JPH0361515B2 - - Google Patents
Info
- Publication number
- JPH0361515B2 JPH0361515B2 JP1345882A JP1345882A JPH0361515B2 JP H0361515 B2 JPH0361515 B2 JP H0361515B2 JP 1345882 A JP1345882 A JP 1345882A JP 1345882 A JP1345882 A JP 1345882A JP H0361515 B2 JPH0361515 B2 JP H0361515B2
- Authority
- JP
- Japan
- Prior art keywords
- mine water
- ferrous
- liquid
- ions
- ferric
- 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
Links
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 34
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910001447 ferric ion Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000696 magnetic material Substances 0.000 claims 1
- 229910000859 α-Fe Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】
本発明はシリコン（Si）が共存する第一鉄イオ
ン含有坑水の処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating mine water containing ferrous ions in which silicon (Si) coexists.
従来第一鉄イオン含有坑水は第一鉄イオンを第
二鉄イオンに酸化後、アルカリを加えて水酸化物
を生成して除去する方法がよく知られている。他
方、第一鉄イオン含有液をアルカリ性に保持し、
空気中で撹拌して第一鉄イオンを酸化し、フエラ
イトを生成する方法が知られている。この方法に
よる生成物は、極めて安定で、再溶出しにくく、
投棄に伴う二次公害の危険性の少ない非常に好ま
しい処理方法である。しかしながら第一鉄イオン
含有液中にSiが共存するとフエライトの生成が阻
害され又は不可能になる。すなわちSiO2を
30ppm〜100ppm程度含有する第一鉄イオン含有
坑水からフエライトを生成することは難かしく、
通常Siが共存する第一鉄イオン含有坑水な第一鉄
イオンを第二鉄イオンに酸化後、アルカリを添加
して水酸化第二鉄を生成して処理される。この方
法によつて多量の坑水を処理して生成する沈殿物
は埋立て投棄されるが、将来にわたつて多量に発
生する膨大な沈殿物量に対拠しうる埋立て地の選
定には困難を来たしており、沈殿物の有効利用が
早急に望まれている。 Conventionally, a well-known method for removing ferrous ion-containing mine water is to oxidize the ferrous ions to ferric ions, then add an alkali to generate hydroxides. On the other hand, keeping the ferrous ion-containing liquid alkaline,
A method is known in which ferrous ions are oxidized by stirring in air to produce ferrite. The product produced by this method is extremely stable and difficult to re-elute.
This is a very preferable disposal method as there is little risk of secondary pollution associated with dumping. However, if Si coexists in the ferrous ion-containing liquid, the production of ferrite is inhibited or becomes impossible. i.e. SiO 2
It is difficult to produce ferrite from mine water containing ferrous ions, which contains about 30ppm to 100ppm.
Normally, mineral water containing ferrous ions in which Si coexists is treated. After oxidizing ferrous ions to ferric ions, alkali is added to produce ferric hydroxide. This method treats a large amount of mine water and disposes of the sediment that is generated in a landfill, but it is difficult to select a landfill site that can handle the enormous amount of sediment that will be generated in the future. Therefore, effective utilization of the sediment is urgently desired.
本発明の目的はこれら問題点を解決し、第一鉄
イオン含有坑水から、有効利用可能なフエライト
を常温で生成する方法を提供することにある。 An object of the present invention is to solve these problems and provide a method for producing ferrite that can be effectively used at room temperature from mine water containing ferrous ions.
