JP2008188536A - Method for treating selenium-containing drainage - Google Patents
Method for treating selenium-containing drainage Download PDFInfo
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- JP2008188536A JP2008188536A JP2007026040A JP2007026040A JP2008188536A JP 2008188536 A JP2008188536 A JP 2008188536A JP 2007026040 A JP2007026040 A JP 2007026040A JP 2007026040 A JP2007026040 A JP 2007026040A JP 2008188536 A JP2008188536 A JP 2008188536A
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 352
- 239000011669 selenium Substances 0.000 title claims abstract description 352
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 352
- 238000000034 method Methods 0.000 title claims description 29
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000007800 oxidant agent Substances 0.000 claims abstract description 37
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 98
- 230000033116 oxidation-reduction process Effects 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012085 test solution Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
Description
セレンが溶解しているセレン含有液の処理方法に関し、とくに産業のため発生したセレン含有排水やセレン含有処理水の処理方法に関する。また、セレンが含まれている天然由来の水の処理方法に関する。 The present invention relates to a method for treating a selenium-containing liquid in which selenium is dissolved, and particularly relates to a method for treating selenium-containing wastewater and selenium-containing treated water generated for industry. In addition, the present invention relates to a method for treating naturally occurring water containing selenium.
排水中のセレンは、法的に規制された濃度があり、具体的には０．１ｍｇ／Ｌ以下にしなければならない。このためセレンを排水中から除去、分離するためさまざまな排水処理技術が提唱されている。 Selenium in wastewater has a legally regulated concentration, and specifically, it must be 0.1 mg / L or less. For this reason, various wastewater treatment techniques have been proposed to remove and separate selenium from wastewater.
特許文献１には、６価のセレンを酸性条件下にて樹脂を用いて吸着し、アルカリ溶液を用いて吸着させたセレンを樹脂から脱着させることによって、セレンを排水中から除去する処理技術が開示されている。
しかしながら、セレン含有排水中のセレンは、一般に、４価のセレン（以下、４価セレン（難吸着性セレン）と呼ぶ）と６価のセレン（以下、６価セレン（易吸着性セレン）と呼ぶ）の２種類の形態で存在している。上記特許文献１の排水処理技術を用いた場合には、樹脂によりセレン含有排水から６価セレン（易吸着性セレン）を吸着除去することはできるが、４価セレン（難吸着性セレン）については６価セレン（易吸着性セレン）と異なり、吸着の選択性が小さく、硫酸イオン等、他の妨害元素の影響を受け易いという問題があるため、樹脂に確実に吸着させることができず、セレン含有排水からの吸着除去が難しかった。このため、上記特許文献１の排水処理技術では、樹脂を用いてセレン含有排水からセレンを効果的に吸着除去することができなかった。
However, selenium in selenium-containing wastewater is generally called tetravalent selenium (hereinafter referred to as tetravalent selenium (non-adsorptive selenium)) and hexavalent selenium (hereinafter referred to as hexavalent selenium (easily adsorbable selenium)). ) Exist in two forms. When the wastewater treatment technology of
本発明は上記課題に鑑みてなされたものであり、樹脂を用いてセレン含有排水からセレンを効果的に吸着除去することが可能なセレン含有排水の処理技術の提供をその目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a selenium-containing wastewater treatment technique that can effectively adsorb and remove selenium from selenium-containing wastewater using a resin.
上記課題を解決するために、本発明によれば、セレン含有排水中の難吸着性セレン（４価セレン）を除去した後、前記セレン含有排水中のセレンを樹脂で吸着除去することを特徴とする、セレン含有排水の処理方法が提供される。 In order to solve the above problems, according to the present invention, after removing hardly adsorbing selenium (tetravalent selenium) in selenium-containing wastewater, selenium in the selenium-containing wastewater is adsorbed and removed with a resin. A method for treating selenium-containing wastewater is provided.
上記処理方法において、前記セレン含有排水中のセレンを樹脂で吸着除去する前に、前記セレン含有排水にアルカリを添加し、ｐＨを1０以上にするようにしてもよい。 In the above processing method, before adsorbing and removing selenium in the selenium-containing wastewater with a resin, an alkali may be added to the selenium-containing wastewater so as to have a pH of 10 or more.
上記処理方法において、前記セレン含有排水中の難吸着性セレンの除去は、前記セレン含有排水中の難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化することにより行うようにしてもよい。 In the above treatment method, the removal of hardly adsorbable selenium in the selenium-containing wastewater is performed by oxidizing the hardly adsorbable selenium (tetravalent selenium) in the selenium-containing wastewater to easily adsorbable selenium (hexavalent selenium). You may do it.
上記処理方法において、前記セレン含有排水中の難吸着性セレン（４価セレン）の易吸着性セレン（６価セレン）への酸化は、酸化剤の添加により行うようにしてもよい。 In the treatment method, oxidation of the hardly adsorbing selenium (tetravalent selenium) in the selenium-containing waste water to the easily adsorbing selenium (hexavalent selenium) may be performed by adding an oxidizing agent.
