JP3273901B2 - Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolved - Google Patents
Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolvedInfo
- Publication number
- JP3273901B2 JP3273901B2 JP12009797A JP12009797A JP3273901B2 JP 3273901 B2 JP3273901 B2 JP 3273901B2 JP 12009797 A JP12009797 A JP 12009797A JP 12009797 A JP12009797 A JP 12009797A JP 3273901 B2 JP3273901 B2 JP 3273901B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- waste liquid
- zinc
- sulfuric acid
- iron
- 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 - Fee Related
Links
Landscapes
- Removal Of Specific Substances (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、鉄鋼製品を溶融亜鉛
メッキする際に発生する不良品から、メッキ層を除去し
て鉄鋼製品を再利用するためあるいは亜鉛を回収するた
めに、メッキ層を塩酸で溶解した際等に発生する亜鉛と
鉄を含有する塩酸廃液の処理方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a method for removing a plating layer from defective products generated when hot-dip galvanizing a steel product, to remove the plating layer and reuse the steel product, or to recover zinc. The present invention relates to a method for treating a hydrochloric acid waste liquid containing zinc and iron generated when dissolved with hydrochloric acid.
【０００２】[0002]
【従来の技術】鉄鋼製品を溶融亜鉛メッキする際には、
それを溶融浴に浸漬するが、鉄鋼製品が大型の場合に
は、浸漬時に温度低下が起こることがあり、その結果不
良品が発生することを完全になくすことは困難であり、
その発生は避けられなかった。そのため従来から、この
不良品のメッキを塩酸で溶解して、大型鉄鋼製品を再利
用していた。その結果、亜鉛及び鉄を多量に溶解した塩
酸廃液が発生することになり、従来このような鉄及び亜
鉛を含有する塩酸廃液は、溶媒抽出法により処理され、
鉄及び亜鉛が回収されるか、あるいは中和法により処理
されていた。2. Description of the Related Art When galvanizing steel products,
It is immersed in a molten bath.If the steel product is large, the temperature may drop during immersion, and as a result, it is difficult to completely eliminate the occurrence of defective products.
Its occurrence was inevitable. For this reason, conventionally, plating of this defective product has been dissolved with hydrochloric acid, and large steel products have been reused. As a result, a hydrochloric acid waste liquid in which zinc and iron are dissolved in a large amount is generated, and such a hydrochloric acid waste liquid containing iron and zinc is conventionally treated by a solvent extraction method.
Iron and zinc were recovered or treated by a neutralization method.
【０００３】この内の溶媒抽出による方法は、有機溶媒
により亜鉛をまず抽出し、抽出残液から浮遊選別により
塩化第一鉄を分離するものである。抽出液は塩酸によっ
て逆抽出し、次いで硫酸を混合しながら遠心分離するこ
とによって硫酸亜鉛を回収するものである。この方法で
は抽出剤が有機溶剤であるから、コスト高及び取り扱い
時における安全性の問題があった。もう一つの中和法
は、塩酸廃液をアルカリで中和するものであり、その中
和には大量のアルカリが消費されただけでなく、中和の
結果水酸化物のスラッジが形成される。このスラッジ
は、鉄と亜鉛が混在することから、水分と分離しても有
効活用することができず、余儀なく投棄処理されること
になる。またスラッジ分離後の中和液も希釈後河川等に
放流されることになり、スラッジも中和液も環境汚染を
引き起こすことになり、望ましいものではなかった。[0003] Among them, a method by solvent extraction involves extracting zinc first with an organic solvent and separating ferrous chloride from the extraction residue by floating separation. The extract is back-extracted with hydrochloric acid, and then centrifuged while mixing sulfuric acid to recover zinc sulfate. In this method, since the extractant is an organic solvent, there are problems of high cost and safety during handling. Another neutralization method neutralizes hydrochloric acid waste liquid with an alkali, which not only consumes a large amount of alkali, but also forms a sludge of hydroxide as a result of the neutralization. Since the sludge is mixed with iron and zinc, it cannot be effectively used even if it is separated from water, and is forced to be discarded. Further, the neutralized liquid after sludge separation is also discharged to rivers and the like after dilution, and both sludge and neutralized liquid cause environmental pollution, which is not desirable.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本願発明者
は、このような問題のない、すなわち有機溶剤を使用す
ることもなく、また投棄処理による環境汚染の問題もな
い、亜鉛及び鉄を含有する塩酸廃液の処理技術を各方面
から検討し、開発を進めていた。その結果硫酸と全金属
量とを所定のモル比にして晶析を行うことにより鉄のみ
が析出することを見出し、塩酸廃液中から鉄と亜鉛を晶
析操作のみで分離し、両者を回収することができる塩酸
廃液の処理技術を開発し、この問題を解消したものであ
る。さらにこの技術では、塩酸を回収することも可能と
せしめており、その結果この塩酸は、不良メッキ鉄鋼製
品の亜鉛の溶解に再利用することができるものである。Therefore, the present inventor of the present invention has no problem with such a problem, that is, without using an organic solvent and with no problem of environmental pollution caused by dumping, containing zinc and iron. He studied the treatment technology of hydrochloric acid waste liquid from various fields and was developing it. As a result, it was found that only iron was precipitated by crystallization with a predetermined molar ratio of sulfuric acid and the total amount of metals, and iron and zinc were separated from the hydrochloric acid waste liquid only by the crystallization operation, and both were recovered. This problem has been solved by developing a technology for treating hydrochloric acid waste liquid that can perform this treatment. In addition, this technique also makes it possible to recover hydrochloric acid, so that this hydrochloric acid can be reused for dissolving zinc in poorly plated steel products.
