JP3417616B2

JP3417616B2 - Production method of ternary roasting liquid

Info

Publication number: JP3417616B2
Application number: JP25132093A
Authority: JP
Inventors: 芳隆山名; 善正池田; 捷成松崎; 惇二大森
Original assignee: TDK Corp
Current assignee: TDK Corp
Priority date: 1993-10-07
Filing date: 1993-10-07
Publication date: 2003-06-16
Anticipated expiration: 2018-06-16
Also published as: JPH07101730A

Description

【発明の詳細な説明】【０００１】【産業上の利用分野】本発明は溶液焙焼法による三元系
焙焼液の製造方法に関するものである。【０００２】【従来の技術】鉄鋼の塩酸酸洗で発生した廃酸中の塩化
鉄水溶液を焙焼して高性能なソフトフェライトを製造す
るためには、原料廃酸中のシリカ、リン及び重金属を除
去した原料溶液が必要である。そのためには従来では特
公昭６３−４９５５２号公報のように、原料廃酸を濃
縮、熟成した後脱硅装置で濾過及び吸着する方法が知ら
れている。また、リンや重金属を除去する方法として特
開昭６３−３１５５２２号公報、特開昭６３−３１５５
２３号公報及び特開昭６３−３１５５１９号公報があ
る。【０００３】すなわち、特開昭６３−３１５５２２号公
報のように塩酸酸洗廃液に鉄を加えて含有するＡｌ，Ｃ
ｒ，Ｃｕ，Ｐの大部分を不溶化物として一括して分別除
去する塩酸酸洗廃液の精製方法や特開昭６３−３１５５
２３号公報のように、塩化鉄溶液を焙焼ガスと接触させ
て加熱濃縮した塩化鉄水溶液中のＳｉ成分を不溶化さ
せ、次いで鉄を加えて液のｐＨを１〜３の範囲で遊離酸
を消費せしめて液中のＡｌ，Ｃｒ，Ｃｕ，Ｐ成分の大部
分を不溶化せしめ、不溶化物を分別除去する塩化鉄水溶
液の精製方法並びに特開昭６３−３１５５１９号公報の
ように、保温または加熱した塩化鉄水溶液に鉄を加えて
塩化鉄水溶液中のＡｌ，Ｃｒ，Ｃｕ，Ｐの大部分および
Ｓｉの一部分を含む不溶化物が十分に生成するのを待っ
て、これを分別する第１段の分別除去した後、液を焙焼
で生成した熱ガスと接触させて加熱・濃縮して液のＳｉ
の大部分を含む不溶化物が十分に生成するのを待って第
２段の分別除去を行い、その後焙焼して高純度の酸化鉄
粉を得る方法がある。【０００４】【発明が解決しようとする課題】上記したように、金属
鉄を溶解してｐＨを高くして発生する水酸化鉄と共沈し
てリン、重金属塔の不純物を除去する方法が示されてい
るが、しかし、このような方法で処理した廃酸を原料に
焙焼液を製造する方法は還元用に金属鉄が必要である。
しかも、廃酸に金属鉄を溶解させるには長時間を要する
ため、廃酸中の遊離酸濃度が高い場合には、溶解時間が
長くなり、処理量が減少するという問題がある。【０００５】【課題を解決するための手段】上述したような問題を解
消すべき、発明者らは鋭意研究を重ねた結果、金属鉄の
代わりに原料として使用する金属マンガンを使用するこ
とにより、水酸化鉄と共沈してリン及びニッケルを含む
重金属が除去出来ることを確認し、この金属マンガン添
加量を定量的に定めることにより、短時間溶解による生
産性の向上及びＮｉ除去を可能としたものである。その
発明の要旨とするところは、溶液焙焼法による三元系ソ
フトフェライトを製造する溶液において、不純物除去装
置に金属マンガンを廃酸中の遊離酸当量の３〜１０倍投
入し、廃酸中の塩酸と反応させ、ｐＨ３．５〜５．０に
調整し、生成する水酸化鉄と共沈して、リン、シリカ及
びニッケルを含む重金属を沈殿・除去し、引続き濃縮塔
で濃縮した廃酸を濾過・吸着して脱硅した後脱硅廃酸を
金属マンガンで塩化第２鉄の還元を行うと同時に塩化亜
鉛溶液及び塩酸を加えて所定のフェライト組成に調整す
ることを特徴とする三元系焙焼液の製造方法にある。【０００６】【作用】以下本発明について図面に従って詳細に説明す
る。図１は本発明に係る製造工程を示すフロー図であ
る。図１に示すように不純物除去装置１では鉄鋼の塩酸
酸洗で発生した塩化鉄水溶液を含む廃酸中に金属マンガ
ンを加えて、廃酸中の塩酸と反応させ、ｐＨを高め生成
した水酸化鉄と共沈して廃酸中に含有するリン及び重金
属を沈殿させフィルターで除去する。その後濃縮塔２で
廃酸は焙焼ガスと接触して濃度が約２０％から４０％に
濃縮された後、脱硅装置３においてシリカが除去され
る。引続き溶解調整槽４に移し、金属マンガンで濃縮塔
２で発生した塩化第２鉄を還元すると共に、塩化亜鉛溶
液及び塩酸を加えて所定の成分に調整する。その調整し
た焙焼液を焙焼炉５で塩化物が三元系酸化物になり、塩
素は塩酸になる。焙焼ガスは集塵機６で粉体を回収した
後、濃縮塔７で精製した廃酸と接触し熱を回収する。排
ガスは塩酸吸収塔８で水に塩酸水溶液として除去後、除
害塔９で塩酸塔の有害ガスを除去して大気に放散する。【０００７】このような製造工程において、本発明に係
る不純物除去条件としては、金属マンガンを廃酸中の遊
離酸当量の３〜１０倍添加する。好ましくは４〜６倍の
添加を行って溶液のｐＨを３．５〜５に調整して沈殿除
去するものである。この場合、金属マンガンの添加量が
多い方が溶液のｐＨは高くなり、水酸化鉄沈殿物は増加
する。しかし、沈殿物濾過後の不純物濃度は当量比で５
倍までは減少するがこれ以上では変化しない。また、所
定ｐＨに達するまでの時間は、当量比で１０倍までは減
少するが、それ以上では変化しない。更に溶解速度は鉄
添加に比べて金属マンガンの方が約５倍の速度で溶解
し、しかも遊離酸濃度が高い場合であっても処理時間は
長くならないことが判明した。【０００８】【実施例】不純物除去装置において不純物を含んだＦｅ
Ｃｌ₂濃度２１％の廃酸１３６２ｋｇに廃酸中の塩酸当
量の５倍の金属マンガン１１８．３ｋｇを投入した。そ
の結果、金属マンガンの１／５に当たる２３．７ｋｇは
塩酸と反応して、ＭｎＣｌ ₂になり、残りは変化しなか
った。この状態でｐＨは４程度となり、ＦｅＣｌ₂の５
％程度が水酸化鉄等となり沈殿し、不純物も除去され
た。この溶液から金属マンガンをストレナー等で分離
し、沈殿物はフィルタープレス等で除去した。このとき
の沈殿物濾過後の不純物濃度は表１に示すように減少し
た。特にＮｉは従来の鉄溶解では除去出来なかったもの
が、本発明により除去可能となった。【０００９】次いでこの溶液を焙焼排ガスと濃縮塔で接
触し、水分が蒸発して濃縮された。この時、ＦｅＣｌ₂
の一部はＦｅＣｌ₃に酸化され、排ガス中の塩酸の一部
も溶液に移動した。引続き濃縮溶液を脱硅装置でシリカ
を除去し、この溶液を目標の溶液組成にするため、及び
濃縮過程で生じたＦｅＣｌ₃を還元するため、金属マン
ガン、ＺｎＣｌ₂溶液及び塩酸を加える。このとき金属
マンガンは精製後除去した一部１７．８ｋｇを使用し、
残りは追加Ｍｎ４１．５ｋｇと共に精製用として再使用
した。このうち９．２ｋｇはＦｅＣｌ₃の還元に使用さ
れ、残りは塩酸と反応しＭｎＣｌ₂となった。なお、Ｚ
ｎＣｌ₂溶液は溶解速度が遅いので別タンクで溶解し
た。このようにして製造されたＦｅＣｌ₂２７３．０ｋ
ｇ，ＭｎＣｌ₂９５．０ｋｇ，ＺｎＣｌ₂２８．０ｋ
ｇ，ＨＣｌ３０．０ｋｇ，Ｈ₂Ｏ５７４．０ｋｇから成
る焙焼溶液１０００ｋｇを焙焼炉にて焙焼した結果、Ｆ
ｅ₂Ｏ ₃７１％，ＭｎＯ２２％，ＺｎＯ７％組成の三元