上記処理方法において、前記酸化剤が、空気、酸素、オゾン、過酸化水素、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、及び過炭酸ナトリウム（Ｎａ２ＣＯ３・２．５Ｈ２Ｏ２）からなる群から選ばれる酸化剤であってもよい。 In the treatment method, the oxidizing agent is air, oxygen, ozone, hydrogen peroxide, sodium hypochlorite, calcium hypochlorite, and sodium percarbonate (Na 2 CO 3 .2.5H 2 O 2 ). An oxidizing agent selected from the group consisting of
上記処理方法において、酸化還元電位が４００ｍＶ以上になるようにして前記酸化剤を添加するようにしてもよい。 In the treatment method, the oxidizing agent may be added so that the oxidation-reduction potential is 400 mV or more.
上記処理方法において、前記セレン含有排水中の難吸着性セレン（４価セレン）の易吸着性セレン（６価セレン）への酸化は、紫外線照射により行うようにしてもよい。 In the above treatment method, oxidation of the hardly adsorbable selenium (tetravalent selenium) in the selenium-containing waste water to the easily adsorbable selenium (hexavalent selenium) may be performed by ultraviolet irradiation.
上記処理方法において、前記樹脂がイオン交換樹脂であってもよい。 In the above processing method, the resin may be an ion exchange resin.
本発明によれば、セレン含有排水中に含まれる難吸着性セレン（４価セレン）を除去した後に、樹脂を用いてセレンの吸着除去を行うようにしたことによって、セレン含有排水からセレンを効果的に吸着除去することが可能になる。特に、難吸着性セレン（４価セレン）の除去を、酸化剤等で難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化することによって行う場合には、セレン含有排水からのセレンの効果的な吸着除去を非常に容易に実施できる。 According to the present invention, after removing the hardly adsorbing selenium (tetravalent selenium) contained in the selenium-containing wastewater, the selenium is effectively removed from the selenium-containing wastewater by removing the selenium using a resin. Can be removed by adsorption. In particular, in the case where removal of hardly adsorbing selenium (tetravalent selenium) is performed by oxidizing hardly adsorbing selenium (tetravalent selenium) to easily adsorbing selenium (hexavalent selenium) with an oxidizing agent or the like, selenium-containing Effective adsorption removal of selenium from waste water can be carried out very easily.
以下、図面を参照しながら、本発明の好適な実施形態について説明をする。図１は、本発明の実施の形態に係るセレン含有排水の処理方法の手順の一例を示すフロー図である。 Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart showing an example of a procedure of a method for treating selenium-containing wastewater according to an embodiment of the present invention.
セレンを含む排水（以下、セレン含有排水又は単に排水とも言う）は、産業上発生した排水等であり、この排水の処理を開始する（ステップ０）にあたって、まず、この排水を例えば配管等により集水する（ステップ１）。本実施の形態では、集水したセレン含有排水には、例えば難吸着性セレン（４価セレン）としてＳｅＯ３ ２−が１０％程度、易吸着性セレン（６価セレン）としてＳｅＯ４ ２−が９０％程度含まれている。なお、セレン含有排水は、産業上発生した排水ではなく、自然由来のものであってもよい。セレン含有排水のセレン濃度は１ｍｇ／Ｌ以下の低濃度であってもよいし、１ｍｇ／Ｌを超過する高濃度、例えば２０ｍｇ／Ｌ程度であってもよい。 Wastewater containing selenium (hereinafter also referred to as selenium-containing wastewater or simply wastewater) is industrially generated wastewater, etc., and when this wastewater treatment is started (step 0), this wastewater is first collected by, for example, piping. Water (step 1). In the present embodiment, the collected selenium-containing wastewater contains, for example, about 10% of SeO 3 2- as hardly adsorbing selenium (tetravalent selenium) and SeO 4 2- as easily adsorbing selenium (hexavalent selenium). About 90% is included. The selenium-containing wastewater may be naturally derived water instead of industrially generated wastewater. The selenium concentration of the selenium-containing wastewater may be a low concentration of 1 mg / L or less, or may be a high concentration exceeding 1 mg / L, for example, about 20 mg / L.
集水したセレン含有排水に酸化剤を添加し、セレン含有排水中の難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化することによって難吸着性セレン（４価セレン）を除去する（ステップ２）。本実施の形態では、酸化剤としてオゾン（Ｏ３）を用いている。なお、酸化剤としては、空気、酸素、過酸化水素、次亜塩素酸ナトリウム、次亜塩素酸カルシウム又は過炭酸ナトリウム等、オゾン以外の酸化剤を用いてもよい。酸化剤を添加する際には、セレン含有排水を撹拌しながら吹込むようにした。また、酸化還元電位（ＯＲＰ）が４００ｍＶ以上になるようにして酸化剤を添加するのが好ましい。酸化剤を添加する際にセレン含有排水のｐＨを調整し、アルカリ性にすることで難吸着性セレン（４価セレン）の酸化反応を促進させるようにしてもよい。特にｐＨを１０以上とするとよい。１０以下ではセレンの挙動が安定しないためである。 An oxidant is added to the collected selenium-containing wastewater, and the hardly adsorbing selenium (tetravalent selenium) in the selenium-containing wastewater is oxidized to easily adsorbable selenium (hexavalent selenium). ) Is removed (step 2). In this embodiment, ozone (O 3 ) is used as the oxidizing agent. As the oxidizing agent, oxidizing agents other than ozone such as air, oxygen, hydrogen peroxide, sodium hypochlorite, calcium hypochlorite, or sodium percarbonate may be used. When adding the oxidizing agent, the selenium-containing wastewater was blown in while stirring. Further, it is preferable to add the oxidizing agent so that the oxidation-reduction potential (ORP) is 400 mV or more. When adding an oxidizing agent, the pH of the selenium-containing wastewater may be adjusted to be alkaline so as to promote the oxidation reaction of hardly adsorbing selenium (tetravalent selenium). In particular, the pH should be 10 or more. This is because the behavior of selenium is not stable at 10 or less.
