JP2018122273A - Method for treating boron-containing water - Google Patents
Method for treating boron-containing water Download PDFInfo
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- containing water
- cerium ions
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 162
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 55
- -1 cerium ions Chemical class 0.000 claims abstract description 48
- 238000000975 co-precipitation Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 150000000703 Cerium Chemical class 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical group O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 32
- 239000007788 liquid Substances 0.000 abstract description 26
- 239000002002 slurry Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 238000000926 separation method Methods 0.000 description 12
- 239000012528 membrane Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- MEXSQFDSPVYJOM-UHFFFAOYSA-J cerium(4+);disulfate;tetrahydrate Chemical compound O.O.O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MEXSQFDSPVYJOM-UHFFFAOYSA-J 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000021112 essential micronutrients Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、ホウ素含有水の処理方法に関する。さらに詳しくは、共沈法によってホウ素含有水からホウ素を除去する方法に関する。 The present invention relates to a method for treating boron-containing water. More specifically, the present invention relates to a method of removing boron from boron-containing water by a coprecipitation method.
ホウ素を含有する水（以下、「ホウ素含有水」という。）は、自然界において地下水、海水などとして存在している。また、ホウ素はホウ素化合物を原材料として使用する工業、例えば、ガラス工業をはじめ、医薬、化粧品原料、石鹸工業、電気めっき工業などで生じる廃水、発電所から生じる廃水、ゴミ焼却場で生じる洗煙廃水などの廃水に含まれている。 Boron-containing water (hereinafter referred to as “boron-containing water”) exists in nature as groundwater, seawater, and the like. Boron is wastewater generated in industries that use boron compounds as raw materials, such as glass industry, pharmaceuticals, cosmetic raw materials, soap industry, electroplating industry, etc., wastewater generated from power plants, and smoke washing wastewater generated in garbage incineration plants. It is contained in wastewater.
ホウ素は、動植物にとって必須の微量栄養素であるが、その反面、農業用水中に数ｍｇ／Ｌ以上の濃度で含まれている場合、植物の成長を阻害することが知られている。また、ホウ素を人体に継続的に摂取したとき、健康障害が生じるおそれがあることから、ホウ素の人体摂取量が法令で規制されている。例えば、水道水の水質基準では水道水に含まれるホウ素濃度が１．０ｍｇ／Ｌ以下に規制されている。また、海域へのホウ素の排水基準ではホウ素濃度が２３０ｍｇ／Ｌ以下、海域外への排水基準ではホウ素濃度が１０ｍｇ／Ｌ以下に規制されている。そこで、ホウ素を含有する廃水は、ホウ素を除去する処理を行った後に、放流される。 Boron is an essential micronutrient for animals and plants, but on the other hand, it is known to inhibit plant growth when contained in agricultural water at a concentration of several mg / L or more. Moreover, since there is a risk of health problems when boron is continuously ingested by the human body, the human intake of boron is regulated by law. For example, in the quality standard for tap water, the concentration of boron contained in tap water is regulated to 1.0 mg / L or less. Moreover, the boron concentration is regulated to 230 mg / L or less in the drainage standard for boron into the sea area, and the boron concentration is regulated to 10 mg / L or less in the drainage standard for outside the sea area. Therefore, wastewater containing boron is discharged after performing a treatment for removing boron.
ホウ素含有水からホウ素を除去する方法として、ジルコニウムやマグネシウムなどの水酸化物にホウ素を吸着させる吸着法、ホウ素含有水を蒸発濃縮してホウ酸を晶析する蒸発濃縮法、アルコール基を有する溶媒によりホウ素を抽出分離する溶媒抽出法、逆浸透膜を用いてホウ素を分離除去する逆浸透膜法などの種々の方法が知られている。 As a method of removing boron from boron-containing water, an adsorption method in which boron is adsorbed on a hydroxide such as zirconium or magnesium, an evaporation concentration method in which boron-containing water is evaporated and concentrated to crystallize boric acid, a solvent having an alcohol group Various methods are known, such as a solvent extraction method for extracting and separating boron by a reverse osmosis and a reverse osmosis membrane method for separating and removing boron using a reverse osmosis membrane.