【０００５】すなわち、この発明には、鉄および亜鉛を
溶存する塩酸廃液に硫酸と全金属とのモル比(SO4 /T-Me
tal)が１．５ないし４．０となるように濃硫酸を混合す
る工程、混合後の塩酸廃液を冷却して硫酸第一鉄を晶析
・分離する工程、硫酸第一鉄分離後の母液を蒸発濃縮す
る工程及び濃縮後の母液を冷却して硫酸亜鉛を晶析・分
離する工程からなる第１の発明と、鉄および亜鉛を溶存
する塩酸廃液に硫酸と全金属とのモル比(SO4 /T-Metal)
が１．５ないし４．０となるように硫酸を混合する工
程、混合後の廃液を蒸発濃縮する工程、濃縮後の塩酸廃
液を冷却して硫酸第一鉄を晶析・分離する工程、硫酸第
一鉄分離後の母液を蒸発濃縮する工程及び濃縮後の母液
を冷却して硫酸亜鉛を晶析・分離する工程からなる第２
の発明がある。この両発明のプロセスを図示すると、図
１及び図２のとおりである。またこの発明では、硫酸と
全金属とのモル比(SO4 /T-Metal)を１．５ないし４．０
とせしめることが最大の特徴であり、このことの存在に
より、鉄と亜鉛を晶析操作により分離することができる
のである。That is, according to the present invention, a molar ratio of sulfuric acid to all metals (SO 4 / T-Me) is added to a hydrochloric acid waste liquid in which iron and zinc are dissolved.
tal) is a step of mixing concentrated sulfuric acid so as to be 1.5 to 4.0, a step of cooling the mixed hydrochloric acid waste liquid to crystallize and separate ferrous sulfate, and a mother liquor after separating ferrous sulfate. Of the present invention, comprising a step of evaporating and concentrating the effluent and a step of cooling and cooling the mother liquor after concentration to crystallize and separate zinc sulfate, and the molar ratio (SO 4 / T-Metal)
Mixing sulfuric acid so that the pH is 1.5 to 4.0, evaporating and concentrating the waste liquid after mixing, cooling the concentrated hydrochloric acid waste liquid to crystallize and separate ferrous sulfate, A second step comprising evaporating and concentrating the mother liquor after ferrous iron separation, and cooling and cooling the concentrated mother liquor to crystallize and separate zinc sulfate.
Invention. FIGS. 1 and 2 illustrate the processes of the two inventions. Further, in the present invention, the molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) is 1.5 to 4.0.
The most important feature is that the iron and zinc can be separated by the crystallization operation.
