JPS5919754B2 - Method for recovering heavy metals from wastewater containing heavy metal ions - Google Patents
Method for recovering heavy metals from wastewater containing heavy metal ionsInfo
- Publication number
- JPS5919754B2 JPS5919754B2 JP55043187A JP4318780A JPS5919754B2 JP S5919754 B2 JPS5919754 B2 JP S5919754B2 JP 55043187 A JP55043187 A JP 55043187A JP 4318780 A JP4318780 A JP 4318780A JP S5919754 B2 JPS5919754 B2 JP S5919754B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- scp
- metal ions
- heavy metals
- heavy metal
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Water Treatment By Sorption (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
本発明はＳＣＰ廃液廃液専焼上る重金属イオン含有排水
からの重金属の回収方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering heavy metals from heavy metal ion-containing wastewater produced by exclusive combustion of SCP waste liquid.
従来、メッキ工場排水、鉱山の杭内水、選鉱排水、製錬
排水などの産業排水のように重金属イオンを含有する水
（一般に酸性）から重金属を除去するには水酸化物とし
て沈殿させる中和法、硫化物として沈殿させる硫化法、
活性炭、イオン交換樹脂などによる吸着法などが行なわ
れている。Conventionally, in order to remove heavy metals from water (generally acidic) containing heavy metal ions, such as industrial wastewater such as plating factory wastewater, mine pile water, ore processing wastewater, and smelting wastewater, neutralization is performed by precipitating them as hydroxides. method, sulfurization method to precipitate as sulfide,
Adsorption methods using activated carbon, ion exchange resins, etc. are being used.
これらの処理法のうち中和法は経済的でまた工程が簡単
であるため広く利用されているが、多量の沈殿を生じる
こと、および液が強アリカリ性になるといったん沈殿し
た金属水酸化物が再溶解すること、また放流に際しては
ＰＨを中性付近迄下げる必要があることなど問題も多い
。Among these treatment methods, the neutralization method is widely used because it is economical and the process is simple, but it produces a large amount of precipitate, and once the liquid becomes strongly alkaline, the precipitated metal hydroxide is There are many problems, such as re-dissolution and the need to lower the pH to around neutrality when discharging.
また硫化法においては沈殿を生成させるために過剰の試
薬添加を必要とするので残留試薬により公害を引起こす
可能性があり、しかも得られる沈殿はきわめて微細なた
め固液分離が難しいという欠点がある。In addition, the sulfurization method requires the addition of an excessive amount of reagent to generate a precipitate, which may cause pollution due to residual reagent, and the resulting precipitate is extremely fine, making solid-liquid separation difficult. .
一方、イオン交換樹脂による吸着法は経費が著しく高く
、また樹脂の再生にも問題がある。On the other hand, the adsorption method using ion exchange resins is extremely expensive and also has problems in regenerating the resin.
また活性炭による吸着法は本発明に近い方法であるが、
活性炭は高価であり、重金属の吸着能力も少ないという
欠点がある。In addition, the adsorption method using activated carbon is a method close to the present invention, but
Activated carbon has the drawbacks of being expensive and having a low ability to adsorb heavy metals.
本発明は以上の従来法における欠点を除去するもので、
簡単な操作で公害問題を起こさずに効率よ（、経済的に
排水中の重金属イオンを除去し、且回収する方法を提供
するものである。The present invention eliminates the drawbacks of the above conventional methods,
It provides a method for efficiently removing and recovering heavy metal ions from wastewater with simple operations and without causing pollution problems.
本発明は前述のような重金属イオン含有排水にＳＣＰ廃
液廃液専焼上加して排水中の重金属をＳＣＰ廃液廃液専
焼上着せしめ、次いで吸着物を固液分離した後、該吸着
物を加熱焼成して行なわれる。The present invention involves adding SCP waste liquid to waste water containing heavy metal ions as described above to coat the waste water with SCP waste liquid, and then separating the adsorbate from solid-liquid, followed by heating and baking the adsorbate. It is done.
