２に示す通りと
した。水とのセメント固化反応によって固化体を得た。
水は、固化材との比率で表２に示す通りの割合で加え
た。固化材中のほう素含有量は、表２に示した通りであ
った。また、一軸圧縮強度は、２０４ｋｇ／ｃｍ2であ
り十分な強度を得ることができた。固化材とリチウムの
混合物を予め準備しておくことができるので、作業が簡
略であった。Example 3 The embodiment shown in FIG. 7 was implemented. After mixing the solidifying material and lithium hydroxide, boric acid, which is an object to be treated, is added as a powder,
This was mixed and stirred in a mixing vessel, and finally water was added. The mixing ratio of the solidified material was as shown in Table 2 below, and the mixing ratio of lithium hydroxide and boric acid powder was as shown in Table 2. A solid was obtained by a cement solidification reaction with water.
Water was added at the ratio shown in Table 2 with respect to the solidifying material. The boron content in the solidified material was as shown in Table 2. Further, the uniaxial compressive strength was 204 kg / cm 2 , and sufficient strength could be obtained. The operation was simplified because a mixture of the solidifying material and lithium could be prepared in advance.
【００２５】[0025]
【表２】 [Table 2]
【００２６】実施例４ 図８の実施の形態を実施した。この実施の形態では、実
施例３と異なり、ほう酸粉末に予め水酸化リチウムを配
合し、そして、配合物を固化材と混合攪拌した。固化材
の配合割合、水酸化リチウムの添加量、ほう酸粉末の
量、水の添加量は、実施例３と同様であった。セメント
固化反応によって固化体を得ることができた。固化材中
のほう素含有量は、表２に示した通りであった。また、
一軸圧縮強度は、２１０ｋｇ／ｃｍ2であり十分な強度
を得ることができた。この実施例では、混合が一回で済
むので、処理が早いという利点が確認された。Example 4 The embodiment of FIG. 8 was implemented. In this embodiment, unlike Example 3, lithium hydroxide was previously blended into boric acid powder, and the blend was mixed and stirred with a solidifying material. The mixing ratio of the solidifying material, the amount of lithium hydroxide added, the amount of boric acid powder, and the amount of water added were the same as in Example 3. A solid was obtained by the cement solidification reaction. The boron content in the solidified material was as shown in Table 2. Also,
The uniaxial compressive strength was 210 kg / cm 2 , and sufficient strength could be obtained. In this example, since the mixing was performed only once, the advantage that the processing was quick was confirmed.
【００２７】実施例５ 図９の実施の形態を実施した。この実施の形態では、ほ
う酸粉末に予め水を加えて、ほう酸溶液を作成し、これ
に水酸化リチウムを添加し、攪拌混合した。次いで、固
化材を加えた。固化材の配合割合、水酸化リチウムの添
加量、ほう酸粉末の量、水の添加量は、実施例３と同様
であった。セメント固化反応によって固化体を得ること
ができた。固化材中のほう素含有量は、表２に示した通
りであった。また、一軸圧縮強度は、２００ｋｇ／ｃｍ
2であり十分な強度を得ることができた。この実施例で
は、混合が一回で済むので、処理が早いという利点が確
認された。Embodiment 5 The embodiment shown in FIG. 9 was implemented. In this embodiment, water was previously added to the boric acid powder to prepare a boric acid solution, and lithium hydroxide was added thereto and mixed with stirring. Next, a solidifying material was added. The mixing ratio of the solidifying material, the amount of lithium hydroxide added, the amount of boric acid powder, and the amount of water added were the same as in Example 3. A solid was obtained by the cement solidification reaction. The boron content in the solidified material was as shown in Table 2. The uniaxial compressive strength is 200 kg / cm
2 , which was sufficient strength. In this example, since the mixing was performed only once, the advantage that the processing was quick was confirmed.
【００２８】[0028]
【発明の効果】上記したところから明かなように、本発
明によれば、多量のほう酸を混入しても固化することを
可能としたほう酸用セメント固化材、ほう酸のセメント
固化方法及び固化体が提供される。As is clear from the above description, according to the present invention, a cement solidifying material for boric acid, a cement solidifying method of boric acid, and a solidified body capable of solidifying even if a large amount of boric acid is mixed. Provided.