上記ステップ２により難吸着性セレン（４価セレン）が除去されたセレン含有排水に樹脂を添加し、セレンをこの樹脂に吸着させる（ステップ３）。本発明の実施の形態では、樹脂として例えばイオン交換樹脂を用いている。なお、イオン交換樹脂は、ＯＨ型を用いるのが好ましい。 A resin is added to the selenium-containing waste water from which the hardly adsorbing selenium (tetravalent selenium) has been removed in Step 2, and selenium is adsorbed on the resin (Step 3). In the embodiment of the present invention, for example, an ion exchange resin is used as the resin. The ion exchange resin is preferably OH type.
セレン含有排水をろ過し、セレンを吸着させた樹脂をセレン含有排水から除去する（ステップ４）。なお、上記ステップ３、４では、セレン含有排水を樹脂に添加した後にろ過し、セレンを吸着させた樹脂をセレン含有排水から除去する場合について説明したが、セレン含有排水を樹脂塔に通液させることによって、セレン含有排水中のセレンを吸着除去するようにしてもよい。 The selenium-containing wastewater is filtered, and the resin adsorbed with selenium is removed from the selenium-containing wastewater (step 4). In steps 3 and 4 described above, the selenium-containing wastewater is filtered after being added to the resin, and the resin having adsorbed selenium is removed from the selenium-containing wastewater. However, the selenium-containing wastewater is passed through the resin tower. Thus, selenium in the selenium-containing waste water may be adsorbed and removed.
上記ステップ０〜４の手順により、セレンを低濃度に減少してセレン濃度を法律で規制される値以下にした排水が得られ、セレン含有排水の処理が完了する（ステップ６）。このようにして得られた排水は、その他規制物質等が基準を十分に満たしていれば放水可能となる。 According to the procedures of Steps 0 to 4, selenium is reduced to a low concentration to obtain waste water having a selenium concentration that is not more than the value regulated by law, and the treatment of selenium-containing waste water is completed (Step 6). The wastewater thus obtained can be discharged if other regulated substances and the like sufficiently satisfy the standards.
以上の実施の形態によれば、セレン含有排水中のセレンを樹脂で吸着除去する前に、セレン含有排水中の難吸着性セレン（４価セレン）を除去したことによって、セレン含有排水中には主として易吸着性セレン（６価セレン）だけが含まれることになる。易吸着性セレン（６価セレン）は、難吸着性セレン（４価セレン）と異なり、樹脂に対する吸着の選択性が高いため、硫酸イオン等の他の妨害元素の影響を受けにくいために樹脂に確実に吸着させることができる。このように、本発明によれば、セレン含有排水中のセレンを樹脂に効果的に吸着させて除去することが可能になる。また、例えばオゾン等の酸化剤を添加し、難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化することによって難吸着性セレン（４価セレン）の除去を行うようにした場合には、上述したようにセレンを効果的に吸着除去可能なセレン含有排水の処理を非常に容易に実施することができる。 According to the above embodiment, before adsorbing and removing selenium in the selenium-containing wastewater with the resin, the non-adsorbing selenium (tetravalent selenium) in the selenium-containing wastewater is removed. Only easily adsorbable selenium (hexavalent selenium) is included. Unlike the hard-to-adsorb selenium (tetravalent selenium), the easy-to-adsorb selenium (hexavalent selenium) has high selectivity for adsorption to the resin, so it is less susceptible to other interfering elements such as sulfate ions. Adsorption can be ensured. Thus, according to the present invention, selenium in the selenium-containing wastewater can be effectively adsorbed and removed by the resin. Further, for example, by adding an oxidizing agent such as ozone and oxidizing the hardly adsorbing selenium (tetravalent selenium) to the easily adsorbing selenium (hexavalent selenium), the hardly adsorbing selenium (tetravalent selenium) is removed. In this case, as described above, the treatment of the selenium-containing wastewater that can effectively adsorb and remove selenium can be performed very easily.
以上、添付図面を参照しながら本発明の好適な実施形態について説明したが、本発明は係る例に限定されない。当業者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例又は修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。 As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, this invention is not limited to the example which concerns. It is obvious for those skilled in the art that various changes or modifications can be conceived within the scope of the technical idea described in the claims, and of course, the technical scope of the present invention is also possible. It is understood that it belongs to.