即ち本発明による方法は、Siが共存する第一鉄
イオン含有坑水の処理に際し、まず酸素や空気を
吹き込んだり、高速撹拌することによつて坑水中
の第一鉄イオンの一部を酸化して第二鉄イオンを
生成するか又は第二鉄塩か第二鉄イオン含有液を
添加した後、次にアルカリ剤を加えてPH６以下で
生成する水酸化第二鉄と一緒にフエライトの生成
反応を阻害する坑水中のSiを共沈させて分離し分
離後の第一鉄イオン含有液はアルカリ剤を添加し
てPH７以上に保持し、酸素や空気などの酸化性ガ
スを吹き込んだり、酸化性雰囲気中で高速撹拌し
て液中第一鉄と第二鉄の組成比がFe（）／Fe
（）＝1.5〜3.0になるように第一鉄を酸化し、次
に該液を静置又は窒素中などの非酸化性雰囲気中
で撹拌することにより沈殿を黒色の強磁性沈殿物
（フエライト）にし、該液に酸素や空気などの酸
化性ガスを吹き込むか、酸化性雰囲気中で撹拌し
て溶残する第一鉄イオンを酸化し、生成する沈殿
物を除去することを特徴とする。 That is, the method according to the present invention, when treating mine water containing ferrous ions in which Si coexists, first oxidizes some of the ferrous ions in the mine water by blowing oxygen or air or stirring at high speed. After adding a ferric salt or a ferric ion-containing solution, an alkaline agent is added to generate ferrite together with ferric hydroxide, which is generated at a pH of 6 or less. Si in the mine water, which inhibits ferrous ions, is separated by co-precipitation, and the ferrous ion-containing liquid after separation is kept at a pH of 7 or higher by adding an alkaline agent, and oxidizing gases such as oxygen and air are blown into the ferrous ion-containing liquid. The composition ratio of ferrous and ferric iron in the liquid is adjusted to Fe()/Fe by stirring at high speed in an atmosphere.
Ferrous iron is oxidized so that ( ) = 1.5 to 3.0, and then the solution is left standing or stirred in a non-oxidizing atmosphere such as nitrogen to convert the precipitate into a black ferromagnetic precipitate (ferrite). The method is characterized by blowing an oxidizing gas such as oxygen or air into the liquid or stirring it in an oxidizing atmosphere to oxidize the remaining ferrous ions and remove the formed precipitate.
本発明の最後の酸化工程において、液の酸化は
酸化還元電位が急激に高くなるまで行なえばよ
い。本発明の方法によつて坑水中の第一鉄イオン
の一部は有効利用可能なフエライトにかえられ
る。本発明の実施によつて生成されるフエライト
は電波吸収材料、磁性流体用原料などとしての再
利用が可能であり、廃棄物の有効利用には誠に好
ましいクローズドサイクルをもたらす。 In the final oxidation step of the present invention, the oxidation of the liquid may be carried out until the redox potential suddenly increases. By the method of the present invention, some of the ferrous ions in mine water are converted into ferrite that can be used effectively. The ferrite produced by carrying out the present invention can be reused as a radio wave absorbing material, a raw material for magnetic fluid, etc., and provides a closed cycle that is very favorable for the effective use of waste.
本発明の方法では、Siの除去効果はPHが高くな
る程高くなるが、PHが６より大きいと、溶存する
第一鉄も沈殿してしまうので望ましくない。水酸
化第一鉄の沈殿物は水に溶解しやすく、その投棄
に伴なう二次公害の危険性が大きい。またフエラ
イト生成のためには、第一鉄の酸化はFe（）／
Fe（）＝２になるように酸化するのが最適であ
るが、Fe（）／Fe（）を1.5〜3.0に限つたのは
組成比Fe（）／Fe（）が1.5より小さいと酸化
が不十分であつてフエライト生成が阻害された
り、フエライト生成時間が異常に長くなり又組成
比Fe（）／Fe（）が3.0より大きいと酸化が進
みすぎてフエライト生成が阻害されたり、フエラ
イト粒子の粒径が小さくなつてしまうからであ
る。酸化の終つた液を静置すると沈殿は黒色の強
磁性沈殿物になるが、廃水の性状によつては、該
液を窒素やヘリウムなどの非酸化性雰囲気中に静
置するのが望ましい。 In the method of the present invention, the effect of removing Si increases as the pH increases, but if the pH is higher than 6, dissolved ferrous iron will also precipitate, which is not desirable. Ferrous hydroxide precipitates are easily dissolved in water, and there is a great risk of secondary pollution associated with their dumping. In addition, for ferrite formation, the oxidation of ferrous iron is Fe()/
It is optimal to oxidize so that Fe() = 2, but the reason for limiting Fe()/Fe() to 1.5 to 3.0 is that if the composition ratio Fe()/Fe() is less than 1.5, oxidation will not occur. If the composition ratio Fe()/Fe() is greater than 3.0, ferrite formation may be inhibited or the ferrite formation time may become abnormally long. This is because the diameter becomes smaller. When the oxidized liquid is allowed to stand still, the precipitate becomes a black ferromagnetic precipitate, but depending on the nature of the wastewater, it is desirable to leave the liquid still in a non-oxidizing atmosphere such as nitrogen or helium.