【図１】廃液中のほう酸濃度と、一軸圧縮強度の関係を
示すグラフである。FIG. 1 is a graph showing the relationship between the concentration of boric acid in a waste liquid and the uniaxial compressive strength.
【図２】アルミン酸ナトリウムの添加率と一軸圧縮強度
との関係を示すグラフである。FIG. 2 is a graph showing the relationship between the addition rate of sodium aluminate and the uniaxial compressive strength.
【図３】減容比と、一軸圧縮強度との関係を示すグラフ
である。FIG. 3 is a graph showing a relationship between a volume reduction ratio and a uniaxial compressive strength.
【図４】給液／固化材混合比と一軸圧縮強度の関係を示
すグラフである。FIG. 4 is a graph showing the relationship between the liquid / solidification material mixture ratio and the uniaxial compressive strength.
【図５】本発明に係るほう酸のセメント固化方法の一実
施の形態を説明する概念的工程図である。FIG. 5 is a conceptual process diagram illustrating an embodiment of a method for solidifying boric acid cement according to the present invention.
【図６】本発明に係るほう酸のセメント固化方法の一実
施の形態を説明する概念的工程図である。FIG. 6 is a conceptual process diagram illustrating an embodiment of a method for solidifying boric acid cement according to the present invention.
【図７】本発明に係るほう酸のセメント固化方法の一実
施の形態を説明する概念的工程図である。FIG. 7 is a conceptual process diagram illustrating an embodiment of a method for solidifying boric acid cement according to the present invention.
【図８】本発明に係るほう酸のセメント固化方法の一実
施の形態を説明する概念的工程図である。FIG. 8 is a conceptual process diagram illustrating an embodiment of a method for solidifying boric acid cement according to the present invention.
【図９】本発明に係るほう酸のセメント固化方法の一実
施の形態を説明する概念的工程図である。FIG. 9 is a conceptual process diagram illustrating one embodiment of a method for solidifying boric acid cement according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石飛 龍彦 兵庫県神戸市兵庫区和田崎町一丁目１番 １号 三菱重工業株式会社 神戸造船所 内 (72)発明者 佐川 寛 兵庫県神戸市兵庫区和田崎町一丁目１番 １号 三菱重工業株式会社 神戸造船所 内 (72)発明者 永島 勝治 大阪府羽曳野市西浦1458番地 王水産業 株式会社内 (72)発明者 西田 清則 兵庫県高砂市荒井町新浜二丁目８番19号 高菱エンジニアリング株式会社内 (72)発明者 塩地 則夫 兵庫県高砂市荒井町新浜２丁目１番１号 ツルイ化学株式会社内 (56)参考文献 特開 昭60−119499（ＪＰ，Ａ) 特開 昭63−115099（ＪＰ，Ａ) 特開 昭61−40594（ＪＰ，Ａ) 特開 昭58−204395（ＪＰ，Ａ) 特開 平８−146194（ＪＰ，Ａ) 特公 平７−35287（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 28/02 B09B 3/00 301 C04B 22/08 G21F 9/16 521 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatsuhiko Ishihi 1-1-1 Wadazakicho, Hyogo-ku, Kobe-shi, Hyogo Mitsubishi Heavy Industries, Ltd. Kobe Shipyard (72) Inventor Hiroshi Sagawa Hyogo-ku, Hyogo-ken 1-1-1 1-1 Wadazakicho Mitsubishi Heavy Industries, Ltd.Kobe Shipyard (72) Inventor Katsuharu Nagashima 1458 Nishiura, Habikino-shi, Osaka Prefecture Omi Suisan Co., Ltd. No. 8-19, Takahashi Engineering Co., Ltd. (72) Inventor Norio Shioji 2-1-1, Aramachi, Arai-cho, Takasago-shi, Hyogo Tsuru Chemical Co., Ltd. (56) References JP-A-60-119499 (JP) JP-A-63-115099 (JP, A) JP-A-61-40594 (JP, A) JP-A-58-204395 (JP, A) JP-A-8-146194 (JP, A) , A) JP 7-35287 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 28/02 B09B 3/00 301 C04B 22/08 G21F 9/16 521
Claims (9)
ナトリウムを配合したことを特徴とするほう酸用セメン
ト固化材。1. A cement solidifying material for boric acid, characterized in that sodium aluminate is blended into cement as a solidifying accelerator.