上述した実施形態では、セレン含有排水中の難吸着性セレン（４価セレン）を除去する際に、難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化することによって除去する（上記ステップ２）場合について説明したが、その他の方法を用いてセレン含有排水の難吸着性セレン（４価セレン）を除去するようにしてもよい。 In the embodiment described above, when removing the hardly adsorbing selenium (tetravalent selenium) in the selenium-containing wastewater, the hardly adsorbing selenium (tetravalent selenium) is oxidized to easily adsorbable selenium (hexavalent selenium). Although the case of removing (step 2 above) has been described, the non-adsorbing selenium (tetravalent selenium) of the selenium-containing wastewater may be removed using other methods.
上述した実施形態では、難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化する際に、酸化剤を添加することによって酸化する場合について説明したが、例えばセレン含有排水に紫外線照射することによって酸化したり、又はＡＯＰ（紫外線、過酸化水素、オゾンの組合わせ）等多くの手段で酸化する等、その他の方法により難吸着性セレン（４価セレン）の酸化を行うようにしてもよい。 In the above-described embodiment, the case of oxidizing by adding an oxidizing agent when oxidizing hardly adsorbing selenium (tetravalent selenium) to easily adsorbing selenium (hexavalent selenium) has been described. Oxidation of hard-to-adsorb selenium (tetravalent selenium) by other methods, such as oxidation by irradiating with UV light or oxidation by many means such as AOP (combination of UV light, hydrogen peroxide and ozone) You may do it.
本発明を実施例と比較例を用いて説明する。 The present invention will be described using examples and comparative examples.
下記表１は、本発明の手順によりセレン含有排水を処理した結果（実施例１、２）と、本発明の手順によらず、樹脂による吸着除去だけでセレン含有排水を処理した結果（比較例１）を示している。 Table 1 below shows the results of treating selenium-containing wastewater according to the procedure of the present invention (Examples 1 and 2) and the results of treating selenium-containing wastewater only by adsorption removal with a resin, regardless of the procedure of the present invention (Comparative Example). 1).
上記表１において、実施例１、２、比較例１の「オゾン添加前の状態」は、処理を行う前の初期状態のセレン含有排水のｐＨ、酸化還元電位（ＯＲＰ）、４価セレン濃度（ｍｇ／Ｌ）、６価セレン濃度（ｍｇ／Ｌ）、全セレン濃度（ｍｇ／Ｌ）を示している。即ち、実施例１、２の「酸化剤添加前の状態」は、セレン含有排水に酸化剤としてのオゾンを添加する（図１に示すステップ２）前の状態を示しており、比較例１の「酸化剤添加前の状態」は、樹脂を用いてセレンを吸着除去する前の状態を示している。 In Table 1 above, the “state before addition of ozone” in Examples 1 and 2 and Comparative Example 1 are the pH, redox potential (ORP), and tetravalent selenium concentration (ORP) of the selenium-containing wastewater in the initial state before treatment. mg / L), hexavalent selenium concentration (mg / L), and total selenium concentration (mg / L). That is, the “state before addition of oxidant” in Examples 1 and 2 shows the state before ozone as an oxidant is added to the selenium-containing wastewater (step 2 shown in FIG. 1). “State before addition of oxidant” indicates a state before selenium is adsorbed and removed using a resin.
上記表１において、実施例１、２の「酸化剤添加後の状態」は、セレン含有排水に酸化剤としてのオゾンを添加し、セレン含有排水中の難吸着性セレン（４価セレン）を酸化して易吸着性セレン（６価セレン）にすることにより難吸着性セレン（４価セレン）を除去した（図１に示すステップ２）後の状態を示しており、セレン含有排水のｐＨ、酸化還元電位（ＯＲＰ）、４価セレン濃度（ｍｇ／Ｌ）、６価セレン濃度（ｍｇ／Ｌ）、全セレン濃度（ｍｇ／Ｌ）を各々示している。 In Table 1 above, “state after addition of oxidizing agent” in Examples 1 and 2 indicates that ozone as an oxidizing agent is added to selenium-containing wastewater to oxidize hardly adsorbable selenium (tetravalent selenium) in the selenium-containing wastewater. This shows the state after removal of hardly adsorbing selenium (tetravalent selenium) by making it easy adsorbing selenium (hexavalent selenium) (step 2 shown in FIG. 1), and the pH and oxidation of selenium-containing wastewater The reduction potential (ORP), tetravalent selenium concentration (mg / L), hexavalent selenium concentration (mg / L), and total selenium concentration (mg / L) are shown.