本発明に使用するＳＣＰ廃液廃液専焼上ＣＰ（セミケミ
カルパルプ）廃液を固瘉分５０％程度に濃縮し、７００
℃前後で還元焼成した後、サイクロンでガスと固形分を
分離し、ガスの主成分であるＳＯ２と固形分の主成分で
あるＮａ２ＣＯ３を再び反応させてＮａ２ＳＯｓ （
蒸解液の主成分）として回収した後の残さいカーボンで
あり、現在このカーボンは焼却処理されている。SCP waste liquid waste liquid used in the present invention The CP (semi-chemical pulp) waste liquid used in the present invention is concentrated to about 50% solid content, and
After reduction firing at around ℃, the gas and solids are separated using a cyclone, and SO2, which is the main component of the gas, and Na2CO3, which is the main component of the solids, are reacted again to form Na2SOs (
This is the carbon left after being recovered as the main component of cooking liquor, and currently this carbon is incinerated.
ＳＣＰ廃液廃液専焼上業分析値およびＪＩＳによる物性
値を表１に示す。Table 1 shows the SCP waste liquid waste liquid professional analysis values and JIS physical property values.
ＳＣＰ廃液廃液専焼側度は１００メツシユ以下であり、
内２００メツシュ以下が７５％以上占める。SCP waste liquid waste liquid exclusive combustion degree is 100 mesh or less,
More than 75% of them have less than 200 meshes.
ここで市販活性炭とＳＣＰ廃液廃液専焼側孔容積の比較
を表２に示す。Table 2 shows a comparison of commercially available activated carbon and SCP waste liquid dedicated combustion side pore volume.
ＳＣＰ廃液廃液専焼側販活性炭に（らべ、マクロ孔とト
ランジショナル孔が著しく多いのが特徴である。SCP waste liquid waste liquid exclusive combustion activated carbon is characterized by a significantly large number of macro pores and transitional pores.
重金属イオンを含む水溶液は一般に酸性であるが、ＳＣ
Ｐ廃液廃液専焼側加するとそれ自身から溶出する塩基性
塩類によってＳＣＰ廃液廃液専焼側面附近で重金属イオ
ンが水酸化物となり、この水酸化物がＳＣＰ廃液廃液専
焼側クロ孔、トランジショナル孔、ミクロ孔に吸着され
、除去されるものと思われる。Aqueous solutions containing heavy metal ions are generally acidic, but SC
When P waste liquid is added to the side of exclusive combustion, heavy metal ions become hydroxides near the side of the exclusive combustion of SCP waste due to the basic salts eluted from itself, and these hydroxides form pores, transitional pores, and micropores on the side of exclusive combustion of SCP waste liquid. It is thought that it is adsorbed and removed.
また、この塩基性塩類によって水溶液のＰＨは上昇し中
性ないし弱アルカリ性を示すので放流に際して特に中和
する必要はない。In addition, the pH of the aqueous solution increases due to the basic salts, making it neutral or weakly alkaline, so there is no need to neutralize the solution when it is discharged.
（Ｃｄ＋＋の場合は中和する必要あり）
ＳＣＰ廃液廃液専焼側加量は処理すべき水中の重金属イ
オンの種類、ＰＨおよび濃度によって変化する。(In the case of Cd++, it is necessary to neutralize it.) The amount of SCP waste liquid on the dedicated combustion side varies depending on the type, pH, and concentration of heavy metal ions in the water to be treated.
なお、本発明においてはＳＣＰ廃液専焼炭添加後、１０
〜３０分位攪拌し、固液分離を行なうことが望ましい。In addition, in the present invention, after adding charcoal to the SCP waste liquid, 10
It is desirable to stir for about 30 minutes to perform solid-liquid separation.
また、ＳＣＰ廃液廃液専焼側０〜７０％の水分を含んだ
状態で使用することが望ましい。Further, it is desirable to use the SCP waste liquid in a state where the dedicated combustion side contains 0 to 70% moisture.
市販活性炭とＳＣＰ廃液廃液専焼側種重金属イオンの吸
着能力の比較を表３．４．５に示す。Table 3.4.5 shows a comparison of commercially available activated carbon and the ability to adsorb heavy metal ions from the SCP waste liquid dedicated combustion side.
表３．４．５より、ＳＣＰ廃液廃液専焼型金属イオン吸
着能力は活性炭のそれを大きく上まわっていることがわ
かる。From Table 3.4.5, it can be seen that the metal ion adsorption capacity of the dedicated SCP waste liquid combustion type greatly exceeds that of activated carbon.