【０００６】[0006]
【発明の実施の形態】この発明で処理対象とする塩酸廃
液は、例えば鉄鋼製品を溶融亜鉛メッキする際に発生す
る不良品から、メッキ層を塩酸で溶解した際に発生する
亜鉛と鉄を高濃度に含有する塩酸廃液であり、この塩酸
廃液の組成を分析すると表１に示すとおりである。処理
対象廃液は、ここに具体的に示されたものに限られるも
のではなく、鉄及び亜鉛を相当量含有するものであれ
ば、処理対象液となる。その濃度は、具体的には、鉄及
び亜鉛の濃度がそれぞれ２０〜１００ｇ／ｌ及び２０〜
１２０ｇ／ｌ程度である。なお、第１の発明では、最初
の工程である濃硫酸を混合する工程の後に、第２の発明
のように蒸発濃縮工程が存在しないので、濃硫酸混合後
硫酸第一鉄を晶析・分離する工程までの間で、廃液中の
鉄及び亜鉛の濃度を上昇せしめることができず、そのた
め両者の廃液中の濃度は、それぞれ８０〜１１０ｇ／ｌ
及び９０〜１２０ｇ／ｌ程度が好ましい。逆に第２の発
明では、前記したように硫酸混合後に蒸発濃縮工程が存
在するから、鉄及び亜鉛の濃度が第１の発明より希薄な
２０〜１００ｇ／ｌ（Ｆｅ）及び２０〜５０ｇ／ｌ（Ｚ
ｎ）のものでも処理可能である。BEST MODE FOR CARRYING OUT THE INVENTION The hydrochloric acid waste liquid to be treated in the present invention is, for example, a method for removing zinc and iron generated when a plating layer is dissolved with hydrochloric acid from defective products generated when hot-dip galvanizing steel products. It is the hydrochloric acid waste liquid contained in the concentration, and the composition of the hydrochloric acid waste liquid is analyzed, as shown in Table 1. The waste liquid to be treated is not limited to those specifically shown here, and is a liquid to be treated as long as it contains a considerable amount of iron and zinc. Specifically, the concentration of iron and zinc is 20 to 100 g / l and 20 to 100 g / l, respectively.
It is about 120 g / l. In the first invention, after the step of mixing concentrated sulfuric acid, which is the first step, there is no evaporative concentration step unlike the second invention, so that ferrous sulfate is crystallized and separated after mixing concentrated sulfuric acid. Until the process, the concentrations of iron and zinc in the waste liquid cannot be increased, so that the concentrations in both waste liquids are 80 to 110 g / l, respectively.
And about 90 to 120 g / l. Conversely, in the second invention, since the evaporative concentration step exists after the mixing of sulfuric acid as described above, the concentration of iron and zinc is 20 to 100 g / l (Fe) and 20 to 50 g / l, which are more dilute than the first invention. (Z
n) can also be processed.
【０００７】[0007]
【表１】 [Table 1]
【０００８】第１の発明においては、濃硫酸を混合する
工程で、硫酸と全金属とのモル比(SO4 /T-Metal)を１．
５ないし４．０とせしめることが最も重要であり、この
発明の最大の特徴点である。このモル比(SO4/T-Metal)
が１．５未満になると結晶中に塩化第一鉄が混在し、純
粋の硫酸第一鉄の結晶が得られなくなる。他方この比が
３．０を越え４．０になっても純粋の硫酸第一鉄結晶が
得られることを我々は確認しているが、この比が３．０
において鉄の大部分が結晶化し回収できるので、この確
認した４．０を上限とした。すなわち、これ以上の比で
硫酸を混合することは、必要以上に硫酸を使用し浪費す
るだけであり、実用性に欠けるので、上限を前記のとお
りとした。いずれにしても硫酸と全金属とのモル比を上
記の範囲すなわち１．５ないし４．０に維持することが
重要である。このように管理することにより、塩酸廃液
から亜鉛を同伴することなく、硫酸第一鉄のみを晶析で
き、亜鉛を分離できるのである。また、塩酸廃液に硫酸
を混合する第２の発明においても、このことは同様であ
り、硫酸と全金属とのモル比(SO4 /T-Metal)を１．５な
いし４．０とせしめることにより、塩酸廃液から亜鉛を
同伴することなく、硫酸第一鉄のみを晶析でき、亜鉛を
分離できるのである。この硫酸を混合する工程は、両発
明とも温度１０〜４０℃で実施するのがよく、好ましく
は２０〜４０℃で行うのがよい。なお、その際に使用す
る濃硫酸の濃度は６０〜９８重量％がよい。 In the first invention, in the step of mixing concentrated sulfuric acid, the molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) is set to 1.
It is most important to set the value to 5 to 4.0, which is the greatest feature of the present invention. This molar ratio (SO 4 / T-Metal)
Is less than 1.5, ferrous chloride is mixed in the crystal, and pure ferrous sulfate crystal cannot be obtained. On the other hand, we have confirmed that pure ferrous sulfate crystals can be obtained even when this ratio exceeds 3.0 and reaches 4.0, but this ratio is 3.0.
