JPS63267494A - Treatment of waste liquid containing hexavalent chromium - Google Patents
Treatment of waste liquid containing hexavalent chromiumInfo
- Publication number
- JPS63267494A JPS63267494A JP62103923A JP10392387A JPS63267494A JP S63267494 A JPS63267494 A JP S63267494A JP 62103923 A JP62103923 A JP 62103923A JP 10392387 A JP10392387 A JP 10392387A JP S63267494 A JPS63267494 A JP S63267494A
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- tank
- sent
- solution
- containing waste
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 28
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 claims abstract description 26
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 24
- 239000000920 calcium hydroxide Substances 0.000 claims description 19
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 19
- 238000009713 electroplating Methods 0.000 claims description 15
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052804 chromium Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 239000000571 coke Substances 0.000 abstract description 3
- 239000006228 supernatant Substances 0.000 abstract description 3
- 230000003009 desulfurizing effect Effects 0.000 abstract description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 3
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 3
- 239000004571 lime Substances 0.000 abstract 3
- 239000008267 milk Substances 0.000 abstract 3
- 210000004080 milk Anatomy 0.000 abstract 3
- 235000013336 milk Nutrition 0.000 abstract 3
- 238000005189 flocculation Methods 0.000 abstract 2
- 230000016615 flocculation Effects 0.000 abstract 2
- 230000003472 neutralizing effect Effects 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 235000010269 sulphur dioxide Nutrition 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、例えば電気メッキ工程で発生するＣｒ＆Ｆ
を含む廃液を確実に、しかも安価に処理する方法に関す
るものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the treatment of Cr&F generated in the electroplating process, for example.
The present invention relates to a method for reliably and inexpensively treating waste liquid containing .
電気メッキ工程では、ティンフリースチールのようなり
ロム酸の電解による皮膜形成や、亜鉛等のメッキをした
後に化成処理によるクロム酸塩の皮膜形成を行ない、耐
食性、防錆性等を付加することが広く行なわれている。In the electroplating process, it is possible to add corrosion resistance, rust prevention, etc. by forming a film by electrolyzing romic acid, such as tin-free steel, or by forming a chromate film by chemical conversion treatment after plating with zinc, etc. It is widely practiced.
一方、Ｃｒ のクロムは、有害元素として取上げられ
ておシ、これを無害にして処理することか厳重に義務付
けられている。On the other hand, chromium (Cr) is considered a harmful element, and it is strictly required to treat it to make it harmless.
前記のような電気メッキ工程では、その廃液にＣｒ’＋
が含むことが多いことから、確実に無害にして処理する
方法が厳重にチェックされながら、実用的に行なわれて
いる。その方法の一つとして、表１に示すような還元剤
による場合が挙げられる。In the electroplating process as mentioned above, the waste liquid contains Cr'+
Since these substances often contain a large number of substances, methods to ensure that they are rendered harmless are being carefully checked and put into practice. One of the methods is to use a reducing agent as shown in Table 1.
表１では、還元剤として鉄、硫酸鉄、亜硫酸ソーダ、重
亜硫酸ソーダ、亜硫酸ガスが挙げられ、Ｃｒ’＋との反
応式及びＣｒ を還元するに要する薬品量（還元剤量
）が示されている。この中で実用的には重亜硫酸ソーダ
が還元剤として広く使用されて１ハる。Table 1 lists iron, iron sulfate, sodium sulfite, sodium bisulfite, and sulfur dioxide gas as reducing agents, and shows the reaction formula with Cr'+ and the amount of chemicals (amount of reducing agent) required to reduce Cr. There is. Among these, sodium bisulfite is widely used as a reducing agent in practice.
第２図は、重亜硫酸ソーダを還元剤として使用した場合
のクロム酸排水処理フローシートである。FIG. 2 is a flow sheet for treating chromic acid wastewater when sodium bisulfite is used as a reducing agent.
