JPH0128633B2 - - Google Patents
Info
- Publication number
- JPH0128633B2 JPH0128633B2 JP15696384A JP15696384A JPH0128633B2 JP H0128633 B2 JPH0128633 B2 JP H0128633B2 JP 15696384 A JP15696384 A JP 15696384A JP 15696384 A JP15696384 A JP 15696384A JP H0128633 B2 JPH0128633 B2 JP H0128633B2
- Authority
- JP
- Japan
- Prior art keywords
- arsenic
- ferric sulfate
- reaction
- added
- 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
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- 229910052785 arsenic Inorganic materials 0.000 claims description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Description
(イ) 技術分野
本発明は含砒素排水の処理方法に関するもので
あり、更に詳しくはフエライトの存在下で硫酸第
２鉄と反応させることにより砒素を除去する方法
に関するものである。
(ロ) 背景技術
従来、液中のAsを除去する方法としては、第
２鉄イオンと反応させ砒酸鉄として沈殿除去する
方法（特開昭59−162897号公報や、磁性粒子を分
散させた抽出溶剤と被処理水を超音波を用いて混
合し、次いで磁気分離する方法（特開昭52−
120547号公報）、また第１鉄塩の存在化で排水の
PHをアルカリ性に調節し、空気等の混入でフエラ
イト化反応を行なわせる方法（特開昭54−41270
号公報）など種々の方法が知られている。
しかし、一般に市販の硫酸第２鉄溶液を使用す
る方法は試薬代等のコストが高いので、排水中の
第１鉄イオンを酸化剤の添加やバクテリア等で第
２鉄に酸化する方法も提案されているが、単に硫
酸第２鉄溶液の添加による処理方法では当量比で
砒素１に対し第２鉄が約30〜50倍位の割合で反応
させなければならない上、反応時間も長時間を要
していた。
(ハ) 発明の開示
本発明者等は硫酸第２鉄溶液の消費量を従来の
使用量の1/10程度に少なくすると共に、短時間で
処理できる方法を鋭意研究していたところ、フエ
ライト微粒子の存在下で硫酸第２鉄を添加すると
短時間で砒素の沈殿を生ずることを見い出したの
である。
本発明法は砒素含有排水に少量のフエライト微
粒子を添加する第１工程と、該工程水に砒素含有
量に対して数当量の硫酸第２鉄溶液を添加して撹
拌し砒酸鉄の沈殿を生成せしめる第２工程とから
なるものである。
この第２工程において、硫酸第２鉄の添加量に
より該工程液のPHは2.0〜6.0、好ましくは3.0〜
5.0の範囲に調整すようにする。
砒酸鉄の生成には、次式の反応が行なわれる。
AsO4 3-＋Fe3＋→FeAsO4
この反応は通常の砒酸鉄生成の反応式である
が、その反応速度は極めて速く且つ硫酸第２鉄の
添加量もわずかに数当量である。
これにより、従来法に比し反応容器の容積を格
段に縮小することができ、同時に硫酸第２鉄の添
加量を従来の1/10程度に節減することが可能とな
る。
この原因としては、第１工程において添加した
フエライト微粒子（MO・Fe2O3、Ｍ＝Ca、Sr、
Na、Li）の周辺に液中の平均濃度より高濃度の
AsO4 -3イオンが存在し、Fe3+イオンとの砒酸鉄
生成反応が効率よく行なわれるからであると考え
られる。
以下、本発明の詳細を実施例により説明する。
(ニ) 実施例
実施例 １
1.54mg/の砒素を含有する原液50を容量75
の反応槽に導入し、次いでバリウムフエライト
微粒子を５ｇ/添加した（第１工程）。
次に、Fe3+として４ｇ/濃度の硫酸第２鉄溶
液43c.c.を該反応槽に添加し、約５分間撹拌した後
（第２工程）、過機に導びいて固液分離した。
その結果を、次の実施例２ならびに比較例の結
果を併せて表に示す。
実施例 ２
1.31mg/の砒素を含有する原液50を容量75
の反応槽に導入し、次いでストロンチウムフエ
ライト微粒子７ｇ/を添加した（第１工程）。
次に、Fe3+として４ｇ/濃度の硫酸第２鉄溶
液41.5c.c.を該反応槽に添加して約６分間撹拌した
後（第２工程）、過機に導き固液分離した。そ
の結果を表に示す。
比較例
1.42mg/の砒素を含有する原液50（ただし、
予めアルカリ中和剤として消石灰を用いてPHを調
整してある）を、フエライト微粒子を添加するこ
となく、実施例１、２と同様の方法で処理した。
この場合には、同一脱砒率を得るまでに添加し
た硫酸第２鉄溶液は当量比で32倍（添加量568c.c.）
を必要とし、処理時間は52分を要した。その結果
を表に示す。
(a) Technical Field The present invention relates to a method for treating arsenic-containing wastewater, and more specifically to a method for removing arsenic by reacting it with ferric sulfate in the presence of ferrite. (b) Background technology Conventionally, as a method for removing As in a liquid, there is a method of reacting with ferric ions to precipitate and remove it as iron arsenate (see Japanese Patent Application Laid-open No. 162897/1984, extraction using dispersed magnetic particles). A method of mixing the solvent and the water to be treated using ultrasonic waves and then magnetically separating the solvent and the water to be treated
(No. 120547), and the presence of ferrous salts also improves wastewater treatment.