を特徴とする請求項１のほう酸用セメント固化材。2. The cement solidifying material for boric acid according to claim 1, wherein lithium hydroxide is used as an auxiliary material.
ｗｔ％含むことを特徴とする請求項１又は２のほう酸用
セメント固化材。3. The method of claim 1, wherein the sodium aluminate comprises at least 15
The cement-solidifying material for boric acid according to claim 1, wherein the cement-solidifying material contains 0.1 wt%.
％含むことを特徴とする請求項１〜３のいずれかのほう
酸用セメント固化材。4. The method according to claim 1, wherein the sodium aluminate is 20 to 40 wt.
%. The cement solidifying material for boric acid according to claim 1, wherein
との重量比で１０％以上含むことを特徴とする請求項１
〜４のいずれかのほう酸用セメント固化材。5. The method according to claim 1, wherein lithium hydroxide is contained by 10% or more by weight with respect to sodium aluminate.
4. The cement solidifying material for boric acid according to any one of items 1 to 4,
との重量比で１０〜１００％の範囲で含むことを特徴と
する請求項１〜５のいずれかのほう酸用セメント固化
材。6. The cement-solidifying material for boric acid according to claim 1, wherein lithium hydroxide is contained in a range of 10 to 100% by weight with respect to sodium aluminate.
ント固化材をほう酸溶液と混合することを含むほう酸の
セメント固化方法。7. A method for solidifying cement of boric acid, comprising mixing the cement solidifying material for boric acid according to claim 1 with a boric acid solution.
ト固化材をほう酸粉末と混合し、加水することを含むほ
う酸のセメント固化方法。8. A method for solidifying boric acid cement comprising mixing the cement solidifying material for boric acid according to claim 1 with boric acid powder and adding water.
法によって、ほう酸、水、セメント、放射能固定材、ア
ルミン酸ナトリウム、水酸化リチウムを混合して固化し
た３ｗｔ-Ｂ％以上のほう酸を含む固化体。9. A boric acid of 3 wt-B% or more solidified by mixing boric acid, water, cement, a radioactive fixing material, sodium aluminate, and lithium hydroxide by the boric acid cement solidifying method according to claim 7 or 8. Including solidified body.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8702833B2 (en) | 2004-07-14 | 2014-04-22 | Nihon Pack Co. | Health food |
| KR20140107308A (en) * | 2011-11-25 | 2014-09-04 | 차이나 제너럴 뉴클리어 파워 코퍼레이션 | Cement curing formulation and method for high-level radioactive boron waste resins from nuclear reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5726412B2 (en) * | 2009-10-19 | 2015-06-03 | 株式会社東芝 | Method of solidifying sodium sulfate concentrated waste liquid containing boric acid |
| JP6672014B2 (en) | 2015-03-16 | 2020-03-25 | 株式会社東芝 | Treatment of radioactive liquid waste |
| CN108585722B (en) * | 2018-04-13 | 2020-09-01 | 武汉理工大学 | Cement-based curing material for curing waste liquid containing high-concentration boric acid nuclei and curing method thereof |
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1999
- 1999-09-30 JP JP27964899A patent/JP3095748B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8702833B2 (en) | 2004-07-14 | 2014-04-22 | Nihon Pack Co. | Health food |
| KR20140107308A (en) * | 2011-11-25 | 2014-09-04 | 차이나 제너럴 뉴클리어 파워 코퍼레이션 | Cement curing formulation and method for high-level radioactive boron waste resins from nuclear reactor |
| KR101720397B1 (en) * | 2011-11-25 | 2017-03-27 | 차이나 제너럴 뉴클리어 파워 코퍼레이션 | Cement curing formulation and method for high-level radioactive boron waste resins from nuclear reactor |
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