JPH0157637B2 - - Google Patents
Info
- Publication number
- JPH0157637B2 JPH0157637B2 JP60153669A JP15366985A JPH0157637B2 JP H0157637 B2 JPH0157637 B2 JP H0157637B2 JP 60153669 A JP60153669 A JP 60153669A JP 15366985 A JP15366985 A JP 15366985A JP H0157637 B2 JPH0157637 B2 JP H0157637B2
- Authority
- JP
- Japan
- Prior art keywords
- edta
- liquid
- cadmium
- wastewater
- adjusting
- 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
- 238000000034 method Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Description
【発明の詳細な説明】
(イ) 技術分野
本発明は、食品分野や水質検査分野での硝酸塩
の分析のために用いられるカドミカラム還元法や
銅化カドミカラム還元法から排水されるEDTA
−Cd含有排水の処理方法に関するものである。[Detailed Description of the Invention] (a) Technical field The present invention relates to EDTA wastewater discharged from a cadmium column reduction method or a copperized cadmium column reduction method used for nitrate analysis in the food field and water quality testing field.
-Relates to a method for treating Cd-containing wastewater.
(ロ) 従来技術
硝酸塩の分析は、従来Hg等を使用して行なつ
ていたが、Hgの有毒性が問題となり、該分析に
Hgを用いない方法に変更せざるを得ない状況と
なつている。(b) Prior art Nitrate analysis has traditionally been carried out using Hg, etc., but the toxicity of Hg has become a problem and
We are now forced to change to a method that does not use Hg.
しかし、今日新しく採用されている分析方法は
カドミウムを使用するため、その排液には
EDTAやCd等が含まれるようになつた。 However, today's newly adopted analytical methods use cadmium, so the effluent must be
Now includes EDTA, CD, etc.
このため、含有する金属はキレート錯体を形成
してその処理が非常に難しく、特にCdはキレー
トとの錯体生成定数からみても除去が難しく、そ
の処理法について種々検討されているが、良法が
ないのが現状である。その中でも、特にEDTA
−Cdを高濃度に含有する活性化液の処理につい
ては、困難を極めている。 For this reason, the contained metals form chelate complexes, which are extremely difficult to treat.Cd in particular is difficult to remove, even from the perspective of the complex formation constant with chelates.Although various treatment methods have been studied, there is no good method. is the current situation. Among them, especially EDTA
- It is extremely difficult to process activation solutions containing high concentrations of Cd.
(ハ) 発明の目的
本発明は、このようなEDTA−Cd含有排水を
一連の操作により、Cdはもちろんのこと、他の
重金属も同時に除去する方法を提案するものであ
る。(c) Purpose of the Invention The present invention proposes a method for simultaneously removing not only Cd but also other heavy metals from such EDTA-Cd-containing wastewater through a series of operations.
(ニ) 発明の開示
即ち、本発明者等は上記EDTA−Cd含有排水
をあらかじめPH５以下に調整しておき、これに酸
化剤を添加して酸化処理した後、中和処理を行な
い、これを固液分離後、液をPH４以下の微酸性
に調整して鉄粉を添加することにより、重金属類
が容易に除去できるという効果的な処理法を見出
したものである。(d) Disclosure of the invention That is, the present inventors previously adjusted the EDTA-Cd-containing wastewater to a pH of 5 or less, added an oxidizing agent to the oxidizing treatment, and then neutralized it. After solid-liquid separation, we have discovered an effective treatment method in which heavy metals can be easily removed by adjusting the liquid to a slightly acidic pH of 4 or less and adding iron powder.
以下、本発明法を詳述する。 The method of the present invention will be explained in detail below.
本発明法で対象とする処理液は、カドミウム還
元法、銅化カドミウム還元法を行なつた試水、洗
浄水、活性化液などである。 The treatment liquids targeted by the method of the present invention include sample water, washing water, activation liquid, etc. that have been subjected to the cadmium reduction method and the cadmium copperide reduction method.