In this case, most of the iron crystallized and could be recovered. Therefore, the confirmed value of 4.0 was set as the upper limit. That is, mixing sulfuric acid at a ratio higher than this simply wastes the use of sulfuric acid more than necessary, and lacks practicality. Therefore, the upper limit is set as described above. In any case, it is important to maintain the molar ratio of sulfuric acid to all metals in the above range, ie, 1.5 to 4.0. By such management, only ferrous sulfate can be crystallized and zinc can be separated from the hydrochloric acid waste liquid without entraining zinc. The same applies to the second invention in which sulfuric acid is mixed with the hydrochloric acid waste liquid, and the molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) is set to 1.5 to 4.0. Thereby, only ferrous sulfate can be crystallized without entraining zinc from the hydrochloric acid waste liquid, and zinc can be separated. The step of mixing sulfuric acid is preferably carried out at a temperature of 10 to 40 ° C., and more preferably at a temperature of 20 to 40 ° C. in both inventions. In this case, use
The concentration of concentrated sulfuric acid is preferably 60 to 98% by weight.
【０００９】第１の発明における硫酸第一鉄を晶析・分
離する工程では、まず濃硫酸を混合した後の塩酸廃液を
冷却して温度低下させることにより、硫酸第一鉄結晶を
形成する。その際の冷却後の温度は０〜２０℃がよく、
好ましくは０〜５℃がよい。冷却速度は２〜１０℃／ｈ
程度がよく、好ましくは３〜５℃／ｈがよい。析出した
結晶の分離は各種の固液分離機が使用可能であるが、真
空濾過機あるいは遠心分離機が好ましい。In the step of crystallizing and separating ferrous sulfate according to the first invention, ferrous sulfate crystals are formed by cooling a hydrochloric acid waste liquid after mixing with concentrated sulfuric acid to lower the temperature. The temperature after cooling at that time is preferably 0 to 20 ° C,
Preferably, the temperature is 0 to 5 ° C. Cooling rate is 2-10 ° C / h
The degree is good, and preferably 3 to 5 ° C / h. Various solid-liquid separators can be used to separate the precipitated crystals, but a vacuum filter or a centrifuge is preferred.
【００１０】第１の発明における、硫酸第一鉄分離後の
母液を蒸発濃縮する工程の蒸発濃縮は、圧力４５〜１２
０ｍｍＨｇ、温度４０〜８０℃の減圧下で行うのがよ
く、好ましくは圧力４５〜７０ｍｍＨｇ、温度４０〜６
０℃で行うのがよい。蒸発した塩化水素含有水蒸気は凝
縮して塩酸として回収するが、その凝縮は約４０℃以下
の冷却液を使用するサーフェスコンデンサーを採用する
のが好ましい。回収した塩酸の濃度は１５〜３９重量％
程度である。その際の濃縮は、硫酸亜鉛の飽和溶液にな
るまで行うのが好ましいが、次の工程である硫酸亜鉛を
晶析・分離する工程において、廃液中の硫酸亜鉛がほぼ
全量晶析・分離できる程度であればよい。In the first invention, the step of evaporating and concentrating the mother liquor after the separation of ferrous sulfate is carried out under a pressure of 45 to 12 pressure.
It is preferably performed under reduced pressure of 0 mmHg and a temperature of 40 to 80 ° C., preferably 45 to 70 mmHg and a temperature of 40 to 6 ° C.
It is better to carry out at 0 ° C. The evaporated hydrogen chloride-containing steam is condensed and recovered as hydrochloric acid, and the condensation preferably employs a surface condenser using a cooling liquid of about 40 ° C. or less. The concentration of recovered hydrochloric acid is 15-39% by weight
It is about. Concentration at this time is preferably performed until a saturated solution of zinc sulfate is obtained.However, in the next step of crystallizing and separating zinc sulfate, zinc sulfate in the waste liquid can be crystallized and separated almost completely. Should be fine.