本発明は重金属を吸着せしめたＳＣＰ廃液専焼、炭を固
液分離した後、該吸着物を加熱焼成し、強熱残分として
重金属を回収するものであるが、図１に市販活性炭とＳ
ＣＰ廃液廃液専焼型熱減量曲線を示す。The present invention is to exclusively burn SCP waste liquid that has adsorbed heavy metals, separate the charcoal into solid and liquid, and then heat and sinter the adsorbed material to recover the heavy metals as an ignition residue.
The heat loss curve of the dedicated combustion type for CP waste liquid waste liquid is shown.
図１より、市販活性炭は４５０℃附近より減量しはじめ
、７００℃附近で灰化が終了しているが、ＳＣＰ廃液廃
液専焼型００℃附近から減量しはじめ、５００℃附近で
灰化が終了していることがわかる。From Figure 1, commercially available activated carbon starts to lose weight around 450°C and ashing ends around 700°C, but it starts to lose weight around 00°C for SCP waste liquid waste liquid combustion type, and ashing ends around 500°C. It can be seen that
このことは吸着物の加熱焼成に際して、ＳＣＰ廃液廃液
専焼型用する本発明は燃料費の点からも有利である。This means that the present invention, which uses a dedicated SCP waste liquid combustion type, is advantageous from the point of view of fuel costs when heating and firing the adsorbed material.
次に実施例を挙げて更に本発明の詳細な説明するが、本
発明はこれら実施例に制限されるものではない。EXAMPLES Next, the present invention will be further explained in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
乾燥重量に換算して１０Ｐ′のＳＣＰ廃液廃液専焼型分
４５％を含む）ＰＨ４，２の硫酸銅溶液（Ｃｕ十十とし
て３００ＰＰｍを含む）ＩＪ中に投入し、２０分間攪拌
したのち、固液分離し、電気炉中で該吸着物を乾燥しな
がら６００℃で３０分間焼成を行なった。Example 1 A copper sulfate solution (containing 45% of SCP waste liquid dedicated to combustion type of 10P' in terms of dry weight) with a pH of 4.2 (containing 300PPm as Cu) was poured into an IJ and stirred for 20 minutes. , solid-liquid separation was performed, and the adsorbed material was baked at 600° C. for 30 minutes while drying in an electric furnace.
その結果、ＣｕＯとして２３．３％を含有する１、５Ｌ
／の強熱残分を得た。As a result, 1.5L containing 23.3% as CuO
An ignition residue of / was obtained.
この強熱残分は他にＣａＳＯ４、Ｎａ２ＳＯ４などを含
む。This ignition residue also contains CaSO4, Na2SO4, etc.
また固液分離後の液はＰＨ７，８で残存Ｃｕ＋十濃度は
０．７ＰＰｍであった。The pH of the liquid after solid-liquid separation was 7.8, and the residual Cu+ concentration was 0.7 PPm.
実施例 ２
乾燥重量に換算して４グのＳＣＰ廃液廃液専焼型分４５
％を含む）をＰ Ｈ５，３の硫酸ニッケル溶液（Ｎｉ＋
十として１０ ｏｐｐｍを含む）ＩＪ中に投入し、３０
分間攪拌したのち、固液分離し、電気炉中で該吸着物を
乾燥しながら６００℃で３０分間焼成を行なった。Example 2 4 grams of SCP waste liquid in terms of dry weight: 45
%) in a nickel sulfate solution (Ni+
(including 10 oppm) into IJ and 30
After stirring for a minute, solid-liquid separation was performed, and the adsorbed material was baked at 600° C. for 30 minutes while drying in an electric furnace.
その結果、ＮｉＯとして２３．６％を含有する０、５３
ｙの強熱残分を得た。As a result, 0.53 containing 23.6% as NiO
An ignition residue of y was obtained.
この強熱残分は他にＣａＳＯ４、Ｎａ２ＳＯ４などを含
む。This ignition residue also contains CaSO4, Na2SO4, etc.
また固液分離後の液はＰＨ８，５で残存Ｎ、＋＋濃度は
１．ＯＰＰｍであった。The liquid after solid-liquid separation has a pH of 8.5, residual N, and a ++ concentration of 1. It was OPPm.