例えば、硝酸塩を定量する一方法として「カド
ミウム還元法」があり、この方法は金属カドミウ
ムを充填したカラムの上部から一定流速で検液を
流すことにより、検液中のNO3 -をNO2 -に還元
し、生じたNO2 -にスルフアニルアミドを作用さ
せてジアゾ化するものである。このカドミカラム
を活性化させるためにEDTAを流し、また安定
な値を得るために、検水にEDTAを加えて流す
ものであり、流出する液はEDTA−Cdを含んで
いる。 For example, one method for quantifying nitrate is the ``cadmium reduction method.'' This method involves flowing a test solution at a constant flow rate from the top of a column filled with metal cadmium, converting NO 3 - in the test solution into NO 2 -. The resulting NO 2 - is reacted with sulfanilamide to diazotize it. EDTA is passed through the cadmium column to activate it, and EDTA is added to the test water to obtain stable values, and the effluent contains EDTA-Cd.
この流出する活性化液、試水、洗浄水を混合し
たものを処理する場合、単に中和処理してもカド
ミウムを除去することはできないが、H2O2等の
強力な酸化剤とCaCO3を併用し、鉄粉を加える
と、カドミウムを除去することができることを本
発明者等は見出した。 When treating this mixture of activation solution, sample water, and washing water that flows out, cadmium cannot be removed simply by neutralization, but with a strong oxidizing agent such as H 2 O 2 and CaCO 3 The present inventors have discovered that cadmium can be removed by using them in combination and adding iron powder.
この場合におけるPHをHCl等により5.0以下、
好ましくはPH3.0〜4.0に調整後、H2O2を添加し、
次にCaCO3を粉状のままで過飽和となるまで過
剰に添加して一定時間撹拌後、高分子凝集剤を添
加して過性の良いフロツクを形成させ、固液分
離を行なう。この液をPH4.0以下、好ましくは
PH2.0〜3.0に調整後、鉄粉を添加して強力撹拌を
行なうと、鉄粉の溶解に伴なつて反応が進行し、
PHが徐々に上昇して５〜６となる。 In this case, adjust the pH to 5.0 or less using HCl, etc.
Preferably, after adjusting the pH to 3.0 to 4.0, add H 2 O 2 ,
Next, CaCO 3 in powder form is added in excess until it becomes supersaturated, and after stirring for a certain period of time, a polymer flocculant is added to form a highly permeable floc, and solid-liquid separation is performed. The pH of this solution is below 4.0, preferably
After adjusting the pH to 2.0 to 3.0, add iron powder and stir vigorously, the reaction will proceed as the iron powder dissolves,
The pH gradually rises to 5-6.
この反応をしばらく持続させた後、PHを８〜10
に保持して更に撹拌を続行すると、ほとんどの重
金属類などの有害物質が除去されるのである。 After allowing this reaction to continue for a while, the pH will be 8 to 10.
If the mixture is maintained at a constant temperature and stirring is continued, most of the heavy metals and other harmful substances will be removed.
このEDTA−Cd排水の処理工程は、H2O2等の
強力な酸化剤による酸化工程とCaCO3の中和剤
との組合せによる第一工程と、鉄粉を加える第二
工程とからなり、EDTA−Cdが第一工程でどの
ような形状になるのかは定かでないが、引き続い
ておこなう第二工程と密接に関係して効果を上げ
るものである。 The treatment process for this EDTA-Cd wastewater consists of a first process that combines an oxidation process using a strong oxidizing agent such as H 2 O 2 and a neutralizing agent such as CaCO 3 , and a second process that adds iron powder. Although it is unclear what shape EDTA-Cd takes in the first step, it is closely related to the subsequent second step to increase its effectiveness.
なお、酸化剤としてはH2O2のほかに、NaClO
等を使用しても同等の効果を有することを確認し
ている。 In addition to H 2 O 2 , NaClO is used as an oxidizing agent.
It has been confirmed that the same effect can be achieved by using
(ホ) 実施例
実施例 １
排液の組成がCd：64.9mg／、Zn：3.8mg／、
Cu：0.9mg／から成るEDTA−Cd含有排液１
を、HClでPH3.0に調整後、H2O2を添加し、次に
CaCO3を添加してPH5.0〜6.0に調整し、次いで高
分子凝集剤を添加して過性の良い沈殿を作り、
これを固液分離した液をHClでPH２〜３に調整
し、鉄粉を12ｇ／加え、15分間強力撹拌を行な
つた。(e) Examples Example 1 The composition of the waste liquid is Cd: 64.9 mg/, Zn: 3.8 mg/,
EDTA-Cd containing effluent 1 consisting of Cu: 0.9mg/
After adjusting the pH to 3.0 with HCl, add H 2 O 2 and then
Add CaCO 3 to adjust the pH to 5.0 to 6.0, then add a polymer flocculant to create a highly transient precipitate.