【００１１】第１の発明における硫酸亜鉛を晶析・分離
する工程では、晶析は濃縮後の溶液を冷却することによ
り行われ、その際の冷却温度は３５℃程度以下に冷却す
るのがよく、好ましくは２５℃以下に冷却するのがよ
い。また冷却速度は、３〜１０℃／ｈとするのがよい。
生成された結晶の分離には、各種の固液分離器が使用で
きるが、真空濾過機あるいは遠心分離機が好ましい。In the step of crystallizing and separating zinc sulfate in the first invention, the crystallization is performed by cooling the concentrated solution, and the cooling temperature at that time is preferably cooled to about 35 ° C. or less. The temperature is preferably cooled to 25 ° C. or less. The cooling rate is preferably 3 to 10 ° C / h.
Various solid-liquid separators can be used to separate the generated crystals, but a vacuum filter or a centrifuge is preferred.
【００１２】第２の発明の硫酸を混合する工程において
使用する硫酸は、この工程の後に蒸発濃縮する工程が存
在することから、低濃度５０％から濃硫酸まで使用可能
であるが、その際に使用する硫酸の濃度は６０〜９８重
量％がよい。また、第１の発明同様、この発明でも硫酸
と全金属とのモル比（ＳＯ4 ／Ｔ−Ｍｅｔａｌ）を１．
５ないし４．０とすることは勿論重要である。[0012] sulfuric acid used in the step of mixing the sulfuric acid in the second invention, since the step of evaporation after this step is present, it can be used from a low concentration of 50% to concentrated sulfuric acid, in the The concentration of sulfuric acid used is 60-98
Amount% is good . Also, as in the first invention, in this invention, the molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) is 1.
It is of course important to set the value to 5 to 4.0.
【００１３】第２の発明における混合後の廃液を蒸発濃
縮する工程における蒸発濃縮は、圧力４５〜１２０ｍｍ
Ｈｇ、温度４０〜８０℃の減圧下で行うのがよく、好ま
しくは圧力４５〜７０ｍｍＨｇ、温度４０〜６０℃で行
うのがよい。第２の発明における濃縮後の塩酸廃液を冷
却して硫酸第一鉄を晶析・分離する工程も、第１の発明
における塩酸廃液を冷却して硫酸第一鉄を晶析・分離す
る工程と同様に行う。In the second invention, the evaporation and concentration in the step of evaporating and condensing the waste liquid after mixing is performed at a pressure of 45 to 120 mm.
Hg is preferably carried out under reduced pressure at a temperature of 40 to 80 ° C, preferably at a pressure of 45 to 70 mmHg and a temperature of 40 to 60 ° C. The step of cooling the concentrated hydrochloric acid waste liquid in the second invention to crystallize and separate ferrous sulfate is also the step of cooling the hydrochloric acid waste liquid and crystallizing and separating ferrous sulfate in the first invention. Do the same.
【００１４】第２の発明における硫酸第一鉄分離後の母
液を蒸発濃縮する工程及び濃縮後の母液を冷却して硫酸
亜鉛を晶析・分離する工程は、第１の発明におけるそれ
らの場合と同様に行う。The step of evaporating and concentrating the mother liquor after ferrous sulfate separation in the second invention and the step of crystallizing and separating zinc sulfate by cooling the concentrated mother liquor are the same as those in the first invention. Do the same.
【００１５】[0015]
【実施例】この実施例では前記した表１に示す組成の塩
酸廃液を使用した。この廃液５００ｍｌに硫酸と全金属
とのモル比(SO4/T-Metal) を０から約３の間で変化さ
せ、生成した結晶及び分離後のろ液の組成を分析した。
その結果をそれぞれ表２及び表３に示すとともに、それ
ぞれ図３及び図４に図示した。これらのこと、特に表２
及び図３から、硫酸と全金属とのモル比(SO4 /T-Metal)
を１．５ないし３．０とせしめることにより、硫酸第一
鉄の結晶が形成されることがわかる。そしてその際に
は、硫酸亜鉛が同伴して析出してこないこともわかる。
特にこの比(SO4/T-Metal) が１前後では硫酸第一鉄では
なく、塩化第一鉄が形成されることがわかる。またその
際のろ液の組成はＳＯ4 ／Ｔ−Ｍｅｔａｌが増加するに
従い、ろ液中のＳＯ4 の量が次第に増加することがわか
る。ろ液中の鉄(Fe)の量は、(SO4/T-Metal) が２以上に
なると極めて少なくなり、ほとんどが硫酸第一鉄結晶と
して析出してくることがわかる。なお図３には図示され
ていないが、我々はこのモル比が４．０においても硫酸
第一鉄結晶が析出することを確認している。EXAMPLE In this example, a hydrochloric acid waste liquid having the composition shown in Table 1 was used. The molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) was varied from 0 to about 3 in 500 ml of the waste liquid, and the composition of the generated crystals and the filtrate after separation were analyzed.