系ソフトフェライト原料を得ることが出来た。【００１０】【表１】【００１１】このように、焙焼液の原料に用いる金属マ
ンガンを用いることにより、溶解速度は従来の鉄に比較
して約５倍速く溶解可能と成り、廃酸中の不純物を短時
間で除去することが可能となった。特に廃酸中の遊離酸
濃度が高い場合には、従来の金属鉄溶解では溶解時間が
非常に長くなり、生産性を著しく低下させていたが、溶
解時間は殆ど変化しないで処理することが可能となっ
た。【００１２】【発明の効果】以上述べたように、本発明による焙焼液
の原料に用いる金属マンガンを用いて廃酸中の不純物を
除去することにより、極めて不純物の少ない焙焼液であ
る高純度の三元系ソフトフェライト原料を得ることが可
能となり、しかも溶解時間の短縮によって生産性が向上
し、特に廃酸中の遊離酸濃度が高い場合には、従来の金
属鉄溶解では長時間の溶解時間を要し、極めて作業性を
阻害していたものを、本発明によって濃度の高い場合で
も溶解時間は殆ど変化しないで処理することが可能とな
った。更には、従来ではＮｉの除去が不可能であったも
のが可能となる等工業上極めて優れた効果を奏するもの
である。DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ternary system by a solution roasting method.
The present invention relates to a method for producing a roasting liquid. [0002] 2. Description of the Related Art Chlorination in waste acid generated by hydrochloric acid pickling of steel
Roasting iron aqueous solution to produce high-performance soft ferrite
To remove silica, phosphorus and heavy metals from the raw material waste acid,
The removed raw material solution is required. For this purpose, the conventional
As disclosed in JP-B-63-49552, the raw material waste acid is concentrated.
Knows how to filter and adsorb by desiliconization after shrinking and aging.
Have been. It is also a special method for removing phosphorus and heavy metals.
JP-A-63-315522, JP-A-63-3155
No. 23 and JP-A-63-315519.
You. [0003] That is, JP-A-63-315522
As shown in the report, Al, C containing iron acid added to the hydrochloric acid pickling waste liquid
Most of r, Cu and P are collectively separated and insoluble as insoluble matter.
A method for purifying a hydrochloric acid pickling waste liquid to be removed and a method disclosed in JP-A-63-3155
As disclosed in JP-A No. 23, an iron chloride solution is brought into contact with a roasting gas.
To insolubilize the Si component in the aqueous solution of iron chloride concentrated by heating
And then add iron to adjust the pH of the solution to between 1 and 3 with free acid.
Al, Cr, Cu, P components in the liquid
Iron chloride solution to insolubilize and separate insolubles.
Liquid purification method and JP-A-63-315519.
Add iron to warm or heated aqueous iron chloride solution
Most of Al, Cr, Cu, P in iron chloride aqueous solution and
Wait until the insolubilized material containing a part of Si is sufficiently generated
And the liquid is roasted after the first stage of separation and removal.
The liquid Si is heated and concentrated by contact with the hot gas generated in
Wait until sufficient insolubilized material containing most of
Two-stage separation and removal, followed by roasting and high-purity iron oxide
There is a way to get the powder. [0004] As described above, as described above, metal
Dissolve iron and raise pH to co-precipitate with iron hydroxide generated
To remove phosphorus and heavy metal tower impurities.
However, waste acid treated in this way is used as a raw material.
The method for producing the roasting liquid requires metallic iron for reduction.
Moreover, it takes a long time to dissolve metallic iron in waste acid
Therefore, when the free acid concentration in the waste acid is high, the dissolution time
However, there is a problem that the processing time becomes longer and the processing amount decreases. [0005] SUMMARY OF THE INVENTION The above-mentioned problem is solved.
As a result of intensive research, the inventors have found that metallic iron