電気メッキ工程で発生したＣｒ を含む廃液１は、ク
ロム還元槽２に送入し、硫酸タンク３がら硫酸４を注入
して、−を２〜３に調整する。ここでは、重亜硫酸ソー
ダ溶液・タンク５から所定量の重亜硫酸ソーダ溶液６が
添加される。そして、攪拌機２によりて充分に攪拌され
、次の反応式に示すようにＣｒ １ｔＣｒ に還元
される。A waste liquid 1 containing Cr generated in the electroplating process is sent to a chromium reduction tank 2, and sulfuric acid 4 is injected from a sulfuric acid tank 3 to adjust - to 2 to 3. Here, a predetermined amount of sodium bisulfite solution 6 is added from the sodium bisulfite solution tank 5. Then, it is sufficiently stirred by the stirrer 2 and reduced to Cr 1tCr as shown in the following reaction formula.
４Ｈ２ＣｒＯ４＋６Ｎ＆Ｈ８０３＋３Ｈ２ｓｏ４→２ｃ
ｒ（ｓｏ４）３＋３Ｎａ２ｓｏ４＋１ｏＨ２゜ついで還
元された溶液８はオーバーフローして中和槽９に送入さ
れ、そこで石灰乳、タンク１゜から石灰乳１１を添加し
て−を７〜８に中和して、Ｃｒ５を水酸化クロムにする
。4H2CrO4+6N&H803+3H2so4→2c
r(so4)3+3Na2so4+1oH2° Then, the reduced solution 8 overflows and is sent to the neutralization tank 9, where milk of lime and milk of lime 11 from tank 1° are added to neutralize - to 7 to 8. , convert Cr5 to chromium hydroxide.
２０ｒ２（８０４）、 ＋３０ａ（ＯＨ）ｚ →２Ｃｒ
（ＯＨ）３＋３０ａＳ０４この中和溶液１２は次の凝集
沈澱槽１３に送入され、そこで水酸化クロム、硫酸カル
シウムを沈澱し、その沈澱物１４を除去し上澄水１５を
排水する。ここにおいて１６はスラッジ排出槽である。20r2(804), +30a(OH)z →2Cr
(OH)3+30aS04 This neutralized solution 12 is sent to the next coagulation-sedimentation tank 13, where chromium hydroxide and calcium sulfate are precipitated, the precipitate 14 is removed, and the supernatant water 15 is drained. Here, 16 is a sludge discharge tank.
〔発明が解決しようとする問題点〕
しかしながら、電気メッキ工程で発生する廃液は大針で
あり、その還元に要する還元剤の量も膨大である。その
ため、電気メッキ設備を有する工場では、それらの還元
剤を安価にして、かつ還元剤としての機能を充分に発揮
出来る代替が得られることを強く要望していた。[Problems to be Solved by the Invention] However, the waste liquid generated in the electroplating process is a large needle, and the amount of reducing agent required for its reduction is also enormous. For this reason, factories with electroplating equipment have strongly desired an alternative reducing agent that can be used at a lower cost and that can fully perform its function as a reducing agent.
本発明の目的は、かかる要望を満足出来る代替を見出し
、Ｃｒ を含む廃液を確実に無害にし、しかも安価に
処理する方法を提供することにある。It is an object of the present invention to find an alternative that can satisfy such demands, and to provide a method for treating waste liquid containing Cr while reliably rendering it harmless and at a low cost.
〔問題点を解決するための手段及び作用〕本発明は、硫
黄又は硫黄化合物を燃焼して得られる亜硫酸がスを石灰
乳で処理し、そこで得られる重亜硫酸カルシウムを含む
廃液をＣｒ を含む廃液に添加して反応させ、中和後
、凝集沈澱処理する廃液の処理方法を特徴とするもので
ある。[Means and effects for solving the problems] The present invention involves treating sulfite obtained by burning sulfur or sulfur compounds with milk of lime, and converting the resulting waste liquid containing calcium bisulfite into a waste liquid containing Cr. The present invention is characterized by a method for treating waste liquid, in which the liquid is added to react, neutralized, and then coagulated and precipitated.
製鉄会社等では、工場内に電気メッキ設備とともに、Ｓ
０３源として考えられるコークス炉ガス脱硫設備等があ
る。それにより回収して得られる硫黄等を燃焼して発生
させた亜硫酸ガスＣ５Ｏ２）を石灰乳で処理し、重亜硫
酸カルシウム溶液を得、それを還元剤の代替に供しよう
とした。Steel companies, etc. have electroplating equipment and S
Coke oven gas desulfurization equipment, etc., can be considered as a source of 03. The sulfur dioxide gas (C5O2) generated by burning the recovered sulfur and the like was treated with milk of lime to obtain a calcium bisulfite solution, which was attempted to be used in place of the reducing agent.
まず、前記重亜硫酸カルシウム溶液が電気メッキ工程で
発生するＣｒ を含んだ廃液の処理に適す（ビーカー
実験）
（１）実験方法：電気メッキ工程で発生したＣｒ’＋を
含んだ廃液をビーカーに３１！採取し、硫酸を加えてｐ
Ｈ２に調整し、攪拌しながら、実験用の重亜硫酸カルシ
ウム溶液を所定量添加し、還元反応を行なった後に、石
灰乳（Ｃａ（ＯＨ）２ ）で声８に中和し、処理した。First, the calcium bisulfite solution is suitable for treating the waste liquid containing Cr generated in the electroplating process (beaker experiment) (1) Experimental method: The waste liquid containing Cr'+ generated in the electroplating process is placed in a beaker at ! Collect it, add sulfuric acid and p
After adjusting to H2 and adding a predetermined amount of experimental calcium bisulfite solution while stirring to perform a reduction reaction, the mixture was neutralized to a concentration of 8 with milk of lime (Ca(OH)2) and treated.
同様に比較として従来のＮａＨ３Ｏｓ溶液により処理し
た。Similarly, a conventional NaH3Os solution was treated as a comparison.
（２）結果：結果を表２に示す。(2) Results: The results are shown in Table 2.
表２から明らかなように、従来のＮａＨ８Ｏｓ溶液の場
合と同様にＣｒ は検出されず、還元剤としての効果
がある。As is clear from Table 2, Cr was not detected as in the case of the conventional NaH8Os solution, and it is effective as a reducing agent.
（モデル還元槽での実験）
（１）実験方法：実設備の約１／（１０００）モデルの
還元橢（容量的３５））を用い、電気メッキ工程で発生
するＣｒ６＋を含んだ廃液をその還元槽に連続的に送入
し、そこで硫酸を加えて声２に調整し、攪拌しながら、
実験用の重亜硫酸カルシウム溶液を所定量添加し、還元
反応を行なった後に、それらの溶液を順次配設した中和
槽で石灰乳（Ｃａ（ＯＨ）２）を加えて−８に中和し、
処理した。(Experiment in a model reduction tank) (1) Experimental method: Using a model reduction tank (approximately 1/(1000) of the actual equipment (capacity: 35)), waste liquid containing Cr6+ generated in the electroplating process is reduced. It is continuously fed into a tank, where sulfuric acid is added to adjust the volume to 2, and while stirring,
After adding a predetermined amount of experimental calcium bisulfite solution and performing a reduction reaction, milk of lime (Ca(OH)2) was added to neutralize the solution to -8 in a neutralization tank in which the solutions were sequentially placed. ,
Processed.
同様に比較として従来のＮａＨ３Ｏｓ溶液によシ処理し
た。Similarly, for comparison, a conventional NaH3Os solution was used.
（２）結果 ：結果を表３に示す。(2) Results: The results are shown in Table 3.
表３から明らかなように、従来のＮａ）ｉｓｏ ３溶液
の場合と同様にＣｒ は検出されず、還元剤としての
効果があること確認出来た。ここでは、連続的に実験用
の重亜硫酸カルシウム溶液を使用し、ついて従来のＮａ
Ｈ８Ｏｓ溶液を使用し、そして実験用の重亜硫酸カルシ
ウム溶液を使用したが、どちらの場合もＣｒ は検出
されなかった。As is clear from Table 3, as in the case of the conventional Na)iso3 solution, Cr was not detected, confirming that it was effective as a reducing agent. Here, we continuously use experimental calcium bisulfite solution, followed by conventional Na
A H8Os solution and an experimental calcium bisulfite solution were used, and no Cr was detected in either case.
以上の実験結果から、硫黄又は硫黄化合物を燃焼して得
られる亜硫酸ガスを石灰乳で処理し、そこで得られた重
亜硫酸カルシウム溶液は、電気メッキ工程で発生するＣ
ｒ を含む廃液の還元剤として使用されている重亜硫
酸ソーダ溶液（ＮａＨ３Ｏ３）と同程度の効果があり、
充分還元剤の代替として使用出来ることを確認した。From the above experimental results, it was found that when sulfur dioxide gas obtained by burning sulfur or sulfur compounds is treated with milk of lime, the resulting calcium bisulfite solution is free from carbon dioxide generated during the electroplating process.
It is as effective as sodium bisulfite solution (NaH3O3), which is used as a reducing agent for waste liquid containing r.
It was confirmed that it can be used as a sufficient substitute for reducing agents.
本発明の方法では、硫黄等を燃焼して得られる亜硫酸ガ
スを石灰乳で処理して得られる重亜硫酸カルシウムを含
む廃液を還元剤として使用すること、特に連続的に使用
することに特徴がある。特にコークス炉発生ガス等を水
酸化アンモニウム等で脱硫して得られた硫黄を燃焼して
発生させた亜硫酸ガスは不純物がほとんどなく、それを
石灰乳で処理して得られた重亜硫酸カルシウムを含む廃
液も表４に示すように不純物がほとんどないものである
。The method of the present invention is characterized in that a waste liquid containing calcium bisulfite obtained by treating sulfur dioxide gas obtained by burning sulfur etc. with milk of lime is used as a reducing agent, particularly in that it is used continuously. . In particular, the sulfur dioxide gas generated by burning the sulfur obtained by desulfurizing coke oven gas etc. with ammonium hydroxide has almost no impurities, and contains calcium bisulfite obtained by treating it with milk of lime. As shown in Table 4, the waste liquid also contains almost no impurities.
この重亜硫酸カルシウムを含む廃液は、電気メッキ工程
で発生するＣｒ を含む廃液にクロム還元槽内で連続
的に所定量添加して使用されるが、工場内での燃焼によ
シ発生する亜硫酸ガスの量とのバランスを図るために石
灰乳で処理して得られる重亜硫酸カルシウム溶液は、還
元剤に使用しないものは、酸化塔に送シ、そこで空気に
よる酸化を行ない脱水機を経て石膏として回収される。This waste liquid containing calcium bisulfite is used by continuously adding a predetermined amount to the waste liquid containing Cr generated in the electroplating process in a chromium reduction tank, but the sulfur dioxide gas generated by combustion in the factory is used. Calcium bisulfite solution obtained by treating with milk of lime to balance the amount of water is sent to an oxidation tower, where it is oxidized with air and recovered as gypsum through a dehydrator, unless it is used as a reducing agent. be done.
本発明の方法では、工場内での燃焼によシ発生 ・す
る亜硫酸ガスを利用して、石灰乳による処理で重亜硫酸
カルシウムを含む廃液を多量に得られるので、電気メツ
中工程等で発生するＣｒ を含む廃液に、そのＣｒ’
＋を無害のＣｒ″に還元するに充分な量が添加出来る。In the method of the present invention, a large amount of waste liquid containing calcium bisulfite can be obtained by processing with milk of lime by using sulfur dioxide gas, which is generated due to combustion in the factory, so that it is possible to obtain a large amount of waste liquid containing calcium bisulfite. In the waste liquid containing Cr, the Cr'
A sufficient amount can be added to reduce + to harmless Cr''.
以下本発明によシミ気メッキ廃液を処理する方法を図に
よって説明する。Hereinafter, a method for treating stain plating waste liquid according to the present invention will be explained with reference to the drawings.
第１図は、電気メッキ廃液を処理するフローシートであ
る。Ｓ０３源としてのコークス炉発生ガス２１は脱硫塔
２２で脱硫液（水酸化アンモニウム）２３と触媒とで処
理され、脱硫ガスは燃焼用ガス２４に供される。ここで
回収された硫黄２５は、熱焼炉２６で燃焼されて亜硫酸
がス２７としてＳＯ□吸収塔２８に送入される。FIG. 1 is a flow sheet for treating electroplating waste liquid. Coke oven generated gas 21 as a source of S03 is treated in a desulfurization tower 22 with a desulfurization liquid (ammonium hydroxide) 23 and a catalyst, and the desulfurization gas is provided as combustion gas 24. The sulfur 25 recovered here is burned in a thermal furnace 26 and sulfurous acid is sent to the SO□ absorption tower 28 as soot 27.
ここで石灰乳２９を加えて反応し、重亜硫酸カルシウム
を含む廃液３０を得る。それは重亜硫酸カルシウム廃液
タンク３１に貯留され、還元剤タンク３ノに送入される
。還元剤に使用しなり重亜濃酸カルシウム廃液３０は、
酸化塔３２に送られ、そこで空気によシ石膏スラリーと
し、脱水機３３で脱水して石膏３４として回収される。Here, milk of lime 29 is added and reacted to obtain a waste liquid 30 containing calcium bisulfite. It is stored in the calcium bisulfite waste liquid tank 31 and sent to the reducing agent tank 3. The flexible calcium binitite waste liquid 30 used as a reducing agent is
It is sent to an oxidation tower 32, where it is oxidized with air to form a gypsum slurry, dehydrated in a dehydrator 33, and recovered as gypsum 34.
電気メッキ工程で発生したＣｒ＆＋を含む廃液１はクロ
ム還元槽２に送入され、硫酸タンク３から硫俊４を加え
てＰ）（２に調整される。その溶液に還元ＩＪタンク３
５から連続的に重亜硫酸カルシウム廃夜３６が添加され
、還元反応が行なわれる。ここでは廃液は攪拌機７によ
シ充分に攪拌され、還元反応は瞬時に終了する。The waste liquid 1 containing Cr&+ generated in the electroplating process is sent to the chromium reduction tank 2, and adjusted to P) by adding sulfuric acid 4 from the sulfuric acid tank 3.The solution is added to the chromium reduction tank 3.
Calcium bisulfite waste 36 is continuously added from step 5 to carry out a reduction reaction. Here, the waste liquid is sufficiently stirred by the stirrer 7, and the reduction reaction is completed instantaneously.
還元反応の終了した溶液８は中和槽９ＶＣオーバーフロ
ーして送られ、そこで石灰乳タンク１０から石灰乳１１
の添加により声８に中和され念後、その中和溶液１２は
、凝集沈澱槽１３に送られ、そこで高分子凝集剤等が加
えられて水酸化りはム。The solution 8 that has undergone the reduction reaction overflows into the neutralization tank 9VC and is sent there to the milk of lime 11 from the milk of lime tank 10.
The neutralized solution 12 is then sent to a coagulation and sedimentation tank 13, where a polymer flocculant and the like are added to form a hydroxide solution.
硫酸カルシウムとして沈澱し、沈澱物１４を除去し、上
澄液１５は排水される。ここＫＴｈいて１６はスラッジ
排出槽である。It precipitates as calcium sulfate, the precipitate 14 is removed and the supernatant liquid 15 is drained. KTh here 16 is a sludge discharge tank.
次に本発明方法により実験した結果を表５に示す。Next, Table 5 shows the results of experiments conducted using the method of the present invention.
表５から明らかなようにＣｒ は検出されず、他の有
害物質も検出されない。As is clear from Table 5, Cr was not detected, nor were other harmful substances.
以上のことから従来使用されていたＮ＊Ｈ８Ｏｓ還元剤
の代替として、重亜硫酸カルシウムを含む廃液を使用し
て、Ｃｒ ｔ−含む廃液を確実に無害にすることが出
来ることがわかる。From the above, it can be seen that by using a waste liquid containing calcium bisulfite as a substitute for the conventionally used N*H8Os reducing agent, it is possible to reliably render the waste liquid containing Cr t- harmless.
本発明方法によれば、工場内で発生する硫黄等を燃焼し
て得られる亜硫酸ガスを石灰乳で処理した重亜硫酸カル
シウムを含む廃液を還元剤として使用することによって
、従来の重亜硫酸ソーダ溶液の還元剤と同種度の効果を
挙げることが出来、Ｃｒ’＋を無害にすることが出来る
。この場合重亜硫酸カルシウムを含む廃液は工場内で容
易に、安価に得ることが出来るので、本発明方法は産業
上利用両値の非常に大きな発明である。According to the method of the present invention, by using a waste liquid containing calcium bisulfite obtained by treating sulfur dioxide gas obtained by burning sulfur etc. generated in a factory with milk of lime as a reducing agent, the conventional sodium bisulfite solution can be reduced. It can produce the same effect as a reducing agent and can render Cr'+ harmless. In this case, the waste liquid containing calcium bisulfite can be easily obtained in a factory at a low cost, so the method of the present invention is an invention with great industrial utility.
４、簡単な図面の説明
２６・・・燃焼炉、２ Ｆ−・・亜硫酸ガス、２８・・
・ＳＯ□吸収塔、２９・・・石灰乳、３ｏ・・・重亜硫
酸カルシウムを含む廃液、３１・・・重亜硫酸カルシウ
ム溶液貯留槽、３５・・・還元剤タンク、１・・・廃水
、２・・・クロム還元槽、９・・・中和槽、１３・・・
凝集沈澱槽。4. Brief explanation of drawings 26... Combustion furnace, 2 F-... Sulfur dioxide gas, 28...
・SO□ absorption tower, 29...milk of lime, 3o...waste liquid containing calcium bisulfite, 31...calcium bisulfite solution storage tank, 35...reducing agent tank, 1...waste water, 2 ... Chromium reduction tank, 9... Neutralization tank, 13...
Coagulation sedimentation tank.
出創人代理人 弁理士 鈴 江 武 彦手続補正書
１．事件の表示
特願昭６２−１０３９２３号
２、発明の名称
六価クロムを含む廃液の処理方法
３、補正をする者
事件との関係 特許出願人
（４１２） 日本鋼管株式会社
４、代理人
東京都千代田区霞が関３丁目７番２号 ＵＢＥビル７、
補正の内容
（１） 明細書第４頁第１６行にｒ ２Ｃｒ（ＳＯ４
） ３ ｊとあるをｒ２ｃｒ２（ＳＯ４） ３Ｊと訂正
する。Founder's agent Patent attorney Takehiko Suzue Procedural amendment 1. Display of the case Japanese Patent Application No. 62-103923 2, Name of the invention Method for treating waste liquid containing hexavalent chromium 3, Person making the amendment Relationship to the case Patent applicant (412) Nippon Kokan Co., Ltd. 4, Agent Tokyo UBE Building 7, 3-7-2 Kasumigaseki, Chiyoda-ku,
Contents of amendment (1) r2Cr(SO4
) 3 j should be corrected as r2cr2(SO4) 3J.
（２） 同第１０頁第３行に「あること確認」とある
を「あることが確認」と訂正する。(2) On page 10, line 3 of the same page, the phrase ``Confirmation of certain things'' is corrected to ``Confirmation of certain things.''
（３）同第１２頁、表４、の横欄の項目（第４行口）に
、「（濃度％）」とあるを「（濃度％）」と訂正する。(3) On page 12, in the horizontal column of Table 4 (line 4, opening), the text "(concentration %)" is corrected to "(concentration %)."
（４） 同第１４頁第７行〜第８行に「還元剤タンク
３１」とあるを「還元剤タンク３５」と訂正する。(4) On page 14, lines 7 and 8, "reducing agent tank 31" is corrected to "reducing agent tank 35."
（５） 同第１４頁第１４行にｒｐＨ２Ｊとあるをｒ
ｐＨ２〜３」と訂正する。(5) rpH2J on page 14, line 14.
pH 2-3” is corrected.
（６） 同第１４頁第１５行に「連続的に」とあるを
削除する。(6) Delete "continuously" from page 14, line 15.
（７）同第１６頁、表５の還元剤使用量の単位（第４行
）にｒｍ３／）ン」とあるを「ノ／トン」と訂正する。(7) On page 16 of the same page, in Table 5, the unit for the amount of reducing agent used (line 4) is corrected to read ``rm3/ton'' as ``no/ton.''
（８）同第１８頁第３行に「１・・・廃水」とあるを「
１・・・廃液」と訂正する。(8) On page 18, line 3 of the same page, replace “1...wastewater” with “
1...Correct to "waste liquid".
（９）第３頁の表１を下記の通り訂正する。(9) Table 1 on page 3 is corrected as follows.
（ｌＯ）第７頁の表２を下記の通り訂正する。(IO) Table 2 on page 7 is corrected as follows.
（１１）図面第１図に別紙の通り符号１２を加える。(11) Add numeral 12 to Figure 1 of the drawing as per the attached sheet.
Claims (1)
灰乳で処理し、それによって得られた重亜硫酸カルシウ
ムを含む廃液をＣｒ＾６＾＋を含む電気メッキ廃液に添
加して、反応させ、中和後、凝集沈澱処理することを特
徴とする六価クロムを含む廃液の処理方法。The sulfur dioxide gas obtained by burning sulfur or sulfur compounds is treated with milk of lime, and the resulting waste solution containing calcium bisulfite is added to the electroplating waste solution containing Cr^6^+, reacted, and 1. A method for treating waste liquid containing hexavalent chromium, which comprises performing a coagulation and precipitation treatment after immersion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103923A JPS63267494A (en) | 1987-04-27 | 1987-04-27 | Treatment of waste liquid containing hexavalent chromium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103923A JPS63267494A (en) | 1987-04-27 | 1987-04-27 | Treatment of waste liquid containing hexavalent chromium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267494A true JPS63267494A (en) | 1988-11-04 |
| JPH0521636B2 JPH0521636B2 (en) | 1993-03-25 |
Family
ID=14366946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62103923A Granted JPS63267494A (en) | 1987-04-27 | 1987-04-27 | Treatment of waste liquid containing hexavalent chromium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63267494A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100345296B1 (en) * | 1998-12-11 | 2002-11-18 | 재단법인 포항산업과학연구원 | Treatment method of waste water containing hexavalent chromium compound_ |
| CN102758080A (en) * | 2012-07-25 | 2012-10-31 | 福建省双旗山矿业有限责任公司 | Method for microwave roasting and non-cyanogen gold leaching of sulfur-bearing gold mineral |
| CN102758081A (en) * | 2012-07-25 | 2012-10-31 | 福建省双旗山矿业有限责任公司 | Method for microwave plasma roasting and non-cyanogen gold leaching of sulfur-bearing gold mineral |
| CN105776466A (en) * | 2016-03-14 | 2016-07-20 | 湖北徐风环保科技有限公司 | Purification method of sodium sulphate waste water |
| JP2017121604A (en) * | 2016-01-06 | 2017-07-13 | 日新製鋼株式会社 | Treatment method of hexavalent chromium-containing waste liquid |
| JP2020164346A (en) * | 2019-03-28 | 2020-10-08 | 宇部興産株式会社 | Manufacturing method of sulfur-based composition and cement composition, and manufacturing system of cement composition |
| JP2021109796A (en) * | 2020-01-08 | 2021-08-02 | 宇部興産株式会社 | Method for producing sulfur-based composition and cement composition, system for producing cement composition, and cement-based solidifying material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS575598A (en) * | 1980-06-13 | 1982-01-12 | Hitachi Ltd | Operation controller for turborefrigerator |
| JPS57204289A (en) * | 1981-06-09 | 1982-12-14 | Showa Denko Kk | Removal of metallic component |
-
1987
- 1987-04-27 JP JP62103923A patent/JPS63267494A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS575598A (en) * | 1980-06-13 | 1982-01-12 | Hitachi Ltd | Operation controller for turborefrigerator |
| JPS57204289A (en) * | 1981-06-09 | 1982-12-14 | Showa Denko Kk | Removal of metallic component |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100345296B1 (en) * | 1998-12-11 | 2002-11-18 | 재단법인 포항산업과학연구원 | Treatment method of waste water containing hexavalent chromium compound_ |
| CN102758080A (en) * | 2012-07-25 | 2012-10-31 | 福建省双旗山矿业有限责任公司 | Method for microwave roasting and non-cyanogen gold leaching of sulfur-bearing gold mineral |
| CN102758081A (en) * | 2012-07-25 | 2012-10-31 | 福建省双旗山矿业有限责任公司 | Method for microwave plasma roasting and non-cyanogen gold leaching of sulfur-bearing gold mineral |
| JP2017121604A (en) * | 2016-01-06 | 2017-07-13 | 日新製鋼株式会社 | Treatment method of hexavalent chromium-containing waste liquid |
| CN105776466A (en) * | 2016-03-14 | 2016-07-20 | 湖北徐风环保科技有限公司 | Purification method of sodium sulphate waste water |
| JP2020164346A (en) * | 2019-03-28 | 2020-10-08 | 宇部興産株式会社 | Manufacturing method of sulfur-based composition and cement composition, and manufacturing system of cement composition |
| JP2021109796A (en) * | 2020-01-08 | 2021-08-02 | 宇部興産株式会社 | Method for producing sulfur-based composition and cement composition, system for producing cement composition, and cement-based solidifying material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0521636B2 (en) | 1993-03-25 |
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