上記表１において、実施例１、２、比較例１の「樹脂によるセレン除去後の結果」は、処理を行った結果のセレン含有排水のｐＨ、酸化還元電位（以下、ＯＲＰとも呼ぶ）、４価セレン濃度（ｍｇ／Ｌ）、６価セレン濃度（ｍｇ／Ｌ）、全セレン濃度（ｍｇ／Ｌ）、樹脂１ｍＬ当たりのセレンの吸着量（ｍｇ／ｍＬ）を示している。即ち、実施例１、２の「樹脂によるセレン除去後の結果」は、酸化剤の添加によりセレン含有排水から難吸着性セレン（４価セレン）を除去した（図１に示すステップ２）後に、このセレン含有排水に樹脂を添加してろ過し、セレンを吸着させた樹脂をセレン含有排水から除去した（即ち、図１に示すステップ３、４）後の結果を示しており、比較例１の「樹脂によるセレン除去後の結果」は、初期状態のセレン含有排水を樹脂で処理した後の結果を示している。なお、表１において樹脂１ｍＬ当たりのセレンの吸着量は、後述するように（全セレン濃度の処理前後差（ｍｇ／Ｌ））×（試験溶液の体積（Ｌ））÷（樹脂の体積（ｍＬ））の計算により行った。 In Table 1 above, “Results after removal of selenium by resin” in Examples 1 and 2 and Comparative Example 1 are the pH, redox potential (hereinafter also referred to as ORP) of selenium-containing wastewater as a result of treatment, 4 The selenium concentration (mg / L), the hexavalent selenium concentration (mg / L), the total selenium concentration (mg / L), and the adsorption amount of selenium per 1 mL of resin (mg / mL) are shown. That is, “results after removal of selenium by resin” in Examples 1 and 2 were obtained after removing hardly adsorbing selenium (tetravalent selenium) from selenium-containing wastewater by adding an oxidizing agent (step 2 shown in FIG. 1). The resin is added to the selenium-containing wastewater and filtered, and the resin adsorbed with selenium is removed from the selenium-containing wastewater (ie, steps 3 and 4 shown in FIG. 1). “Result after removal of selenium with resin” shows the result after treating the selenium-containing wastewater in the initial state with resin. In Table 1, the amount of selenium adsorbed per mL of resin is (total selenium concentration before and after treatment (mg / L)) × (volume of test solution (L)) ÷ (volume of resin (mL )).
以下、実施例１、２、比較例１の各々について詳細に説明する。 Hereinafter, each of Examples 1 and 2 and Comparative Example 1 will be described in detail.
＜実施例１＞
まず、セレンを含む排水を用意した。上記表１に示すように、この排水のｐＨは６．９、ＯＲＰは２６１ｍＶ、４価セレン濃度は０．５ｍｇ／Ｌ、６価セレン濃度は５．２ｍｇ／Ｌ、全セレン濃度は５．７ｍｇ／Ｌであった（以下、ｍｇ／Ｌは各濃度を示す）。この排水１Ｌを撹拌した状態で酸化剤としてオゾンガスを添加した。添加する際の流量はオゾンガス体積１．０Ｌ／分とし、添加時間を５分とした。オゾン添加後のセレン含有排水のｐＨは７．２、ＯＲＰは６４４ｍＶ、４価セレン濃度は０．２ｍｇ／Ｌ、６価セレン濃度は５．５ｍｇ／Ｌ、全セレン濃度は５．７ｍｇ／Ｌであった。このように、オゾン添加の前後において、全セレン濃度の値は一定であるが、難吸着性セレン（４価セレン）の濃度が減少し、易吸着性セレン（６価セレン）の濃度が増大していることから、オゾンの添加により、難吸着性セレン（４価セレン）が易吸着性セレン（６価セレン）に酸化されたことがわかる。
<Example 1>
First, drainage containing selenium was prepared. As shown in Table 1, the pH of this waste water is 6.9, ORP is 261 mV, tetravalent selenium concentration is 0.5 mg / L, hexavalent selenium concentration is 5.2 mg / L, and total selenium concentration is 5.7 mg. / L (hereinafter, mg / L indicates each concentration). Ozone gas was added as an oxidant while stirring 1 L of this waste water. The flow rate during the addition was set to an ozone gas volume of 1.0 L / min, and the addition time was set to 5 minutes. The pH of selenium-containing wastewater after addition of ozone is 7.2, ORP is 644 mV, tetravalent selenium concentration is 0.2 mg / L, hexavalent selenium concentration is 5.5 mg / L, and total selenium concentration is 5.7 mg / L. there were. As described above, the value of total selenium concentration is constant before and after ozone addition, but the concentration of hardly adsorbable selenium (tetravalent selenium) decreases and the concentration of easily adsorbable selenium (hexavalent selenium) increases. From this, it can be seen that hardly adsorbable selenium (tetravalent selenium) was oxidized to easily adsorbable selenium (hexavalent selenium) by the addition of ozone.
この試験溶液５０ｍＬを１００ｍＬのポリエチレン製の密閉容器に貯留した。試験溶液中のセレンを除去するため、吸着材として市販されているイオン交換樹脂を０．０５ｍＬ添加した。２０時間振とうして試験溶液と樹脂を接触させた後、ろ過して樹脂と液を分離し、セレン除去処理を終了した。ろ液に含まれるセレンの測定はＩＣＰ−ＨＹＤを使用した。 50 mL of this test solution was stored in a 100 mL polyethylene sealed container. In order to remove selenium in the test solution, 0.05 mL of an ion exchange resin marketed as an adsorbent was added. After shaking for 20 hours to bring the test solution into contact with the resin, the resin was separated from the liquid by filtration, and the selenium removal treatment was completed. ICP-HYD was used for the measurement of selenium contained in the filtrate.