Instead, use metallic manganese, which is used as a raw material.
Contains phosphorus and nickel by co-precipitation with iron hydroxide
Confirm that heavy metals can be removed,
By quantitatively determining the amount added,
It is possible to improve productivity and remove Ni. That
The gist of the invention is that a ternary system by a solution roasting method is used.
In the solution for producing soft ferrite,
Metal manganese at a rate of 3 to 10 times the free acid equivalent in the waste acid.
And react with hydrochloric acid in waste acid to reach pH 3.5-5.0
Adjusted and co-precipitated with iron hydroxide to form, phosphorus, silica and
Precipitation and removal of heavy metals including nickel and nickel
Filtration, adsorption and desiliconization of waste acid concentrated in
Reduction of ferric chloride with metallic manganese
Add lead solution and hydrochloric acid to adjust the specified ferrite composition
And a method for producing a ternary roasting liquid. [0006] The present invention will be described below in detail with reference to the drawings.
You. FIG. 1 is a flowchart showing a manufacturing process according to the present invention.
You. As shown in FIG.
Metal manganese in waste acid containing aqueous solution of iron chloride generated by pickling
React with hydrochloric acid in waste acid to raise the pH and produce
And heavy metals contained in waste acid after co-precipitation with iron hydroxide
The genus is precipitated and removed with a filter. Then in the concentration tower 2
Waste acid is brought into contact with the roasting gas and the concentration is reduced from about 20% to 40%.
After being concentrated, the silica is removed in the desiliconizer 3.
You. Continue to dissolution adjustment tank 4 and concentrate with metal manganese
The ferric chloride generated in Step 2 is reduced and the zinc chloride
Adjust to the prescribed components by adding liquid and hydrochloric acid. That adjustment
Chloride is converted into a ternary oxide in the roasting furnace 5 by using
The element becomes hydrochloric acid. As for the roasting gas, the powder was collected by the dust collector 6.
Thereafter, the wastewater is brought into contact with the purified acid in the concentration tower 7 to recover heat. Exhaustion
The gas is removed as water solution of hydrochloric acid in water in hydrochloric acid absorption tower 8 and then removed.
The harmful gas in the hydrochloric acid tower is removed by the harmful tower 9 and released to the atmosphere. In such a manufacturing process, the present invention
The conditions for removing impurities are as follows.
Add 3 to 10 times the acid equivalent. Preferably 4 to 6 times
Addition is performed to adjust the pH of the solution to 3.5 to 5 to remove precipitate.
To leave. In this case, the addition amount of metallic manganese is
The higher the pH, the higher the pH of the solution and the more the iron hydroxide precipitate
I do. However, the impurity concentration after sediment filtration is 5
It decreases up to twice, but does not change any more. Also,
The time required to reach a constant pH is reduced by up to 10 times in equivalent ratio.
Less, but not more. Furthermore, the dissolution rate is iron
Metal manganese dissolves about 5 times faster than added