The results are shown in Tables 2 and 3, respectively, and are also shown in FIGS. 3 and 4, respectively. These things, especially Table 2
From FIG. 3 and FIG. 3, the molar ratio of sulfuric acid to all metals (SO 4 / T-Metal)
From 1.5 to 3.0, it can be seen that ferrous sulfate crystals are formed. At that time, it is also understood that zinc sulfate does not accompany and precipitate.
In particular, when the ratio (SO 4 / T-Metal) is about 1, not ferrous sulfate but ferrous chloride is formed. In addition, it can be seen that the composition of the filtrate at that time gradually increases the amount of SO 4 in the filtrate as SO 4 / T-Metal increases. It can be seen that the amount of iron (Fe) in the filtrate becomes extremely small when (SO 4 / T-Metal) is 2 or more, and almost all precipitates as ferrous sulfate crystals. Although not shown in FIG. 3, we have confirmed that ferrous sulfate crystals precipitate even at this molar ratio of 4.0.
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 [Table 3]
【００１７】[0017]
【発明の効果】この発明では、従来法の溶媒抽出による
方法のように有機溶媒を使用することに伴うコスト面及
び取り扱い時の安全性の問題もなく、またもう一つの中
和法のように、処理後の排出されるスラッジ及び中和液
による環境汚染を心配する問題もない優れた塩酸廃液の
処理方法を提供するものである。According to the present invention, there is no problem in terms of cost and safety in handling due to the use of an organic solvent as in the conventional method by solvent extraction, and there is also a problem in another neutralization method. Another object of the present invention is to provide an excellent method for treating hydrochloric acid waste liquid without having to worry about environmental pollution due to sludge and neutralized liquid discharged after treatment.
【００２６】[0026]
【図面の簡単な説明】[Brief description of the drawings]
【図１】この図は、第１の発明の廃液処理のフローロー
図である。FIG. 1 is a flow chart of waste liquid treatment of the first invention.
【図２】この図は、第２の発明の廃液処理のフローロー
図である。FIG. 2 is a flow chart of the waste liquid treatment of the second invention.
【図３】この図は、硫酸添加量と形成された結晶の組成
との関係を示す図である。FIG. 3 is a diagram showing the relationship between the amount of sulfuric acid added and the composition of formed crystals.
【図４】この図は、硫酸添加量とろ液の組成との関係を
示す図である。FIG. 4 is a diagram showing the relationship between the amount of sulfuric acid added and the composition of the filtrate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 折笠 実 東京都西多摩郡日の出町平井字欠下２番 １号 日鉄鉱業株式会社内 (72)発明者 桂 洋介 東京都西多摩郡日の出町平井字欠下２番 １号 日鉄鉱業株式会社内 (56)参考文献 特開 平３−5327（ＪＰ，Ａ) 特開 昭59−137302（ＪＰ，Ａ) 特開 平５−17160（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 25/00 - 57/00 C01G 9/06 ＷＰＩ（ＤＩＡＬＯＧ)──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Orikasa No. 2 in Hirai-cho, Hinodecho, Nishitama-gun, Tokyo Nippon Mining Co., Ltd. (72) Inventor Yosuke Katsura No. 2-1 below Nippon Steel Mining Co., Ltd. (56) References JP-A-3-5327 (JP, A) JP-A-59-137302 (JP, A) JP-A-5-17160 (JP, A) ( 58) Field surveyed (Int. Cl. 7 , DB name) C01G 25/00-57/00 C01G 9/06 WPI (DIALOG)
Claims (5)
と全金属とのモル比（ＳＯ4 ／Ｔ−Ｍｅｔａｌ）が１．
５ないし４．０となるように濃硫酸を混合する工程、混
合後の塩酸廃液を冷却して硫酸第一鉄を晶析・分離する
工程、硫酸第一鉄分離後の母液を蒸発濃縮する工程及び
濃縮後の母液を冷却して硫酸亜鉛を晶析・分離する工程
からなる鉄及び亜鉛を溶存する塩酸廃液の処理方法。1. A hydrochloric acid waste solution in which iron and zinc are dissolved has a molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) of 1.