The solid-liquid separated liquid was adjusted to pH 2 to 3 with HCl, 12 g of iron powder was added, and the mixture was vigorously stirred for 15 minutes.
その後、NaOHでPH９〜10に調整し、15分間
強力撹拌を行ない、高分子凝集剤を加えて過し
た。 Thereafter, the pH was adjusted to 9 to 10 with NaOH, vigorously stirred for 15 minutes, and a polymer flocculant was added and filtered.
その結果、液の分析値はCd：0.01mg／、
Zn：0.2mg／、Cu：Trであつた。 As a result, the analysis value of the liquid was Cd: 0.01mg/,
Zn: 0.2 mg/, Cu: Tr.
比較例 １
実施例１と同様な排液を単にNaOHでPH９〜
10に調整して過を行つたものは、Cd：59.5mg／
であり、ほとんど除去できなかつた。Comparative Example 1 The same waste liquid as in Example 1 was adjusted to pH 9~ with NaOH.
For those adjusted to 10, Cd: 59.5mg/
and could hardly be removed.
(ヘ) 発明の効果
以上の通り、本発明法によれば従来処理が困難
とされていたEDTA−Cd含有排水から効率よく
しかも低コストでCdを除去することができ、簡
単に排水規制値以下に処理することができる効果
がある。(f) Effects of the invention As described above, according to the method of the present invention, Cd can be removed efficiently and at low cost from wastewater containing EDTA-Cd, which was conventionally considered difficult to treat, and it is easy to reduce wastewater below the regulatory value. There are effects that can be processed.
Claims (1)
酸化剤を添加した後、粉状CaCO3を過飽和にな
るまで過剰に添加し撹拌して固液分離し、さらに
その液をPH２〜３に調整後鉄粉を添加して撹拌
し、次にアルカリ剤によつてPH８〜10に調整して
固液分離を行なうことを特徴とするEDTA−Cd
含有排水の処理方法。1 After adjusting the EDTA-Cd-containing wastewater to pH 3 to 4 and adding an oxidizing agent, add powdered CaCO 3 in excess until supersaturated, stir to separate solid and liquid, and further adjust the liquid to pH 2 to 3. EDTA-Cd characterized by adding iron powder after adjustment and stirring, then adjusting the pH to 8 to 10 with an alkali agent and performing solid-liquid separation.
Treatment method for wastewater containing wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15366985A JPS6214994A (en) | 1985-07-12 | 1985-07-12 | Treatment of water containing edta-cd |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15366985A JPS6214994A (en) | 1985-07-12 | 1985-07-12 | Treatment of water containing edta-cd |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6214994A JPS6214994A (en) | 1987-01-23 |
| JPH0157637B2 true JPH0157637B2 (en) | 1989-12-06 |
Family
ID=15567582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15366985A Granted JPS6214994A (en) | 1985-07-12 | 1985-07-12 | Treatment of water containing edta-cd |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6214994A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100613727B1 (en) | 2004-10-27 | 2006-08-22 | 한국전력공사 | The continuous disposal method and apparatus of chemical cleaning waste water by non-catalytic oxidant treatment |
| CN110153157B (en) * | 2019-04-23 | 2020-09-11 | 中南大学 | Porous iron-based adsorption material, preparation method thereof and application thereof in heavy metal contaminated soil remediation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163555A (en) * | 1974-11-29 | 1976-06-02 | Teikoku Hormone Mfg Co Ltd | JUKINZOKUSAKUENSUIYOEKINO SHORIHOHO |
| JPS5411614A (en) * | 1977-06-27 | 1979-01-27 | Nec Corp | Code conversion unit for digital signal |
-
1985
- 1985-07-12 JP JP15366985A patent/JPS6214994A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163555A (en) * | 1974-11-29 | 1976-06-02 | Teikoku Hormone Mfg Co Ltd | JUKINZOKUSAKUENSUIYOEKINO SHORIHOHO |
| JPS5411614A (en) * | 1977-06-27 | 1979-01-27 | Nec Corp | Code conversion unit for digital signal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6214994A (en) | 1987-01-23 |
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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 |