However, even when the free acid concentration is high, the treatment time is
It turned out not to be long. [0008] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In an impurity removing device, Fe containing impurities is used.
Cl_TwoTo 1362 kg of 21% waste acid, add hydrochloric acid in waste acid.
118.3 kg of metal manganese five times the amount was charged. So
As a result, 23.7 kg, which is 1/5 of metallic manganese,
Reacts with hydrochloric acid to produce MnCl _TwoAnd the rest will not change
Was. In this state, the pH becomes about 4 and FeCl_TwoOf 5
% Is precipitated as iron hydroxide etc., and impurities are also removed.
Was. Metal manganese is separated from this solution with a strainer
The precipitate was removed with a filter press or the like. At this time
The impurity concentration after filtration of the precipitate decreased as shown in Table 1.
Was. In particular, Ni cannot be removed by conventional iron dissolution
Can be removed by the present invention. Next, this solution is contacted with the roasted exhaust gas in a concentration tower.
Upon touch, the water was evaporated and concentrated. At this time, FeCl_Two
Is partly FeCl_ThreeOxidized to a part of hydrochloric acid in exhaust gas
Also moved into solution. Subsequently, the concentrated solution was silica
To remove the solution to the desired solution composition, and
FeCl generated during the concentration process_ThreeTo reduce the metal man
Gun, ZnCl_TwoAdd solution and hydrochloric acid. At this time metal
Manganese uses 17.8 kg of part removed after purification,
The rest is reused for purification together with 41.5 kg of additional Mn
did. 9.2 kg of this is FeCl_ThreeUsed to reduce
And the remainder reacts with hydrochloric acid to produce MnCl_TwoIt became. Note that Z
nCl_TwoThe solution dissolves in a separate tank due to the slow dissolution rate.
Was. FeCl thus produced_Two273.0k
g, MnCl_Two95.0 kg, ZnCl_Two28.0k
g, HCl 30.0 kg, H_TwoO574.0kg
As a result of roasting 1000 kg of the roasting solution in a roasting furnace,
e_TwoO _ThreeTernary composition of 71%, MnO 22%, ZnO 7%
A soft ferrite raw material was obtained. [0010] [Table 1] As described above, the metal mask used as the raw material for the roasting liquid is used.
Dissolution rate compared to conventional iron
About 5 times faster to dissolve impurities in waste acid
It became possible to remove between. Especially free acid in waste acid
When the concentration is high, the dissolution time is
It became very long and significantly reduced productivity.
Solution time can be processed with little change
Was. [0012] As described above, the roasting liquid according to the present invention
Of impurities in waste acid using metallic manganese used as raw material
By removing it, a roasting liquid with extremely few impurities can be obtained.
High purity ternary soft ferrite raw material
And improved productivity due to reduced dissolution time
Especially when the free acid concentration in the waste acid is high,
Metallic iron dissolution requires a long dissolution time and extremely workability
In the case of high concentration according to the present invention,
Can be treated with little change in dissolution time
Was. Further, conventionally, it has been impossible to remove Ni.
That have extremely excellent industrial effects, such as
It is.