A method of adjusting the pH to alkaline and causing a ferrite reaction by mixing air etc. (Japanese Patent Application Laid-Open No. 54-41270
Various methods are known, such as Japanese Patent Publication No. However, since the method of using a commercially available ferric sulfate solution is generally expensive due to the cost of reagents, other methods have also been proposed in which ferrous ions in wastewater are oxidized to ferric iron by adding an oxidizing agent or using bacteria. However, in a treatment method simply adding a ferric sulfate solution, the reaction must be carried out at an equivalent ratio of about 30 to 50 times ferric iron to 1 arsenic, and the reaction time also takes a long time. Was. (C) Disclosure of the Invention The present inventors were conducting intensive research into a method that could reduce the consumption of ferric sulfate solution to about 1/10 of the conventional amount and process it in a short time. They discovered that when ferric sulfate is added in the presence of ferric sulfate, arsenic precipitates in a short period of time. The method of the present invention includes a first step of adding a small amount of ferrite fine particles to arsenic-containing wastewater, and adding a ferric sulfate solution of several equivalents to the arsenic content to the process water and stirring to form a precipitate of iron arsenate. The process consists of a second step of forcing. In this second step, the pH of the process solution is 2.0 to 6.0, preferably 3.0 to 6.0, depending on the amount of ferric sulfate added.
Adjust to 5.0 range. To produce iron arsenate, the following reaction takes place.
AsO 4 3- +Fe 3 +→FeAsO 4 This reaction is a general reaction formula for producing iron arsenate, but the reaction rate is extremely fast and the amount of ferric sulfate added is only a few equivalents. As a result, the volume of the reaction vessel can be significantly reduced compared to conventional methods, and at the same time, the amount of ferric sulfate added can be reduced to about 1/10 of the conventional method. This is due to the ferrite fine particles (MO・Fe 2 O 3 , M=Ca, Sr,
around Na, Li) with a higher concentration than the average concentration in the liquid.
This is thought to be due to the presence of AsO 4 -3 ions, and the iron arsenate production reaction with Fe 3+ ions takes place efficiently. Hereinafter, the details of the present invention will be explained with reference to Examples. (D) Examples Example 1 A volume of 75 ml of stock solution containing 1.54 mg of arsenic
was introduced into a reaction tank, and then 5 g/fine barium ferrite particles were added (first step). Next, 43 c.c. of a ferric sulfate solution with a concentration of 4 g/concentration as Fe 3+ was added to the reaction tank, and after stirring for about 5 minutes (second step), it was introduced into a filter for solid-liquid separation. . The results are shown in the table together with the results of Example 2 and Comparative Example below. Example 2 Volume 75 of stock solution containing 1.31mg/arsenic
was introduced into a reaction tank, and then 7 g of strontium ferrite fine particles were added (first step). Next, 41.5 cc of a ferric sulfate solution with a concentration of 4 g/concentration as Fe 3+ was added to the reaction tank and stirred for about 6 minutes (second step), and then introduced into a filter for solid-liquid separation. The results are shown in the table. Comparative Example Stock solution 50 containing 1.42mg/arsenic (however,
(pH had been adjusted in advance using slaked lime as an alkali neutralizer) was treated in the same manner as in Examples 1 and 2 without adding ferrite fine particles. In this case, the equivalent ratio of ferric sulfate solution added to obtain the same arsenic removal rate is 32 times (addition amount 568c.c.)