実施例 ３
乾燥重量に換算して２グのＳＣＰ廃液廃液専焼水分４５
％を含む）をＰＨ５，２の硝酸銀溶液（Ａｇとして１０
０ＰＰｍを含む）ｌｌ中に投入し、１０分間攪拌したの
ち、固液分離し、電気炉中で該吸着物を乾燥しながら６
００°Ｇ３０分間焼成を行なった。Example 3 SCP waste liquid waste liquid exclusive combustion moisture of 2 g in terms of dry weight 45
%) was added to a silver nitrate solution at pH 5.2 (10% as Ag).
After stirring for 10 minutes, solid-liquid separation was carried out, and the adsorbed material was dried in an electric furnace for 6 hours.
Firing was performed at 00°G for 30 minutes.
その結果、Ａｇ十として２８．２％を含有する０、３６
ｒの強熱残分を得た。As a result, 0.36 containing 28.2% as Ag
An ignition residue of r was obtained.
この強熱残分は他にＣａＳＯ４、Ｎａ２ＳＯ４などを含
む。This ignition residue also contains CaSO4, Na2SO4, etc.
また固液分離後の液はＰ Ｈ７，６で残存Ａｇ＋濃度は
０．４６ ｐｐｍであった。The pH of the liquid after solid-liquid separation was 7.6, and the residual Ag+ concentration was 0.46 ppm.
以上、本発明の方法により、排水中に溶存する重金属類
を効果的にかつ容易に除去、回収できることが明らかで
ある。As described above, it is clear that heavy metals dissolved in wastewater can be effectively and easily removed and recovered by the method of the present invention.
また本発明は現在焼却処理されているＳＣＰ廃液廃液専
焼水用するため、産業廃棄物の再利用という面からも有
意義である。Furthermore, since the present invention uses SCP waste liquid waste water that is currently incinerated, it is also significant from the perspective of reusing industrial waste.
Claims (1)
プ）廃液専焼炭（ＳＣＰ廃液を処理して得られた残さい
カーボン）を添加して排水中の重金属をＳＣＰ廃液廃液
専焼上着せしめ、次いで吸着物を固液分離した後、該吸
着物を加熱焼成し、強熱残分として重金属を回収するこ
とを特徴とする重金属イオン含有排水から重金属を回収
する方法。1 Add 5CP (semi-chemical pulp) waste liquid special combustion charcoal (residual carbon obtained by treating SCP waste liquid) to heavy metal ion-containing wastewater to coat the heavy metals in the wastewater with SCP waste liquid waste liquid special combustion, and then remove the adsorbent. 1. A method for recovering heavy metals from wastewater containing heavy metal ions, which comprises, after solid-liquid separation, heating and calcining the adsorbed material and recovering the heavy metals as an ignition residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55043187A JPS5919754B2 (en) | 1980-04-02 | 1980-04-02 | Method for recovering heavy metals from wastewater containing heavy metal ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55043187A JPS5919754B2 (en) | 1980-04-02 | 1980-04-02 | Method for recovering heavy metals from wastewater containing heavy metal ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56139190A JPS56139190A (en) | 1981-10-30 |
| JPS5919754B2 true JPS5919754B2 (en) | 1984-05-08 |
Family
ID=12656904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55043187A Expired JPS5919754B2 (en) | 1980-04-02 | 1980-04-02 | Method for recovering heavy metals from wastewater containing heavy metal ions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5919754B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012006000A (en) * | 2010-06-28 | 2012-01-12 | Iwate Univ | Heavy metal treating agent, method of treating heavy-metal-containing liquid, and method of recovering heavy metal |
| CN104909417B (en) * | 2015-05-27 | 2017-02-01 | 沈阳理工大学 | Waste liquid drying treatment system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4987585A (en) * | 1972-12-25 | 1974-08-21 | ||
| JPS515283A (en) * | 1974-07-02 | 1976-01-16 | Jujo Paper Co Ltd | TANSOSHITSUKYUCHAKUZAINO SEIZOHO |
| JPS5341909B2 (en) * | 1974-08-31 | 1978-11-07 |
-
1980
- 1980-04-02 JP JP55043187A patent/JPS5919754B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56139190A (en) | 1981-10-30 |
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