しかしながら、吸着法は、ジルコニウムやマグネシウムなどの水酸化物へのホウ素の吸着容量が低いため、多量の吸着剤の添加が不可欠であり、効率性と経済性において実用的でない。蒸発濃縮法は、ホウ素含有水を濃縮しホウ酸を晶析させるために熱源が必要であり、特にホウ素濃度が低い廃水を対象とする場合には、莫大なエネルギーを必要とするので経済的でない。しかも、晶析後のホウ素含有水の中和処理が必要となる。溶媒抽出法は、有機溶媒からホウ素を逆抽出して得られるホウ素含有液の処理のほかに、有機溶媒が微量溶解している処理後の廃水の処理が不可欠である。活性炭などにより有機溶媒を回収除去するなどの処理が必要であり経済的でない。逆浸透膜法は、この方法のみで低濃度になるまでホウ素を除去することが困難であるので、他の方法との併用が必要である。また、膜の閉塞による効率悪化の問題がある。 However, since the adsorption method has a low adsorption capacity of boron to hydroxides such as zirconium and magnesium, it is indispensable to add a large amount of adsorbent, which is impractical in terms of efficiency and economy. The evaporative concentration method requires a heat source to concentrate boron-containing water and crystallize boric acid, and is not economical because it requires enormous energy, especially when wastewater with a low boron concentration is targeted. . Moreover, it is necessary to neutralize the boron-containing water after crystallization. In the solvent extraction method, in addition to the treatment of the boron-containing liquid obtained by back-extracting boron from the organic solvent, the treatment of the waste water after the treatment in which a trace amount of the organic solvent is dissolved is indispensable. A treatment such as recovery and removal of the organic solvent with activated carbon or the like is required, which is not economical. In the reverse osmosis membrane method, it is difficult to remove boron until the concentration becomes low only by this method, and therefore, it is necessary to use in combination with other methods. In addition, there is a problem of deterioration in efficiency due to the blockage of the membrane.
特許文献１には、溶存ホウ素を含有する被処理水中に、希土類元素イオンと多価陰イオン性物質とを存在させ、溶存ホウ素を難溶性物質として沈殿分離することが開示されている。また、特許文献２には、無機性陰イオンを含有する被処理水に、希土類元素の塩溶液と水酸化マグネシウムとを存在させ、無機性陰イオンを難溶性物質として沈殿分離することが開示されている。しかし、希土類元素としてセリウムを選択した場合、沈殿物はセリウムの水酸化物であり、ゲル状またはゼリー状となって固液分離が困難であることが知られている。 Patent Document 1 discloses that rare earth element ions and polyanionic substances are present in water to be treated containing dissolved boron, and dissolved boron is precipitated and separated as a hardly soluble substance. Patent Document 2 discloses that a rare earth salt solution and magnesium hydroxide are present in water to be treated containing inorganic anions, and the inorganic anions are precipitated and separated as hardly soluble substances. ing. However, when cerium is selected as the rare earth element, the precipitate is a hydroxide of cerium, and it is known that solid-liquid separation is difficult due to gel or jelly form.
本発明は上記事情に鑑み、固液分離性の高い沈殿物が得られるホウ素含有水の処理方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a method for treating boron-containing water from which a precipitate having a high solid-liquid separation property is obtained.