その結果、セレン含有排水のｐＨが９．６、ＯＲＰが２５７ｍＶ、４価セレン濃度は０．１ｍｇ／Ｌ、６価セレン濃度は３．０ｍｇ/Ｌ、全セレン濃度は３．１ｍｇ／Ｌであった。表１に示すように、全セレン濃度の値は、樹脂によるセレン除去の前後においてその値が低減しており、セレンが樹脂に吸着除去されていることがわかる。しかし、難吸着性セレン（４価セレン）については易吸着性セレン（６価セレン）と比較して吸着されにくいことがわかる。以下、具体的に樹脂１ｍＬ当たりのセレンの吸着量を算出して説明する。難吸着性セレン（４価セレン）の吸着量については、０．１ｍｇ（４価セレン濃度の前後差）×０．０５Ｌ（試験溶液の体積）÷０．０５ｍＬ（樹脂の体積）＝０．１ｍｇ／ｍＬであった。同様に易吸着性セレン（６価セレン）では２．５ｍｇ／ｍＬ、全セレンでは２．６ｍｇ／ｍＬとなった。即ち、易吸着性セレン（６価セレン）の吸着量が２．５ｍｇ／ｍＬであるのに対し、難吸着性セレン（４価セレン）の吸着量は０．１ｍｇ／ｍＬと、２５分の１以下の値になっている。 As a result, the pH of the selenium-containing wastewater was 9.6, the ORP was 257 mV, the tetravalent selenium concentration was 0.1 mg / L, the hexavalent selenium concentration was 3.0 mg / L, and the total selenium concentration was 3.1 mg / L. It was. As shown in Table 1, the value of the total selenium concentration is reduced before and after selenium removal by the resin, and it can be seen that selenium is adsorbed and removed by the resin. However, it can be seen that hardly adsorbing selenium (tetravalent selenium) is less likely to be adsorbed than easily adsorbing selenium (hexavalent selenium). Hereinafter, the amount of adsorption of selenium per mL of resin will be specifically calculated and described. About the amount of adsorption of hardly adsorbing selenium (tetravalent selenium), 0.1 mg (difference before and after tetravalent selenium concentration) × 0.05 L (volume of test solution) ÷ 0.05 mL (volume of resin) = 0.1 mg / ML. Similarly, the easily adsorbable selenium (hexavalent selenium) was 2.5 mg / mL, and the total selenium was 2.6 mg / mL. That is, the adsorption amount of easily adsorbable selenium (hexavalent selenium) is 2.5 mg / mL, whereas the adsorption amount of hardly adsorbable selenium (tetravalent selenium) is 0.1 mg / mL, which is 1/25. The values are as follows.
＜実施例２＞
オゾンの吹き込み時間を１５分にした以外は実施例１と同様の条件で試験を実施した。オゾン吹き込み後のｐＨは７．５、ＯＲＰは８８０ｍＶ、４価セレン濃度は０．１ｍｇ／Ｌ未満、６価セレン濃度は５．７ｍｇ／Ｌ、全セレン濃度５．７ｍｇ／Ｌであった。実施例１の場合におけるオゾン添加後の状態の４価セレン濃度が０．２ｍｇ／Ｌであるのに対し、実施例２の場合におけるオゾン添加後の状態の４価セレン濃度が０．１ｍｇ／Ｌ未満と小さくなっている。このことからオゾンの添加量を増やしたことでＯＲＰが実施例１の６４４ｍｖよりも高くなり、難吸着性セレン（４価セレン）の酸化が進んだことがわかる。
<Example 2>
The test was performed under the same conditions as in Example 1 except that the ozone blowing time was 15 minutes. The pH after ozone blowing was 7.5, the ORP was 880 mV, the tetravalent selenium concentration was less than 0.1 mg / L, the hexavalent selenium concentration was 5.7 mg / L, and the total selenium concentration was 5.7 mg / L. The tetravalent selenium concentration in the state after ozone addition in Example 1 is 0.2 mg / L, whereas the tetravalent selenium concentration in the state after ozone addition in Example 2 is 0.1 mg / L. Less than and smaller. From this, it can be seen that the ORP became higher than 644 mv of Example 1 by increasing the amount of ozone added, and oxidation of hardly adsorbing selenium (tetravalent selenium) progressed.
樹脂でセレンを除去した後の結果は、セレン含有排水のｐＨが９．６、ＯＲＰが２８３ｍＶ、４価セレン濃度は０．０５ｍｇ／Ｌ未満、６価セレン濃度は２．９ｍｇ／Ｌであった。樹脂１ｍＬ当たりのセレンの吸着量を算出すると、易吸着性セレン（６価セレン）は２．９ｍｇ／Ｌ、全セレンも２．９ｍｇ／ｍＬとなった。難吸着性セレン（４価セレン）についてはオゾン添加時点でその値が０．０５ｍｇ／Ｌ未満であり、ほとんど無くなっていたため省略する。 As a result after removing selenium with the resin, the pH of the selenium-containing wastewater was 9.6, the ORP was 283 mV, the tetravalent selenium concentration was less than 0.05 mg / L, and the hexavalent selenium concentration was 2.9 mg / L. . When the adsorption amount of selenium per 1 mL of resin was calculated, 2.9 mg / L of easily adsorbable selenium (hexavalent selenium) and 2.9 mg / mL of all selenium were obtained. The value of hardly adsorbing selenium (tetravalent selenium) is less than 0.05 mg / L at the time of ozone addition, and is omitted because it is almost lost.