なお、本発明の方法によれば、坑水中に共存す
る重金属イオンもフエライトに取り込んで一括処
理することができる。 In addition, according to the method of the present invention, heavy metal ions coexisting in mine water can also be incorporated into ferrite and treated all at once.
以下、実施例により、本発明についてさらに詳
細に説明する。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例
全Fe3400ppm、Fe2+3360ppm、SiO250ppm、
Al320ppm、Zn100ppm、Cn20ppmを含有する坑
水を本発明の方法により以下のように処理した。
すなわち、該液500mlをビーカーにとり、該液に
空気をガラス管の先端から１／分の速度で吹き
込んだ。液中のFe2+濃度をJIS K0101−60.1吸光
光度法によつて分析し、Fe2+濃度1000ppmにな
つたところで空気の吹き込みを止めた。次に
CaCO3を添加してPH5.5に調節後過した。液
中の溶存イオン濃度はFe980ppm、Al1.1ppm、
SiO22.4ppm、Zn42ppm、Cu0.3ppmであつた。
該液400mlを500mlビーカーにとり、水酸化カル
シユウムを添加してPH8.5を保持しながら該液に
空気を１／分の速度でガラス管の先端より吹き
こんだ。液中のFe2+濃度が330ppm（Fe3+／Fe2+
＝２）になつたところで空気の吹き込みを止め、
該液を窒素雰囲気中に静置した。Example Total Fe 3400ppm, Fe 2+ 3360ppm, SiO 2 50ppm,
Mine water containing 320 ppm Al, 100 ppm Zn, and 20 ppm Cn was treated as follows by the method of the present invention.
That is, 500 ml of the liquid was placed in a beaker, and air was blown into the liquid from the tip of a glass tube at a rate of 1/min. The Fe 2+ concentration in the liquid was analyzed by JIS K0101-60.1 spectrophotometry, and air blowing was stopped when the Fe 2+ concentration reached 1000 ppm. next
The pH was adjusted to 5.5 by adding CaCO 3 and filtered. Dissolved ion concentration in the liquid is Fe980ppm, Al1.1ppm,
It contained 2.4 ppm of SiO 2 , 42 ppm of Zn, and 0.3 ppm of Cu.
400 ml of this liquid was placed in a 500 ml beaker, and while calcium hydroxide was added to maintain the pH of 8.5, air was blown into the liquid at a rate of 1/min from the tip of a glass tube. The Fe 2+ concentration in the liquid is 330 ppm (Fe 3+ /Fe 2+
Stop blowing air when it reaches =2),
The solution was left standing in a nitrogen atmosphere.
静置12時間後、沈殿物は黒色で強い磁性を示し
た。次に、静置12時間後の溶液を空気中で撹拌す
ると、約20分後に酸化還元電位は−400mVから
＋250mV迄変化したので反応を終了した。反応
後上澄液中の溶存イオン濃度はFe-0.1ppm、
Zn0.02ppmでいずれも排水基準値以下であり、本
発明の方法は第一鉄イオン以外の処理についても
有効であつた。得られた沈殿物をＸ線回折によつ
て固定するとマグネタイトに一致した。 After 12 hours of standing, the precipitate was black and showed strong magnetism. Next, the solution after 12 hours of standing was stirred in the air, and the redox potential changed from -400 mV to +250 mV after about 20 minutes, so the reaction was terminated. The dissolved ion concentration in the supernatant after the reaction is Fe - 0.1ppm,
At 0.02 ppm of Zn, all values were below the wastewater standard value, and the method of the present invention was also effective for treating other than ferrous ions. When the obtained precipitate was fixed by X-ray diffraction, it was found to be magnetite.
なお実施例に示したように、本発明の方法によ
つて第一鉄イオンを一部酸化させてSiを共沈除去
しない場合には磁性フエライトを生成しなかつ
た。なお本発明において用いるアルカリは実施例
に示し炭酸カルシユウム、水酸化カルシユウム以
外に水酸化ナトリウムを用いても本発明の効果は
変らない。 As shown in the examples, when ferrous ions were partially oxidized by the method of the present invention and Si was not coprecipitated and removed, magnetic ferrite was not produced. The alkali used in the present invention is shown in the examples, and the effect of the present invention does not change even if sodium hydroxide is used in addition to calcium carbonate and calcium hydroxide.