第１発明のホウ素含有水の処理方法は、ホウ素含有水中に４価のセリウムイオンを存在させ、前記ホウ素含有水のｐＨを調整することで、共沈反応によりホウ素を沈殿させることを特徴とする。
第２発明のホウ素含有水の処理方法は、第１発明において、前記ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させることを特徴とする。
第３発明のホウ素含有水の処理方法は、第１発明において、前記ホウ素含有水に４価のセリウム塩を添加することで、前記ホウ素含有水中に４価のセリウムイオンを存在させることを特徴とする。
第４発明のホウ素含有水の処理方法は、第２発明において、前記ホウ素含有水に３価のセリウム塩を添加した後、酸化剤を添加して３価のセリウムイオンを酸化することで、前記ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させることを特徴とする。
第５発明のホウ素含有水の処理方法は、第４発明において、前記酸化剤は過酸化水素水であることを特徴とする。
第６発明のホウ素含有水の処理方法は、第５発明において、過酸化水素水の添加量が、セリウムに対する過酸化水素の添加モル比が１以下となる量であることを特徴とする。
The method for treating boron-containing water according to the first invention is characterized in that tetravalent cerium ions are present in the boron-containing water, and boron is precipitated by a coprecipitation reaction by adjusting the pH of the boron-containing water. .
The method for treating boron-containing water of the second invention is characterized in that, in the first invention, trivalent cerium ions are present together with tetravalent cerium ions in the boron-containing water.
The method for treating boron-containing water of the third invention is characterized in that, in the first invention, tetravalent cerium ions are present in the boron-containing water by adding a tetravalent cerium salt to the boron-containing water. To do.
The method for treating boron-containing water according to a fourth invention is the method according to the second invention, wherein a trivalent cerium salt is added to the boron-containing water and then an oxidizing agent is added to oxidize trivalent cerium ions. Trivalent cerium ions are present together with tetravalent cerium ions in boron-containing water.
The method for treating boron-containing water of the fifth invention is characterized in that, in the fourth invention, the oxidizing agent is hydrogen peroxide water.
The boron-containing water treatment method of the sixth invention is characterized in that, in the fifth invention, the amount of hydrogen peroxide added is such that the molar ratio of hydrogen peroxide to cerium is 1 or less.
本発明によれば、ホウ素含有水中に４価のセリウムイオンを存在させることで、３価のセリウムイオンのみを存在させた場合に比べて、固液分離性の高い沈殿物が得られる。 According to the present invention, by allowing tetravalent cerium ions to be present in boron-containing water, a precipitate having a high solid-liquid separation property can be obtained as compared with the case where only trivalent cerium ions are present.
つぎに、本発明の実施形態を説明する。
本願発明者らは、ホウ素含有水にセリウムイオンを存在させ、共沈反応によりホウ素を沈殿させる場合において、セリウムイオンの価数に着目して研究したところ、ホウ素含有水に４価のセリウムイオンを存在させれば、得られる沈殿物の固液分離性が高くなるとの知見を得た。
Next, an embodiment of the present invention will be described.
In the case where cerium ions are present in boron-containing water and boron is precipitated by coprecipitation reaction, the inventors of the present application have studied focusing on the valence of cerium ions. The knowledge that the solid-liquid separability of the resulting precipitate is improved if it is present.
すなわち、本発明の一実施形態に係るホウ素含有水の処理方法は、ホウ素含有水中に４価のセリウムイオンを存在させ、ホウ素含有水のｐＨを調整することで、共沈反応によりホウ素を沈殿させることを特徴とする。 That is, in the method for treating boron-containing water according to one embodiment of the present invention, boron is precipitated by a coprecipitation reaction by allowing tetravalent cerium ions to be present in the boron-containing water and adjusting the pH of the boron-containing water. It is characterized by that.
より詳細には、まず、ホウ素含有水に４価のセリウム塩を添加する（セリウム添加工程）。これにより、ホウ素含有水中に４価のセリウムイオンを存在させる。４価のセリウム塩としては硫酸セリウム(IV)、酸化セリウム(IV)などが挙げられる。 More specifically, first, a tetravalent cerium salt is added to boron-containing water (cerium addition step). As a result, tetravalent cerium ions are present in the boron-containing water. Examples of the tetravalent cerium salt include cerium sulfate (IV) and cerium oxide (IV).