＜比較例１＞
オゾンを添加しない以外は実施例１と同様の条件で試験を実施した。表１に示すように、樹脂でセレンを除去した後の結果は、セレン含有排水のｐＨが９．２、ＯＲＰ１８１ｍＶ、４価セレン濃度は０．４ｍｇ／Ｌ、６価セレン濃度は３．２ｍｇ／Ｌ、全セレン濃度は３．６ｍｇ／Ｌであった。樹脂１ｍＬ当たりのセレンの吸着量を算出すると、難吸着性セレン（４価セレン）は０．１ｍｇ／ｍＬ、易吸着性セレン（６価セレン）は２．０ｍｇ／ｍＬ、全セレンは２．１ｍｇ／ｍＬとなった。
<Comparative Example 1>
The test was performed under the same conditions as in Example 1 except that ozone was not added. As shown in Table 1, the results after removing selenium with the resin are as follows: pH of selenium-containing wastewater is 9.2, ORP181 mV, tetravalent selenium concentration is 0.4 mg / L, and hexavalent selenium concentration is 3.2 mg / L. L and the total selenium concentration were 3.6 mg / L. When the adsorption amount of selenium per 1 mL of resin is calculated, 0.1 mg / mL of hard-adsorbing selenium (tetravalent selenium), 2.0 mg / mL of easy-adsorbing selenium (hexavalent selenium), 2.1 mg of total selenium / ML.
＜考察＞
実施例１と比較例１を比較すると、セレン含有排水の処理による全セレンの吸着量が比較例１の場合には、２．１ｍｇ／ｍＬであるのに対し、実施例１では２．６ｍｇ／ｍＬと比較例１よりも大きくなっている。このように、本発明の手順に従ってセレン含有排水に酸化剤を添加することにより難吸着性セレン（４価セレン）を易吸着性セレン（６価セレン）に酸化し、難吸着性セレン（４価セレン）を除去することで、本発明を用いない場合に比べて樹脂のセレン全体の吸着量を高めることができることが分かる。
<Discussion>
When Example 1 is compared with Comparative Example 1, the amount of adsorption of all selenium by the treatment of selenium-containing wastewater is 2.1 mg / mL in the case of Comparative Example 1, whereas 2.6 mg / mL in Example 1. mL and larger than Comparative Example 1. As described above, by adding an oxidizing agent to the selenium-containing wastewater according to the procedure of the present invention, the hardly adsorbing selenium (tetravalent selenium) is oxidized to the easily adsorbing selenium (hexavalent selenium), and the hardly adsorbing selenium (tetravalent selenium). It can be seen that by removing (selenium), the adsorption amount of the entire resin selenium can be increased as compared with the case where the present invention is not used.
また、実施例１と実施例２を比較することによって、酸化剤の添加量を増やすことでセレン含有排水中の難吸着性セレン（４価セレン）をより易吸着性セレン（６価セレン）に酸化することができ、その結果、樹脂のセレン吸着量を向上できることがわかる。 In addition, by comparing Example 1 and Example 2, increasing the amount of oxidant added makes the hard-to-adsorb selenium (tetravalent selenium) in the selenium-containing wastewater more easily adsorbable selenium (hexavalent selenium). As a result, it can be seen that the selenium adsorption amount of the resin can be improved.
図２は、本発明の手順によりセレン含有排水を処理する際に、セレン含有排水に酸化剤としてのオゾンを吹き込む際の酸化還元電位（以下、ＯＲＰとも呼ぶ）と、オゾン添加後の４価セレン濃度との関係を示すグラフである。なお、酸化剤としてのオゾンを吹き込む前のセレン含有排水の４価セレン濃度は１．３ｍｇ／Ｌに設定した。 FIG. 2 shows the oxidation-reduction potential (hereinafter also referred to as ORP) when ozone as an oxidizing agent is blown into selenium-containing wastewater when treating selenium-containing wastewater according to the procedure of the present invention, and tetravalent selenium after addition of ozone. It is a graph which shows the relationship with a density | concentration. In addition, the tetravalent selenium density | concentration of the selenium containing waste water before blowing in ozone as an oxidizing agent was set to 1.3 mg / L.
図２に示すように、酸化剤（オゾン）を添加する際に酸化還元電位（ＯＲＰ）の値を４００ｍＶ以上に維持した状態で酸化剤を添加した場合には、酸化剤による酸化が著しく促進されて４価セレン濃度が非常に低くなっていることが分かる。従って、本発明によりセレン含有排水を処理する際に、酸化還元電位が４００ｍＶ以上になるようにして酸化剤を添加することによって、セレン含有排水中の難吸着性セレン（４価セレン）の大部分を易吸着性セレン（６価セレン）に酸化し、セレンを効果的に吸着除去できることが判明した。特に、酸化還元電位（ＯＲＰ）を８００ｍＶ以上に設定した場合には、図２に示すように、セレン含有排水中のほとんどの難吸着性セレン（４価セレン）が易吸着性セレン（６価セレン）に酸化されている。 As shown in FIG. 2, when an oxidizing agent is added in a state where the oxidation-reduction potential (ORP) value is maintained at 400 mV or higher when the oxidizing agent (ozone) is added, oxidation by the oxidizing agent is remarkably promoted. It can be seen that the tetravalent selenium concentration is very low. Therefore, when treating selenium-containing wastewater according to the present invention, most of the hardly adsorbable selenium (tetravalent selenium) in the selenium-containing wastewater is added by adding an oxidizing agent so that the oxidation-reduction potential is 400 mV or more. Was oxidized to easily adsorbable selenium (hexavalent selenium), and it was found that selenium can be effectively adsorbed and removed. In particular, when the oxidation-reduction potential (ORP) is set to 800 mV or more, as shown in FIG. 2, most hardly adsorbing selenium (tetravalent selenium) in the selenium-containing waste water is easily adsorbed selenium (hexavalent selenium). ) Is oxidized.