A step of mixing concentrated sulfuric acid to 5 to 4.0, a step of cooling the mixed hydrochloric acid waste liquid to crystallize and separate ferrous sulfate, and a step of evaporating and concentrating the mother liquor after separating ferrous sulfate. And a step of cooling the concentrated mother liquor to crystallize and separate zinc sulfate, and a method for treating a hydrochloric acid waste liquid in which iron and zinc are dissolved.
と全金属とのモル比（ＳＯ4 ／Ｔ−Ｍｅｔａｌ）が１．
５ないし４．０となるように硫酸を混合する工程、混合
後の廃液を蒸発濃縮する工程、濃縮後の塩酸廃液を冷却
して硫酸第一鉄を晶析・分離する工程、硫酸第一鉄分離
後の母液を蒸発濃縮する工程、濃縮後の母液を冷却して
硫酸亜鉛を晶析・分離する工程からなる鉄及び亜鉛を溶
存する塩酸廃液の処理方法。2. The hydrochloric acid waste solution in which iron and zinc are dissolved has a molar ratio of sulfuric acid to all metals (SO 4 / T-Metal) of 1.
Mixing sulfuric acid to 5 to 4.0, evaporating and concentrating the waste liquid after mixing, cooling the concentrated hydrochloric acid waste liquid to crystallize and separate ferrous sulfate, ferrous sulfate A method for treating hydrochloric acid waste liquor in which iron and zinc are dissolved, comprising a step of evaporating and concentrating the separated mother liquor and a step of cooling and cooling the concentrated mother liquor to crystallize and separate zinc sulfate.
る工程において、使用する硫酸濃度を６０〜９８重量％
とせしめる請求項１又は２記載の塩酸廃液の処理方法。3. A step of mixing concentrated sulfuric acid or mixing sulfuric acid.
The concentration of sulfuric acid used is 60 to 98% by weight.
The method for treating a hydrochloric acid waste liquid according to claim 1 or 2, wherein the treatment is performed.
工程における、蒸発濃縮を温度６０〜８０℃、圧力４５
〜１２０ｍｍＨｇの減圧下で行う請求項１ないし３のい
ずれか１に記載の塩酸廃液の処理方法。4. In the step of evaporating and concentrating the mother liquor after the separation of ferrous sulfate, the evaporating and concentrating is performed at a temperature of 60 to 80 ° C. and a pressure of 45.
The method for treating hydrochloric acid waste liquid according to any one of claims 1 to 3, wherein the method is performed under a reduced pressure of 120 to 120 mmHg.
工程において、蒸発した塩化水素含有水蒸気を凝縮して
塩酸を回収する請求項１ないし４のいずれか１に記載の
塩酸廃液の処理方法。5. The treatment of hydrochloric acid waste liquid according to claim 1, wherein in the step of evaporating and concentrating the mother liquor after the separation of ferrous sulfate, the evaporated hydrogen chloride-containing steam is condensed to recover hydrochloric acid. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12009797A JP3273901B2 (en) | 1997-04-24 | 1997-04-24 | Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolved |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12009797A JP3273901B2 (en) | 1997-04-24 | 1997-04-24 | Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolved |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10297926A JPH10297926A (en) | 1998-11-10 |
| JP3273901B2 true JP3273901B2 (en) | 2002-04-15 |
Family
ID=14777847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12009797A Expired - Fee Related JP3273901B2 (en) | 1997-04-24 | 1997-04-24 | Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolved |
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| Country | Link |
|---|---|
| JP (1) | JP3273901B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100881122B1 (en) | 2007-11-21 | 2009-02-02 | 경남정보대학 산학협력단 | Process for manufacturing of high quality zinc sulfate from waste liquor of uv stabilizer manufacturing processes |
| CN103539302B (en) * | 2013-10-31 | 2015-04-22 | 惠州市斯瑞尔环境化工有限公司 | Treatment method of zinc-containing and iron-containing waste acid |
| CN104313320B (en) * | 2014-10-23 | 2017-04-05 | 云南煜锜环保科技有限公司 | The strong acid saturated crystallization separation method of zinc-magnesium in a kind of zinc electrolyte |
| CN108085489B (en) * | 2017-11-17 | 2019-06-07 | 昆明理工大学 | A kind of method that ferrous sulfate is precipitated in the crystallization of zinc hydrometallurgy solution |
-
1997
- 1997-04-24 JP JP12009797A patent/JP3273901B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10297926A (en) | 1998-11-10 |
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