つぎに、ホウ素含有水にｐＨ調整剤を添加して、ホウ素含有水のｐＨを７〜９に調整する（共沈工程）。これにより、共沈反応が生じ、ホウ素の沈殿物が得られる。ｐＨ調整剤としてはアンモニア水、水酸化ナトリウムなどが用いられる。 Next, a pH adjuster is added to the boron-containing water to adjust the pH of the boron-containing water to 7 to 9 (coprecipitation step). Thereby, a coprecipitation reaction occurs and a boron precipitate is obtained. As the pH adjuster, aqueous ammonia, sodium hydroxide, or the like is used.
最後に、共沈工程で得られたスラリーを固液分離して、沈殿物を除去した処理液を得る（固液分離工程）。ホウ素含有水中に４価のセリウムイオンを存在させることで、３価のセリウムイオンのみを存在させた場合に比べて、固液分離性の高い沈殿物が得られる。そのため、固液分離にかかる時間を短縮でき、効率よくホウ素を除去できる。 Finally, the slurry obtained in the coprecipitation step is subjected to solid-liquid separation to obtain a treatment liquid from which the precipitate has been removed (solid-liquid separation step). By allowing tetravalent cerium ions to be present in the boron-containing water, a precipitate having a high solid-liquid separation property can be obtained as compared with the case where only trivalent cerium ions are present. Therefore, the time required for solid-liquid separation can be shortened, and boron can be efficiently removed.
ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させてもよい。ホウ素含有水に４価のセリウム塩と３価のセリウム塩とを添加することで、ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させることができる。あるいは、つぎの手順を採用してもよい。 Trivalent cerium ions may be present together with tetravalent cerium ions in the boron-containing water. By adding the tetravalent cerium salt and the trivalent cerium salt to the boron-containing water, the trivalent cerium ion can be present together with the tetravalent cerium ion in the boron-containing water. Alternatively, the following procedure may be adopted.
すなわち、まず、ホウ素含有水に３価のセリウム塩を添加する（セリウム添加工程）。これにより、ホウ素含有水中に３価のセリウムイオンを存在させる。３価のセリウム塩としては硝酸セリウム(III)、塩化セリウム(III)、リン酸セリウム(III)、炭酸セリウム(III)などが挙げられる。 That is, first, a trivalent cerium salt is added to boron-containing water (cerium addition step). Thereby, trivalent cerium ions are present in the boron-containing water. Examples of the trivalent cerium salt include cerium (III) nitrate, cerium (III) chloride, cerium (III) phosphate, and cerium (III) carbonate.
つぎに、ホウ素含有水に酸化剤を添加して３価のセリウムイオンの一部を酸化して４価のセリウムイオンにする（酸化工程）。これにより、ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させる。 Next, an oxidizing agent is added to the boron-containing water to oxidize a part of trivalent cerium ions to form tetravalent cerium ions (oxidation step). Thereby, trivalent cerium ions are allowed to exist together with tetravalent cerium ions in the boron-containing water.
酸化剤としては過酸化水素水、過マンガン酸カリウム、オゾンガスなどが用いられる。特に過酸化水素水は液体であって、濃度調整可能であるので取り扱いが容易である。酸化剤の添加量は３価のセリウムイオンの所定割合を４価のセリウムイオンに酸化できる量に設定される。また、過酸化水素水の添加量は、セリウムに対する過酸化水素の添加モル比（以下、「Ｈ2Ｏ2／Ｃｅ」と称する。）が１以下となる量とすることが好ましい。そうすれば、ホウ素を十分に除去できる。 As the oxidizing agent, hydrogen peroxide, potassium permanganate, ozone gas, or the like is used. In particular, the hydrogen peroxide solution is liquid and can be easily handled because the concentration can be adjusted. The addition amount of the oxidizing agent is set to an amount that can oxidize a predetermined proportion of trivalent cerium ions to tetravalent cerium ions. The amount of hydrogen peroxide solution added is preferably such that the molar ratio of hydrogen peroxide to cerium (hereinafter referred to as “H 2 O 2 / Ce”) is 1 or less. Then, boron can be sufficiently removed.
ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンを存在させれば、固液分離性の高い沈殿物が得られるとともに、ホウ素の除去効率を高めることができる。なお、４価のセリウムイオンと３価のセリウムイオンとの割合は、固液分離性と除去効率とを考慮して設定すればよい。 If trivalent cerium ions are present together with tetravalent cerium ions in the boron-containing water, a precipitate having a high solid-liquid separation property can be obtained and the boron removal efficiency can be increased. The ratio of tetravalent cerium ions and trivalent cerium ions may be set in consideration of solid-liquid separability and removal efficiency.
まず、ホウ素含有水へのセリウム塩の添加と、沈殿物の固液分離性との関係について試験を行った。 First, the relationship between the addition of cerium salt to boron-containing water and the solid-liquid separability of the precipitate was tested.
（実施例１）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは３であった。ホウ素含有水に純度９８％の硫酸セリウム(IV)・四水和物試薬を４５ｇ添加した。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
Example 1
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 3. 45 g of 98% pure cerium (IV) sulfate tetrahydrate reagent was added to the boron-containing water. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーをビーカー内で静置した。すると、沈殿物が沈降しはじめ上澄み液と沈殿物との界面が現れた。この界面が１ｃｍ低下するのにかかる時間を沈降速度と定義し、これを測定した。その結果、沈降速度は８０分／ｃｍであった。 The obtained slurry was allowed to stand in a beaker. Then, the precipitate began to settle, and an interface between the supernatant and the precipitate appeared. The time taken for this interface to drop by 1 cm was defined as the sedimentation velocity and measured. As a result, the sedimentation rate was 80 minutes / cm.
前記と同様の手順で新たに沈殿物を含むスラリーを得た。得られたスラリーを孔径０．４５μｍのメンブレンフィルター（ＡＤＶＡＮＴＥＣ社製、型番Ａ０４５Ａ０９０Ｃ、以下同じ。）に通過させ固液分離した。固液分離に要した時間（濾過時間）は４５分であった。 A slurry containing a new precipitate was obtained by the same procedure as described above. The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm (manufactured by ADVANTEC, model number A045A090C, the same shall apply hereinafter) for solid-liquid separation. The time required for solid-liquid separation (filtration time) was 45 minutes.
得られた濾液をＩＣＰ分析（ＩＣＰ分析装置としてセイコーインスツルメンツ社製、型番ＳＰＳ−７８００を用いた。以下同じ。）して、残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は１０．１ｍｇ／Ｌであった。また、ホウ素含有水の体積当りの沈殿物の乾燥重量は９８．５ｇ／Ｌであり、ホウ素の除去効率は１０．０ｍｇ／ｇであった。ここで、除去効率とは除去されたホウ素の重量［ｍｇ］を沈殿物の乾燥重量［ｇ］で除算した値である。 The obtained filtrate was subjected to ICP analysis (Seiko Instruments Inc., model number SPS-7800 was used as an ICP analyzer, the same applies hereinafter), and the residual boron concentration was measured. As a result, the residual boron concentration was 10.1 mg / L. The dry weight of the precipitate per volume of boron-containing water was 98.5 g / L, and the boron removal efficiency was 10.0 mg / g. Here, the removal efficiency is a value obtained by dividing the weight [mg] of the removed boron by the dry weight [g] of the precipitate.
（実施例２）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは３であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。つぎに、ホウ素含有水に濃度１０ｍｏｌ／Ｌの過酸化水素水を１０ｃｃ添加した。１時間撹拌した後のホウ素含有水のｐＨは１であった。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
(Example 2)
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 3. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. Next, 10 cc of hydrogen peroxide solution having a concentration of 10 mol / L was added to the boron-containing water. The pH of the boron-containing water after stirring for 1 hour was 1. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーをビーカー内で静置し、沈降速度を測定した。その結果、沈降速度は６０分／ｃｍであった。 The obtained slurry was allowed to stand in a beaker, and the sedimentation rate was measured. As a result, the sedimentation rate was 60 minutes / cm.