Claims (1)
処理に際し、坑水中の第一鉄イオンの一部を酸化
して第二鉄イオンを生成し、次にアルカリ剤を加
えPH６以下で生成する水酸化第二鉄と、坑水中の
シリコン成分を共沈させて分離し、残つた第一鉄
イオン含有液にさらにアルカリ剤を加え、次に該
液を酸化して液中の第一鉄（Fe（））と第二鉄
（Fe（））の組成比がFe（）／Fe（）＝1.5〜
3.0になるように酸化後、該液を静置又は非酸化
性雰囲気中で撹拌して沈殿を磁性体に変えた後、
溶残する第一鉄イオンを酸化したのち沈殿物を除
去する工程からなることを特徴とする第一鉄イオ
ン含有坑水の処理方法。 ２ シリコンが共存する第一鉄イオン含有坑水の
処理に際し、坑水に第二鉄塩又は第二鉄イオン含
有液を添加し、次にアルカリ剤を加えPH６以下で
生成する水酸化第二鉄と、坑水中のシリコン成分
を共沈させて分離し、残つた第一鉄イオン含有液
にさらにアルカリ剤を加え、次に該液を酸化して
液中の第一鉄（Fe（））と第二鉄（Fe（））の
組成比がFe（）／（Fe（））＝1.5〜3.0になるよ
うに酸化後、該液を静置又は非酸化性雰囲気中で
撹拌して沈殿を磁性体に変えた後、溶残する第一
鉄イオンを酸化したのち沈殿物を除去する工程か
らなることを特徴とする第一鉄イオン含有坑水の
処理方法。[Claims] 1. When treating mine water containing ferrous ions in which silicon coexists, a part of the ferrous ions in the mine water is oxidized to generate ferric ions, and then an alkaline agent is added. The ferric hydroxide produced at pH 6 or below and the silicon component in the mine water are co-precipitated and separated, an alkali agent is further added to the remaining ferrous ion-containing liquid, and then the liquid is oxidized to dissolve the silicon component in the mine water. The composition ratio of ferrous iron (Fe()) and ferric iron (Fe()) is Fe()/Fe()=1.5~
After oxidizing to 3.0, the solution is left standing or stirred in a non-oxidizing atmosphere to convert the precipitate into a magnetic material,
A method for treating mine water containing ferrous ions, comprising the steps of oxidizing remaining ferrous ions and then removing precipitates. 2. When treating mine water containing ferrous ions in which silicon coexists, ferric salt or a liquid containing ferric ions is added to the mine water, and then an alkaline agent is added to produce ferric hydroxide at a pH of 6 or less. Then, the silicon component in the mine water is co-precipitated and separated, an alkaline agent is further added to the remaining ferrous ion-containing liquid, and then the liquid is oxidized to separate the ferrous iron (Fe()) in the liquid. After oxidizing the composition ratio of ferric iron (Fe()) to Fe()/(Fe()) = 1.5 to 3.0, the solution is left standing or stirred in a non-oxidizing atmosphere to magnetically transform the precipitate. 1. A method for treating mine water containing ferrous ions, which comprises a step of oxidizing remaining ferrous ions and removing precipitates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1345882A JPS58131190A (en) | 1982-01-29 | 1982-01-29 | Treatment of ferrous ion-contg. mine water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1345882A JPS58131190A (en) | 1982-01-29 | 1982-01-29 | Treatment of ferrous ion-contg. mine water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58131190A JPS58131190A (en) | 1983-08-04 |
| JPH0361515B2 true JPH0361515B2 (en) | 1991-09-20 |
Family
ID=11833696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1345882A Granted JPS58131190A (en) | 1982-01-29 | 1982-01-29 | Treatment of ferrous ion-contg. mine water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58131190A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10604414B2 (en) | 2017-06-15 | 2020-03-31 | Energysource Minerals Llc | System and process for recovery of lithium from a geothermal brine |
-
1982
- 1982-01-29 JP JP1345882A patent/JPS58131190A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58131190A (en) | 1983-08-04 |
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