【図面の簡単な説明】【図１】本発明に係る製造工程を示すフロー図である。【符号の説明】１不純物除去装置２、７濃縮塔３脱硅装置４溶解調整槽５焙焼炉６集塵機８塩酸吸収塔９除害塔[Brief description of the drawings] FIG. 1 is a flowchart showing a manufacturing process according to the present invention. [Explanation of symbols] 1 impurity removal equipment 2,7 Concentration tower 3 Silica removal equipment 4 Dissolution adjustment tank 5 Roasting furnace 6 dust collector 8 Hydrochloric acid absorption tower 9 detoxification tower

───────────────────────────────────────────────────── フロントページの続き (72)発明者大森惇二東京都千代田区大手町２−６−３新日本製鐵株式会社内 (56)参考文献特開平３−5324（ＪＰ，Ａ) 特開平３−40922（ＪＰ，Ａ) 特開平５−170453（ＪＰ，Ａ) 特公昭63−49552（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.⁷，ＤＢ名) C01G 49/00 ──────────────────────────────────────────────────続き Continued on the front page (72) Inventor Junji Omori 2-6-3 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Steel Corporation (56) References JP-A-3-5324 (JP, A) JP-A-3-40922 (JP, A) JP-A-5-170453 (JP, A) JP-B-63-49552 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01G 49/00

Claims

(57) [Claims 1] In a solution for producing a ternary soft ferrite by a solution roasting method, metal manganese is introduced into an impurity removing device at 3 to 10 times the free acid equivalent in waste acid. Then, it is reacted with hydrochloric acid in waste acid, adjusted to pH 3.5 to 5.0, co-precipitated with the produced iron hydroxide to precipitate and remove heavy metals including phosphorus, silica and nickel. After filtering and adsorbing the waste acid concentrated in step 1 and removing the silicon, the ferrous chloride is reduced with metal manganese, and the zinc oxide solution and hydrochloric acid are added to adjust the desired ferrite composition. A method for producing a ternary roasted liquid characterized by the above-mentioned.