前記と同様の手順で新たに沈殿物を含むスラリーを得た。得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。濾過時間は４０分であった。 A slurry containing a new precipitate was obtained by the same procedure as described above. The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The filtration time was 40 minutes.
得られた濾液をＩＣＰ分析して残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は９．２ｍｇ／Ｌであった。また、ホウ素含有水の体積当りの沈殿物の乾燥重量は９３．２ｇ／Ｌであり、ホウ素の除去効率は１０．６ｍｇ／ｇであった。 The obtained filtrate was subjected to ICP analysis to determine the residual boron concentration. As a result, the residual boron concentration was 9.2 mg / L. The dry weight of the precipitate per volume of boron-containing water was 93.2 g / L, and the boron removal efficiency was 10.6 mg / g.
（比較例１）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは３であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を２０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
(Comparative Example 1)
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 3. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. While the boron-containing water was stirred, 20 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーをビーカー内で静置し、沈降速度を測定しようとしたが、界面が現れず測定不能であった。 The obtained slurry was allowed to stand in a beaker and an attempt was made to measure the sedimentation speed, but the interface did not appear and measurement was impossible.
前記と同様の手順で新たに沈殿物を含むスラリーを得た。得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。濾過時間は６４０分であった。 A slurry containing a new precipitate was obtained by the same procedure as described above. The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The filtration time was 640 minutes.
得られた濾液をＩＣＰ分析して残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は１．０６ｍｇ／Ｌであった。また、ホウ素含有水の体積当りの沈殿物の乾燥重量は８１．０ｇ／Ｌであり、ホウ素の除去効率は１２．３ｍｇ／ｇであった。 The obtained filtrate was subjected to ICP analysis to determine the residual boron concentration. As a result, the residual boron concentration was 1.06 mg / L. The dry weight of the precipitate per volume of boron-containing water was 81.0 g / L, and the boron removal efficiency was 12.3 mg / g.
実施例１、２および比較例１を表１にまとめる。
表１より、実施例１、２は比較例１に比べて濾過時間が１０分の１以下となっていることが分かる。これより、ホウ素含有水中に４価のセリウムイオンを存在させれば、固液分離性の高い沈殿物が得られることが確認された。 From Table 1, it can be seen that Examples 1 and 2 have a filtration time of 1/10 or less as compared with Comparative Example 1. From this, it was confirmed that if tetravalent cerium ions are present in the boron-containing water, a precipitate having a high solid-liquid separation property can be obtained.
また、４価のセリウム塩を添加した実施例１に比べて、３価のセリウム塩を添加した後に酸化剤を添加した実施例２の方が、濾過時間が短いことが分かる。発明者らはこの現象について、３価のセリウムイオンが全て酸化されるわけではなく、わずかに残留するためであると考えている。３価のセリウムイオンにより得られる沈殿物は非常に微細な粒子である。この微粒子が４価のセリウムイオンにより得られる沈殿物が生じる核として働いていると考えられる。ホウ素含有水中に４価のセリウムイオンとともに３価のセリウムイオンが存在した方が、より固液分離性の高い沈殿物が得られると考えられる。 Moreover, it turns out that the filtration time of Example 2 which added the oxidizing agent after adding trivalent cerium salt is shorter than Example 1 which added tetravalent cerium salt. The inventors consider that this phenomenon is because not all trivalent cerium ions are oxidized but remain slightly. The precipitate obtained by trivalent cerium ions is very fine particles. It is considered that these fine particles function as nuclei for generating precipitates obtained by tetravalent cerium ions. The presence of trivalent cerium ions together with tetravalent cerium ions in boron-containing water is considered to yield a precipitate with higher solid-liquid separation.