実施例１の排水を用いて、ろ過前（樹脂の除去前）のｐＨを７．２（比較例２）、８（比較例３）、９（比較例４）、１０（実施例３）、１２（実施例４）に調整し、オゾンを添加しない以外は実施例１と同様に行った場合の結果を下記表２に示す。なお、ｐＨの調整は苛性ソーダを用いた。 Using the waste water of Example 1, the pH before filtration (before removal of the resin) was 7.2 (Comparative Example 2), 8 (Comparative Example 3), 9 (Comparative Example 4), 10 (Example 3), Table 2 below shows the results when the same procedure as in Example 1 was performed except that the amount was adjusted to 12 (Example 4) and ozone was not added. Note that caustic soda was used to adjust the pH.
上記表２に示すように、セレンの吸着量は、比較例２が１．１ｍｇ／ｍＬ、比較例３が１．２ｍｇ／ｍＬ、比較例４が１．５ｍｇ／ｍＬ、実施例３が２．２ｍｇ／ｍＬ、実施例４が２．５ｍｇ／ｍＬとなった。このように、樹脂に吸着前の処理として、セレン含有水のｐＨを１０以上とすることによって、セレン含有排水中のセレンを効果的に吸着除去できていることがわかる。 As shown in Table 2, the adsorption amount of selenium was 1.1 mg / mL in Comparative Example 2, 1.2 mg / mL in Comparative Example 3, 1.5 mg / mL in Comparative Example 4, and 2. 2 mg / mL and Example 4 were 2.5 mg / mL. Thus, it turns out that selenium in the selenium-containing wastewater can be effectively adsorbed and removed by setting the pH of the selenium-containing water to 10 or more as a treatment before adsorption to the resin.
本発明は、産業のため発生したセレン含有排水や、セレン含有処理水の処理に特に有用である。また、天然由来の水にセレンが含まれている場合の処理にも適用可能である。 The present invention is particularly useful for treatment of selenium-containing wastewater generated for industry and selenium-containing treated water. Moreover, it is applicable also to the process in the case where selenium is contained in naturally derived water.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011189300A (en) * | 2010-03-16 | 2011-09-29 | Taiheiyo Cement Corp | Method for removing selenium |
| JP2013522008A (en) * | 2010-03-10 | 2013-06-13 | ナルコ カンパニー | Selenium removal from refinery effluent |
| WO2014207905A1 (en) * | 2013-06-28 | 2014-12-31 | 三菱重工メカトロシステムズ株式会社 | Method for removing selenium and apparatus for removing selenium |
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| JP2019037930A (en) * | 2017-08-24 | 2019-03-14 | 清水建設株式会社 | Method for treating selenium-containing soil or rock |
| JP2019037929A (en) * | 2017-08-24 | 2019-03-14 | 清水建設株式会社 | Method for treating selenium-containing soil and rock |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013522008A (en) * | 2010-03-10 | 2013-06-13 | ナルコ カンパニー | Selenium removal from refinery effluent |
| JP2011189300A (en) * | 2010-03-16 | 2011-09-29 | Taiheiyo Cement Corp | Method for removing selenium |
| WO2014207905A1 (en) * | 2013-06-28 | 2014-12-31 | 三菱重工メカトロシステムズ株式会社 | Method for removing selenium and apparatus for removing selenium |
| CN105246839A (en) * | 2013-06-28 | 2016-01-13 | 三菱重工机电系统株式会社 | Method for removing selenium and apparatus for removing selenium |
| US10919790B2 (en) | 2013-06-28 | 2021-02-16 | Mitsubishi Power Environmental Solutions, Ltd. | Method for removing selenium and apparatus for removing selenium |
| WO2015056588A1 (en) * | 2013-10-16 | 2015-04-23 | 三菱重工業株式会社 | Wastewater treatment method and wastewater treatment device |
| JP2015077553A (en) * | 2013-10-16 | 2015-04-23 | 三菱重工業株式会社 | Wastewater treatment method and device |
| CN105593173A (en) * | 2013-10-16 | 2016-05-18 | 三菱重工业株式会社 | Wastewater treatment method and wastewater treatment device |
| US10336631B2 (en) | 2013-10-16 | 2019-07-02 | Mitsubishi Heavy Industries Engineering, Ltd. | Wastewater treatment method and wastewater treatment apparatus |
| JP2019037930A (en) * | 2017-08-24 | 2019-03-14 | 清水建設株式会社 | Method for treating selenium-containing soil or rock |
| JP2019037929A (en) * | 2017-08-24 | 2019-03-14 | 清水建設株式会社 | Method for treating selenium-containing soil and rock |
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