The processing time was 52 minutes. The results are shown in the table.
【表】
(ホ) 発明の効果
本発明法は前記表示される如く、硫酸第２鉄の
添加量（Fe／As重量比）が少なくて済み、かつ
反応時間も短時間で済む利点がある。
なお、上記実施例では過機としてフイルター
プレスを用いたが、これはスーパーデカンター等
であつても差しつかえないことは勿論である。[Table] (e) Effects of the Invention As indicated above, the method of the present invention has the advantage that the amount of ferric sulfate added (Fe/As weight ratio) can be small and the reaction time can be shortened. In the above embodiments, a filter press was used as the filter, but it goes without saying that a super decanter or the like may also be used.
図は本発明法のフローシートである。 The figure is a flow sheet of the method of the present invention.
Claims (1)
微粒子の存在下において硫酸第２鉄溶液を添加し
て撹拌することにより極めて短時間に処理液中の
砒素を沈殿分離せしめることを特徴とする排水中
の砒素の除去方法。1. Arsenic in wastewater, which is characterized in that when treating arsenic-containing wastewater, arsenic in the treatment solution is precipitated and separated in an extremely short time by adding and stirring a ferric sulfate solution in the presence of ferrite fine particles. How to remove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15696384A JPS6135894A (en) | 1984-07-27 | 1984-07-27 | Removal of arsenic in waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15696384A JPS6135894A (en) | 1984-07-27 | 1984-07-27 | Removal of arsenic in waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6135894A JPS6135894A (en) | 1986-02-20 |
| JPH0128633B2 true JPH0128633B2 (en) | 1989-06-05 |
Family
ID=15639141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15696384A Granted JPS6135894A (en) | 1984-07-27 | 1984-07-27 | Removal of arsenic in waste water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6135894A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980914A (en) * | 2019-12-09 | 2020-04-10 | 昆明理工大学 | Method for removing arsenic by adsorbing high-alkalinity ferric hydroxide gel |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09192677A (en) * | 1996-01-16 | 1997-07-29 | Mitsubishi Heavy Ind Ltd | Treatment of arsenic-containing waste water |
| JP2005000823A (en) * | 2003-06-12 | 2005-01-06 | Japan Science & Technology Agency | How to treat geothermal water |
| WO2006080587A1 (en) * | 2005-01-31 | 2006-08-03 | Egs Company, Limited | Immobilizing agent and immobilization method for harmful component |
| AU2007277825B2 (en) * | 2006-07-27 | 2012-01-19 | Dowa Metals & Mining Co., Ltd. | Iron arsenate powder |
| JP4822445B2 (en) * | 2007-07-13 | 2011-11-24 | Ｄｏｗａメタルマイン株式会社 | Arsenic treatment method with seed crystals added |
| JP4538481B2 (en) * | 2007-09-25 | 2010-09-08 | 日鉱金属株式会社 | Method for producing scorodite and method for recycling liquid after synthesis of scorodite |
| JP5059081B2 (en) * | 2009-10-26 | 2012-10-24 | Ｊｘ日鉱日石金属株式会社 | Method for producing scorodite and method for recycling liquid after synthesis of scorodite |
| CN102642974B (en) * | 2012-05-07 | 2014-05-07 | 昆明理工大学 | Method for treating high-acid high-chlorine waste water |
| JP2015166080A (en) * | 2014-02-14 | 2015-09-24 | Jnc株式会社 | How to remove harmful substances in aqueous solution |
-
1984
- 1984-07-27 JP JP15696384A patent/JPS6135894A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980914A (en) * | 2019-12-09 | 2020-04-10 | 昆明理工大学 | Method for removing arsenic by adsorbing high-alkalinity ferric hydroxide gel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6135894A (en) | 1986-02-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |