JPS63190696A - Treatment of waste liquid of 'ruthener' electrolytic cell - Google Patents
Treatment of waste liquid of 'ruthener' electrolytic cellInfo
- Publication number
- JPS63190696A JPS63190696A JP1829887A JP1829887A JPS63190696A JP S63190696 A JPS63190696 A JP S63190696A JP 1829887 A JP1829887 A JP 1829887A JP 1829887 A JP1829887 A JP 1829887A JP S63190696 A JPS63190696 A JP S63190696A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- ferrite
- electrolytic cell
- ruthener
- hexavalent chromium
- 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.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims description 22
- 239000002699 waste material Substances 0.000 title claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000005554 pickling Methods 0.000 claims abstract description 13
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 6
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000011651 chromium Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000007832 Na2SO4 Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ステンレス鋼酸洗工程で発生する６価クロム
含有のルスナー電解槽廃液の処理方法、すなわち廃液か
らフェライトを回収し、ＮａｚＳＯ４を再利用する方法
に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for treating waste liquid from a Lussner electrolyzer containing hexavalent chromium generated in a stainless steel pickling process, that is, recovering ferrite from the waste liquid and recycling NazSO4. It is about how to use it.
〈従来の技術〉
ステンレス鋼酸洗工程は、鋼種によりその酸洗方法は異
なるが、例えば第１楢は３０％ＮａｚＳＯ４によるルス
ナー電解法、第２槽は硫酸、第３槽は混酸というように
何種類かの酸を組合せて行われている。<Prior art> In the stainless steel pickling process, the pickling method differs depending on the steel type, but for example, the first tank uses Lussner electrolysis with 30% NazSO4, the second tank uses sulfuric acid, and the third tank uses mixed acid. It is done by combining different types of acids.
ステンレス鋼酸洗のうち、ルスナー電解法から排出した
溶液中には脱離スケール、溶出金属特に６価クロムが多
く含有されている。During stainless steel pickling, the solution discharged from the Rusner electrolysis process contains a large amount of detached scale and eluted metals, particularly hexavalent chromium.
ルスナー電解槽から排出された液の一部は、脱離スケー
ルを除去し、リサイクルされるが、一部はメイクアップ
のために廃液とされていた。A portion of the liquid discharged from the Lussner electrolytic cell is recycled after removal of scale, but a portion is used as waste for make-up.
すなわち、このルスナー電解槽廃液は、従来水処理設備
で他の排水と共に処理され廃棄されていた。That is, this Rusner electrolyzer waste liquid has conventionally been treated and discarded together with other wastewater in water treatment equipment.
なお、排水中のを害金属の除去方法として排水中に第１
鉄イオンを添加した後、アルカリによる中和、空気など
による酸化をして、第１鉄イオンをマグネタイトまたは
オキシ水酸化鉄としマグネタイト結晶格子中に該有害金
属イオンを取込むか、またはオキシ水酸化鉄に吸着させ
て除去する方法が特公昭５１−２２３０７号、特公昭５
１−３９９４０号に開示されているが、Ｃｒイオンは結
晶格子中に取込みにく＜ 、Ｃｒイオンを除去するため
には、Ｃｒイオンの約１００倍もの第１銖イオンが必要
であり、効率が悪く、また廃棄物の発生量が多く、その
処理費が嵩んでいた。In addition, as a method of removing harmful metals from wastewater,
After adding iron ions, they are neutralized with alkali and oxidized with air to convert the ferrous ions into magnetite or iron oxyhydroxide, incorporating the harmful metal ions into the magnetite crystal lattice, or oxidizing them with oxyhydroxide. The method of removing iron by adsorption is described in Tokoku No. 51-22307 and Tokkoku No. 5
1-39940, Cr ions are difficult to incorporate into the crystal lattice, and in order to remove Cr ions, approximately 100 times as many first ion ions as Cr ions are required, resulting in low efficiency. Moreover, the amount of waste generated was large, and the cost of processing it was high.
〈発明が解決しようとする問題点〉
本発明は、従来ルスナー電解廃液からの重金属の回収は
されずに、また一部廃液は利用されず廃棄されていたの
で、このルスナー電解廃液中の重金属類を効率よく回収
し、さらに廃液をＮａｚＳＯ。<Problems to be Solved by the Invention> The present invention solves the problem of heavy metals in the Rusner electrolytic waste, since conventionally the heavy metals were not recovered from the Rusner electrolytic waste and some of the waste was discarded without being used. is efficiently collected, and the waste liquid is converted into NazSO.
水溶液として再利用できる方法を提供するためになされ
たものである。This was done to provide a method that can be reused as an aqueous solution.
〈問題点を解決するための手段〉
本発明者らは、幾多の研究を重ねた結果、従来の方法に
比べてより少ない量の第−銖イオン量でＣｒイオンを除
去できる方法を見い出し、この知見にもとづいて本発明
をなすに至った。<Means for solving the problem> As a result of numerous studies, the present inventors have discovered a method that can remove Cr ions with a smaller amount of primary ions than conventional methods, and have developed this method. The present invention was made based on this knowledge.
本発明は、ステンレスＥの酸洗工程で発生する６価りロ
ム含存のルスナー電解槽ＮａｚＳＯ，溶液に２価鉄／
６ 価クロムのモル比が５〜５０になるように硫酸第１
鉄を添加し、つぎにこれに苛性ソーダを添加し、ｐＨを
１０立１に調整し、空気などの酸化性ガスを吹き込んで
酸化し、フェライトを生成させた後、このフェライトを
分離回収し、さらに分離液としてＮａｚＳＯ，溶液を回
収するルスナー電解槽廃液の処理方法である。The present invention uses a Lussner electrolytic cell NazSO containing hexavalent rom generated in the pickling process of stainless steel E, and a solution containing divalent iron/
Add sulfuric acid first so that the molar ratio of hexavalent chromium is 5 to 50.
Iron is added, then caustic soda is added to this, the pH is adjusted to 10 to 1, and oxidizing gas such as air is blown in to oxidize to produce ferrite, and this ferrite is separated and recovered. This is a method for treating waste liquid from a Rusner electrolytic cell, in which NazSO is used as a separation liquid, and a solution is recovered.
く作 用〉 本発明の構成、作用について以下に説明する。For Kusaku The structure and operation of the present invention will be explained below.
ルスナー電解槽廃液中には、通常１００〜１．０００ｐ
ｐｍの６価クロムが含まれているが、ルスナー電解槽廃
液に添加する硫酸第１鉄の量としては、２価鉄（第１鉄
）７６価クロムのモル比が５〜５０になるように添加す
る。５より少ないと正常なフェライト、（スピネル型フ
ェライト）が生成しない。Usually 100 to 1,000 p is contained in the Rusner electrolytic cell waste liquid.
PM of hexavalent chromium is included, but the amount of ferrous sulfate added to the Rusner electrolyzer waste liquid should be such that the molar ratio of divalent iron (ferrous iron) to 76-valent chromium is 5 to 50. Added. If it is less than 5, normal ferrite (spinel type ferrite) will not be produced.
５０より多いと、処理液の総量が増え、好ましくない。When it is more than 50, the total amount of processing liquid increases, which is not preferable.
使用する硫酸第１鉄としては、ステンレス網硫酸酸洗槽
の廃液を使用することが工程上好ましいが、その他の目
板の酸洗、酸化チタン製造の際物として大量に発生する
硫酸第１銖を用いることもできる。As the ferrous sulfate to be used, it is preferable to use the waste liquid from the stainless steel mesh sulfuric acid pickling tank, but other ferrous sulfuric acid pickling tanks, which are generated in large quantities during the pickling of battens and the production of titanium oxide, can also be used. You can also use
ついで、苛性ソーダを添加し、ｐＨを１０＝１に調整す
る。これは、次工程の酸化工程でフェライトを効率よく
生成させるためである。Then add caustic soda and adjust the pH to 10=1. This is to efficiently generate ferrite in the next oxidation step.
つぎの酸化工程で、酸化に用いるガスとしては酸化性の
ガスであれば何でもよいが最も容易に、かつ安価に供給
できるものとして空気が適当である。In the next oxidation step, any oxidizing gas may be used as the gas for oxidation, but air is suitable as it can be supplied most easily and inexpensively.
また、フェライト化を促進するために酸化温度は７０〜
９０°Ｃにするのが好ましい。In addition, in order to promote ferrite formation, the oxidation temperature is 70~
Preferably, the temperature is 90°C.
生成したフェライトを分離すると、分離後の濾液は、Ｎ
ａｚＳＯａ水溶液となる。When the generated ferrite is separated, the filtrate after separation is N
This becomes an azSOa aqueous solution.
フェライトを分離するには遠心分離等の通常の固液分離
方法が適用出来る。Normal solid-liquid separation methods such as centrifugation can be applied to separate ferrite.
また、磁気分離機を併用すれば、ＮａｚＳＯａ水溶液中
の３３分（金属酸化物）は１０ｐｐｍ以下にすることが
できる。Furthermore, if a magnetic separator is used in combination, the 33% (metal oxide) in the NazSOa aqueous solution can be reduced to 10 ppm or less.
得られたＮａ２ＳＯ４水溶液は、ｐｌ＋が約１０である
のでこれを硫酸で中和する。中和したＮａｚＳＯ，水溶
液は、そのまま、あるいは濃度調整した後、ルスナー電
解液として再使用できる。Since the obtained Na2SO4 aqueous solution has a pl+ of about 10, it is neutralized with sulfuric acid. The neutralized NazSO aqueous solution can be reused as a Lusner electrolyte as it is or after adjusting its concentration.
また、晶析装置で無水芒硝を晶析させ、晶析した結晶を
分離・乾燥して高品質の粉状無水芒硝とすることも可能
である。Furthermore, it is also possible to crystallize anhydrous sodium sulfate in a crystallizer, and then separate and dry the crystallized crystals to obtain high-quality powdered anhydrous sodium sulfate.
〈実施例〉 以下に第１図にしたがって実施例を示す。<Example> An example will be shown below with reference to FIG.
Ｌ 、Ｍｚ共にステンレスＦＩ酸洗廃液で６価クロム、
鉄、クロム、ニッケルを含むルスナー電解槽廃液り、と
鉄、クロム、ニッケルを含む硫酸廃液Ｍ ｚであり、こ
の雨水溶液Ｌ 、 Ｌをラインミキサーなどの混合器で
均一に混合する。調合、混合した水溶液は、中和槽１で
苛性ソーダ水溶液Ｓ、により水素イオン濃度１０立１に
中和する。中和水溶液は中和酸化槽２に送られる。中和
酸化槽２は、撹拌機付きの反応槽で複数からなり、直列
に構成されている。水素イオン濃度１０ｆｌに調整した
中和液を反応槽に連続供給し、複数の反応槽には２価鉄
イオン量に見合った空気Ｓ２を反応槽に供給して中和液
のフェライト化反応を進める。このフェライト化反応に
おいて適正な空気量、反応時間を与えることにより強磁
性フェライト（スピネル型フェライト）が生成する。第
１表に２価の鉄と６価クロムとの比（Ｆｅ”／Ｃｒ“）
を変えて試験じたときの初期条件を示した。Both L and Mz are hexavalent chromium with stainless steel FI pickling waste liquid,
The rainwater solutions L and L are uniformly mixed using a mixer such as a line mixer. The prepared and mixed aqueous solution is neutralized to a hydrogen ion concentration of 10:1 in a neutralization tank 1 with a caustic soda aqueous solution S. The neutralized aqueous solution is sent to the neutralization oxidation tank 2. The neutralization oxidation tank 2 is a reaction tank equipped with a stirrer and is composed of a plurality of reactors arranged in series. A neutralizing solution adjusted to a hydrogen ion concentration of 10 fl is continuously supplied to the reaction tank, and air S2 corresponding to the amount of divalent iron ions is supplied to the plurality of reaction tanks to advance the ferrite reaction of the neutralizing solution. . In this ferrite-forming reaction, ferromagnetic ferrite (spinel type ferrite) is produced by providing an appropriate amount of air and reaction time. Table 1 shows the ratio of divalent iron to hexavalent chromium (Fe"/Cr")
The initial conditions for testing with different values are shown below.
第１表
なお、中和酸化槽の撹拌機は４００ｒｐｃで回ビし、空
気吹込み量はｌｆ／ｍｉｎであり、水溶液は、温度が７
０°Ｃ１水素イオン深度が１０±１（Ｆｅ含有量が０．
１ ｍｏｌ ／ Ｅ ）になるように維持した。この条
件下での反応時間とＦｅ” 、 Ｃｒ”“、 Ｃｒ
“の総和量の変化との関係を第２図に示した。この結果
からＦｅ” 、 Ｃｒ” 、 Ｃｒ″の総和■が当初の
約半分に減少していることが明らかである。Table 1: The stirrer in the neutralization oxidation tank rotates at 400 rpm, the air blow rate is lf/min, and the aqueous solution has a temperature of 7.
0°C1 hydrogen ion depth is 10±1 (Fe content is 0.
1 mol/E). Reaction time under these conditions and Fe", Cr"", Cr
The relationship between changes in the total amount of "Fe", Cr", and Cr" is shown in FIG.
つぎに、フェライトスラリー溶液は、遠心分離機３によ
ってフェライトスラッジＰ、を排出する。Next, the ferrite slurry solution is used to discharge ferrite sludge P by a centrifuge 3.
その分離液は、磁気分離機の中を通過することによって
分離液中のフェライトは磁気吸着され、清澄液かえられ
る。When the separated liquid passes through a magnetic separator, the ferrite in the separated liquid is magnetically adsorbed, and the clarified liquid is changed.
この清澄液いａｒｓｏ４水溶液）は、水素イオン濃度が
１０±１であるがｐ ｌ ＨＪｉ整槽５で硫酸Ｓ、によ
り水素イオン濃度を７±０．５に調整する。水素イオン
濃度を７±０．５に調整されたＮａｚＳＯａ溶液は濃縮
装置６に送られ、ＮａｔｓＯｍ濃度が２０〜３０％にな
るまで濃縮される。この濃縮水溶液の一部を必要に応し
てステンレスｎ第１槽すなわちルスナー電解槽Ｐ。This clarified liquid (arso4 aqueous solution) has a hydrogen ion concentration of 10±1, but the hydrogen ion concentration is adjusted to 7±0.5 using sulfuric acid S in a p l HJi adjustment tank 5. The NazSOa solution whose hydrogen ion concentration has been adjusted to 7±0.5 is sent to the concentrator 6 and concentrated until the NatsOm concentration is 20 to 30%. A portion of this concentrated aqueous solution is transferred to the first stainless steel tank, ie, the Lussner electrolytic tank P, if necessary.
に供給する。また濃縮前の水溶液も補給水として一部を
ｐＨ調整槽５よりルスナー電解槽Ｐ３に供給される。余
剰の２５〜３０％Ｎａ２ＳＯ４水溶液からは、晶析装置
７において無水芒硝を晶析する。その結晶は、遠心分離
機８で分離され、乾燥機９で乾燥され高品質の粉状無水
芒硝Ｐ２がえられる。ＮａｚＳＯ４水溶液の濃縮、晶析
装置としては、蒸気を熱源として用いる多重効用蒸発缶
などがある。supply to. A portion of the aqueous solution before concentration is also supplied as make-up water from the pH adjustment tank 5 to the Rusner electrolytic cell P3. Anhydrous sodium sulfate is crystallized from the surplus 25-30% Na2SO4 aqueous solution in a crystallizer 7. The crystals are separated in a centrifuge 8 and dried in a dryer 9 to obtain high quality powdered anhydrous sodium sulfate P2. As an apparatus for concentrating and crystallizing NazSO4 aqueous solution, there is a multi-effect evaporator using steam as a heat source.
〈発明の効果〉
この発明の方法によると、従来投棄していたステンレス
鋼酸洗廃液から有害な６価クロム重金属を無害化しフェ
ライト（金属酸化物）を資源として回収することができ
、かつ分離液（Ｎａ、５Ｏａｔ９液）はステンレス鋼酸
洗ルスナー電解液として再利用でき、さらに余剰分離液
から無水芒硝を回収することができる。<Effects of the Invention> According to the method of the present invention, harmful hexavalent chromium heavy metals can be rendered harmless from the stainless steel pickling waste liquid that was conventionally disposed of, and ferrite (metal oxide) can be recovered as a resource, and the separated liquid can be (Na, 5Oat 9 solutions) can be reused as a stainless steel pickling Lusner electrolyte, and anhydrous sodium sulfate can be recovered from the excess separated solution.
第１図は、本発明にかかる発明方法の工程図、第２図は
、中和酸化槽における反応時間とＦｅ”＋Ｃｒ’◆、
Ｃｒ“の総和量との関係を示す特性図である。
１・・・中和槽、 ２・・・中和酸化槽、 ３・・・遠
心分離機、 ４・・・磁気分離機、 ５・・・ｐＨ調整
槽、６・・・濃縮装置、 ７・・・晶析装置、 ８・・
・遠心分離機、 ９・・・乾燥機、
Ｐ、・・・フェライト（金属酸化物）、 Ｐｔ・・・無
水芒硝、ＰＪ・・・ルスナー電解槽（中性塩溶ｉ）、Ｓ
ｌ・・・苛性ソーダ溶液、 Ｓ２・・・空 気、Ｓ、・
・・ｇ 酸
特許出願人 川＠製鉄株式会社
第 １ 図
第 ２ 図Fig. 1 is a process diagram of the inventive method according to the present invention, and Fig. 2 shows the reaction time in the neutralization oxidation tank and Fe''+Cr'◆,
It is a characteristic diagram showing the relationship with the total amount of Cr. 1... Neutralization tank, 2... Neutralization oxidation tank, 3... Centrifugal separator, 4... Magnetic separator, 5. ...pH adjustment tank, 6...concentrator, 7...crystallizer, 8...
・Centrifugal separator, 9...Dryer, P...Ferrite (metal oxide), Pt...Anhydrous mirabilite, PJ...Russner electrolytic cell (neutral salt solution I), S
l... Caustic soda solution, S2... Air, S,...
...g Acid patent applicant Kawa@Steel Co., Ltd. Figure 1 Figure 2
Claims (1)
スナー電解槽Ｎａ＿２ＳＯ＿４溶液に２価鉄／６価クロ
ムのモル比が５〜５０になるように硫酸第１鉄を添加し
、つぎにこれに苛性ソーダを添加し、ｐＨを１０±１に
調整し、空気などの酸化性ガスを吹き込んで酸化しフェ
ライトを生成させた後、このフェライトを分離、回収し
、さらに分離液としてＮａ＿２ＳＯ＿４溶液を回収する
ことを特徴とするルスナー電解槽廃液の処理方法。Ferrous sulfate is added to the Rusner electrolytic Na_2SO_4 solution containing hexavalent chromium generated in the pickling process of stainless steel so that the molar ratio of divalent iron/hexavalent chromium is 5 to 50, and then ferrous sulfate is added to this solution. Add caustic soda, adjust the pH to 10±1, blow in oxidizing gas such as air to oxidize and generate ferrite, then separate and collect this ferrite, and further collect Na_2SO_4 solution as a separated liquid. A method for treating Rusner electrolyzer waste liquid, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1829887A JPS63190696A (en) | 1987-01-30 | 1987-01-30 | Treatment of waste liquid of 'ruthener' electrolytic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1829887A JPS63190696A (en) | 1987-01-30 | 1987-01-30 | Treatment of waste liquid of 'ruthener' electrolytic cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63190696A true JPS63190696A (en) | 1988-08-08 |
Family
ID=11967702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1829887A Pending JPS63190696A (en) | 1987-01-30 | 1987-01-30 | Treatment of waste liquid of 'ruthener' electrolytic cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63190696A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006289336A (en) * | 2004-09-27 | 2006-10-26 | Mitsubishi Materials Corp | Apparatus for treating heavy metal-containing water |
| JP2008168289A (en) * | 2006-12-11 | 2008-07-24 | Sumitomo Metal Ind Ltd | Detoxification method of heavy metal-containing basic waste |
| JP2010042341A (en) * | 2008-08-11 | 2010-02-25 | Daiseki:Kk | Method for reducing amount of waste liquid and method for treating waste liquid |
-
1987
- 1987-01-30 JP JP1829887A patent/JPS63190696A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006289336A (en) * | 2004-09-27 | 2006-10-26 | Mitsubishi Materials Corp | Apparatus for treating heavy metal-containing water |
| JP2008168289A (en) * | 2006-12-11 | 2008-07-24 | Sumitomo Metal Ind Ltd | Detoxification method of heavy metal-containing basic waste |
| JP2010042341A (en) * | 2008-08-11 | 2010-02-25 | Daiseki:Kk | Method for reducing amount of waste liquid and method for treating waste liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106745076B (en) | A method of by the produced carnallite recycling of Industrial Wastewater Treatment | |
| CN109250857B (en) | Low-cost treatment method for ammonia nitrogen-containing wastewater of iron phosphate | |
| CN110272144B (en) | Treatment method of iron phosphate production wastewater | |
| CN110331288A (en) | A kind of method that waste lithium iron phosphate material selectivity mentions lithium | |
| CN109536720A (en) | The removal methods of chlorine in a kind of copper-bath | |
| CN108584901B (en) | Method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes | |
| JP6288217B1 (en) | Method and apparatus for treating wastewater containing sulfuric acid, fluorine and heavy metal ions | |
| WO2018072499A1 (en) | Method for recovering basic copper chloride from copper-containing waste liquid in sulfuric acid system | |
| CN107162276A (en) | A kind of method for removing chromium of ferric trichloride etching waste liquor | |
| CN105906129A (en) | Method for reutilization of water resources and transformation and utilization of salt in waste water | |
| CN112850679A (en) | Method for preparing iron phosphate by using waste acid | |
| JPS63190696A (en) | Treatment of waste liquid of 'ruthener' electrolytic cell | |
| CN107416863A (en) | The method that the waste water of ferric phosphate production prepares technical grade ammonium salt | |
| CN111424168A (en) | Water-washing dechlorination system and method for metallurgical precipitator dust | |
| US4104159A (en) | Method of separation of fluoride ion from water | |
| CA1094812A (en) | Preparation of ferric iron solutions | |
| JP4815082B2 (en) | Treatment method of iron-containing sulfuric acid solution | |
| US2618592A (en) | Electrolytic process for recovering by-products from industrial waste liquors | |
| JPH0369515A (en) | Method for recovering high-purity iron sulfate from waste sulfuric acid pickling solution for stainless steel | |
| JPS5858239A (en) | Manufacture of metallic gallium | |
| JP2000093739A (en) | Treatment of magnesium sulfate-containing wastewater | |
| JP2001137864A (en) | Method for treating waste water containing hydrofluoric acid | |
| JPH02124721A (en) | Production of chromium chloride | |
| CN104140126B (en) | The method of trimanganese tetroxide is produced with Resorcinol by product manganese water | |
| CN109775725A (en) | The processing method of Waste Sulfuric Acid in a kind of graphene production process |