つぎに、ホウ素含有水に３価のセリウム塩を添加した後に酸化剤を添加する場合において、過酸化水素水の添加量と残存ホウ素濃度との関係を試験した。 Next, when adding an oxidizing agent after adding a trivalent cerium salt to boron-containing water, the relationship between the amount of hydrogen peroxide added and the residual boron concentration was tested.
（実施例３）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは２であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。つぎに、ホウ素含有水に濃度１０ｍｏｌ／Ｌの過酸化水素水を２．５ｃｃ添加した。Ｈ2Ｏ2／Ｃｅ＝０．２５である。１時間撹拌した後のホウ素含有水のｐＨは１であった。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
(Example 3)
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 2. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. Next, 2.5 cc of hydrogen peroxide solution having a concentration of 10 mol / L was added to the boron-containing water. H 2 O 2 /Ce=0.25. The pH of the boron-containing water after stirring for 1 hour was 1. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。得られた濾液をＩＣＰ分析して残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は２．４ｍｇ／Ｌであった。 The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The obtained filtrate was subjected to ICP analysis to determine the residual boron concentration. As a result, the residual boron concentration was 2.4 mg / L.
（実施例４）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは２であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。つぎに、ホウ素含有水に濃度１０ｍｏｌ／Ｌの過酸化水素水を５ｃｃ添加した。Ｈ2Ｏ2／Ｃｅ＝０．５である。１時間撹拌した後のホウ素含有水のｐＨは１であった。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
Example 4
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 2. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. Next, 5 cc of hydrogen peroxide solution having a concentration of 10 mol / L was added to the boron-containing water. H 2 O 2 /Ce=0.5. The pH of the boron-containing water after stirring for 1 hour was 1. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。得られた濾液をＩＣＰ分析して、残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は８．５ｍｇ／Ｌであった。 The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The obtained filtrate was subjected to ICP analysis to measure the residual boron concentration. As a result, the residual boron concentration was 8.5 mg / L.
（実施例５）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは２であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。つぎに、ホウ素含有水に濃度１０ｍｏｌ／Ｌの過酸化水素水を１０ｃｃ添加した。Ｈ2Ｏ2／Ｃｅ＝１である。１時間撹拌した後のホウ素含有水のｐＨは１であった。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
(Example 5)
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 2. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. Next, 10 cc of hydrogen peroxide solution having a concentration of 10 mol / L was added to the boron-containing water. H 2 O 2 / Ce = 1. The pH of the boron-containing water after stirring for 1 hour was 1. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。得られた濾液をＩＣＰ分析して、残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は１３．５ｍｇ／Ｌであった。 The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The obtained filtrate was subjected to ICP analysis to measure the residual boron concentration. As a result, the residual boron concentration was 13.5 mg / L.
（実施例６）
ホウ素濃度が１，０００ｍｇ／Ｌのホウ素含有水を容量５００ｃｃのビーカーに３００ｃｃ入れた。ホウ素含有水の初期ｐＨは２であった。ホウ素含有水に純度９８％の硝酸セリウム(III)・六水和物試薬を４５ｇ添加した。つぎに、ホウ素含有水に濃度１０ｍｏｌ／Ｌの過酸化水素水を２０ｃｃ添加した。Ｈ2Ｏ2／Ｃｅ＝２である。１時間撹拌した後のホウ素含有水のｐＨは１であった。ホウ素含有水を撹拌しつつ、濃度１５ｍｏｌ／Ｌのアンモニア水を３０ｃｃ添加してｐＨ調整を行った。共沈反応が生じ、沈殿物を含むスラリーが得られた。１時間撹拌した後の液相のｐＨは９であった。
(Example 6)
300 cc of boron-containing water having a boron concentration of 1,000 mg / L was placed in a 500 cc beaker. The initial pH of the boron-containing water was 2. 45 g of 98% pure cerium (III) nitrate hexahydrate reagent was added to the boron-containing water. Next, 20 cc of hydrogen peroxide solution having a concentration of 10 mol / L was added to the boron-containing water. H 2 O 2 / Ce = 2. The pH of the boron-containing water after stirring for 1 hour was 1. While stirring the boron-containing water, 30 cc of 15 mol / L ammonia water was added to adjust the pH. A coprecipitation reaction occurred and a slurry containing the precipitate was obtained. The pH of the liquid phase after stirring for 1 hour was 9.
得られたスラリーを孔径０．４５μｍのメンブレンフィルターに通過させ固液分離した。得られた濾液をＩＣＰ分析して、残存ホウ素濃度を測定した。その結果、残存ホウ素濃度は７６．３ｍｇ／Ｌであった。 The obtained slurry was passed through a membrane filter having a pore diameter of 0.45 μm and separated into solid and liquid. The obtained filtrate was subjected to ICP analysis to measure the residual boron concentration. As a result, the residual boron concentration was 76.3 mg / L.
実施例３〜６を表２にまとめる。
表２より、実施例６（Ｈ2Ｏ2／Ｃｅ＝２）は実施例３〜５（Ｈ2Ｏ2／Ｃｅ＝０．２５、０．５、１）に比べて残存ホウ素濃度が著しく高いことが分かる。沈殿物の様子も実施例６と実施例３〜５とでは異なり、実施例６ではセリウムの水酸化物とは別のものが生成されたと考えられる。したがって、過酸化水素水の添加量はＨ2Ｏ2／Ｃｅが１以下となる量とすることが好ましいことが確認された。 From Table 2, Example 6 (H 2 O 2 / Ce = 2) has a significantly higher residual boron concentration than Examples 3 to 5 (H 2 O 2 /Ce=0.25, 0.5, 1). I understand that. The state of the precipitate is also different between Example 6 and Examples 3 to 5, and it is considered that Example 6 produced something different from the cerium hydroxide. Therefore, it was confirmed that the amount of hydrogen peroxide added was preferably such that H 2 O 2 / Ce was 1 or less.
Claims (6)
前記ホウ素含有水のｐＨを調整することで、共沈反応によりホウ素を沈殿させる
ことを特徴とするホウ素含有水の処理方法。 Tetravalent cerium ions are present in boron-containing water,
A method for treating boron-containing water, wherein the boron is precipitated by coprecipitation reaction by adjusting the pH of the boron-containing water.
ことを特徴とする請求項１記載のホウ素含有水の処理方法。 The method for treating boron-containing water according to claim 1, wherein trivalent cerium ions are present together with tetravalent cerium ions in the boron-containing water.
ことを特徴とする請求項１記載のホウ素含有水の処理方法。 The method for treating boron-containing water according to claim 1, wherein tetravalent cerium ions are present in the boron-containing water by adding a tetravalent cerium salt to the boron-containing water.
ことを特徴とする請求項２記載のホウ素含有水の処理方法。 After adding a trivalent cerium salt to the boron-containing water, an oxidant is added to oxidize the trivalent cerium ions, so that trivalent cerium ions are present together with the tetravalent cerium ions in the boron-containing water. The method for treating boron-containing water according to claim 2, wherein:
ことを特徴とする請求項４記載のホウ素含有水の処理方法。 The method for treating boron-containing water according to claim 4, wherein the oxidizing agent is hydrogen peroxide water.
ことを特徴とする請求項５記載のホウ素含有水の処理方法。 6. The method for treating boron-containing water according to claim 5, wherein the amount of hydrogen peroxide water added is such that the molar ratio of hydrogen peroxide to cerium is 1 or less.
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| WO2022145278A1 (en) * | 2020-12-28 | 2022-07-07 | 株式会社日本海水 | Harmful substance remover and method for treating harmful substance with use of same |
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