JP3417615B2 - Production method of ternary roasting liquid - Google Patents
Production method of ternary roasting liquidInfo
- Publication number
- JP3417615B2 JP3417615B2 JP25131993A JP25131993A JP3417615B2 JP 3417615 B2 JP3417615 B2 JP 3417615B2 JP 25131993 A JP25131993 A JP 25131993A JP 25131993 A JP25131993 A JP 25131993A JP 3417615 B2 JP3417615 B2 JP 3417615B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- concentration
- roasting
- solution
- waste acid
- 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
- 239000007788 liquid Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 37
- 239000002699 waste material Substances 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 235000014413 iron hydroxide Nutrition 0.000 claims description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001035 Soft ferrite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 208000012287 Prolapse Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006196 drop Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Soft Magnetic Materials (AREA)
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、濃縮塔で濃縮した廃酸を濾過
・吸着して脱硅した後、脱硅廃酸に水を加えてＦｅＣｌ
2 換算濃度で３０〜３５％に濃度調整した後不純物除去
装置に移し、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て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・除去させると
共に、塩化第２鉄の還元を行い、引続き金属マンガンと
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に示すように濃縮塔１では鉄鋼の塩酸酸洗で発
生した塩化鉄水溶液を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２においてシリ
カが除去される。この脱硅廃酸は次工程の不純物除去装
置３のフィルター作業で温度低下し、塩化鉄が析出する
ので水を加えて濃度を３０％〜３５％に調整した後不純
物除去装置３に移し、この不純物除去装置３での廃酸中
に金属マンガンを加えて、廃酸中の塩酸と反応させ、ｐ
Ｈ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
時濃縮塔１で生成した塩化第２鉄も還元される。引続き
溶解調整槽４に移し金属マンガン、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。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】不純物を含んだＦｅＣｌ2 濃度２１％の廃酸
１３６２ｋｇは焙焼排ガスと濃縮塔で接触し、水分が蒸
発して濃縮される。この時、ＦｅＣｌ2 の一部はＦｅＣ
ｌ 3 に酸化され、排ガス中の塩酸の一部も溶液に移動す
る。引続き濃縮溶液を脱硅装置でシリカを除去する。脱
硅した濃縮廃酸は濃度が高く、精製工程の濾過時温度が
低下して析出するので、水を添加してＦｅＣｌ2 換算で
濃度約３５％にする。この廃酸に廃酸中の塩酸当量の５
倍の金属マンガン１８８．０ｋｇを投入した。その結
果、金属マンガンの１／５に当たる３７．６ｋｇは塩酸
及びＦｅＣｌ2と反応して、ＭｎＣｌ2 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、Ｆｅ
Ｃｌ2 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、本発明により完全に除去可能となった。
【０００９】この溶液を目標の溶液組成にするため、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３．９ｋｇ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。なおＺｎＣｌ2 溶液は溶解速度が遅いので別
のタンクで溶解した。このようにして製造されたＦｅＣ
ｌ2 ２７３．０ｋｇ，ＭｎＣｌ2 ９５．０ｋｇ，ＺｎＣ
ｌ2 ２８．０ｋｇ，ＨＣｌ２０．０ｋｇ，Ｈ2 Ｏ６６
１．６ｋｇから成る焙焼溶液１０７７．６ｋｇを焙焼炉
にて焙焼した結果、Ｆｅ2 Ｏ3 ７１％，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.
Removes phosphorus and heavy metals by co-precipitation with iron hydroxide
The amount of metal manganese added quantitatively
To improve productivity by dissolving in a short time and
This enables Ni removal. Summary of the invention
Ternary soft ferrite by solution roasting
Of waste acid concentrated in the concentration tower
・ After adsorption and desiliconization, add water to desiliconized waste acid to add FeCl
TwoImpurity removal after adjusting the concentration to 30-35% in reduced concentration
Transfer to the device and remove metallic manganese from the free acid equivalent of waste acid
Charge 10 times and react with hydrochloric acid in waste acid to make pH 3.5-
Adjusted to 5.0, co-precipitated with the produced iron hydroxide, phosphorus,
Precipitation and removal of heavy metals including silica and nickel
In both cases, ferric chloride is reduced, and metal manganese is
Add zinc chloride solution and hydrochloric acid to the specified ferrite composition
Adjusting the ternary roasting liquid.
You.
[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. 1, in the concentration tower 1, the steel is washed with hydrochloric acid and pickled.
The resulting aqueous solution of iron chloride is brought into contact with the roasting gas to reduce the concentration to about 20%.
After being concentrated from 40% to 40%,
Mosquito is removed. This desiliconized waste acid is used in the next process to remove impurities.
The temperature drops due to the filter operation in place 3, and iron chloride precipitates
So after adding water to adjust the concentration to 30% to 35%,
The waste acid is transferred to the waste removal device 3
Metal manganese, and react with hydrochloric acid in waste acid to obtain p
H is co-precipitated with the generated iron hydroxide and contained in waste acid
The phosphorus and heavy metals precipitate and are removed by filtration. That
The ferric chloride generated in the time concentration column 1 is also reduced. Continue
Transfer to dissolution adjusting tank 4 for metallic manganese, zinc chloride solution and salt
Adjust to the specified components by adding acid. The adjusted roasting liquid
Is converted into ternary oxide in the roasting furnace 5 and chlorine is converted into hydrochloric acid.
become. The roasting gas is concentrated after collecting the powder with the dust collector 6.
The heat is recovered by contact with the waste acid purified in the tower 7. Exhaust gas is salt
After removal of water as an aqueous hydrochloric acid solution in the acid absorption tower 8,
Remove harmful gas from hydrochloric acid tower and release to 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. Dissolution rate depends on iron addition
Metal manganese dissolves about 5 times faster than
Even if the free acid concentration is high, if the treatment time is long
Turned out not to be.
[0008]
DESCRIPTION OF THE PREFERRED EMBODIMENTS Impurity-containing FeClTwo21% concentration of waste acid
1362 kg contact the roasted exhaust gas with the concentration tower,
Emitted and concentrated. At this time, FeClTwoPart of is FeC
l ThreeAnd some of the hydrochloric acid in the exhaust gas also migrates to the solution.
You. Subsequently, silica is removed from the concentrated solution using a desiliconizer. Prolapse
The concentrated concentrated waste acid has a high concentration, and the temperature during filtration in the purification process is high.
As water drops and precipitates, water is added and FeClTwoIn conversion
Make the concentration about 35%. This waste acid has 5 equivalents of hydrochloric acid equivalent in waste acid.
188.0 kg of double metallic manganese was charged. The result
As a result, 37.6 kg, equivalent to 1/5 of metallic manganese, is hydrochloric acid
And FeClTwoReacts with MnClTwoAnd the rest
Did not change. In this state, the pH becomes about 4, and Fe
ClTwoAbout 5% of iron oxides precipitate as iron hydroxide etc.
Removed. Remove metal manganese from this solution using a strainer
And the precipitate was removed with a filter press or the like. This
The impurity concentration after filtration of the sediment at the time of
Diminished. In particular, Ni cannot be removed by conventional iron dissolution
Can be completely removed by the present invention.
In order to make this solution the target solution composition, gold
Genus manganese, ZnClTwoAdd solution and hydrochloric acid. This and
3.9 kg of metal manganese removed after purification
The rest is recycled for purification together with 41.5 kg of additional Mn.
used. Note that ZnClTwoSolution dissolves slowly, so separate
Was dissolved in the tank. FeC thus produced
lTwo273.0 kg, MnClTwo95.0 kg, ZnC
lTwo28.0 kg, HCl 20.0 kg, HTwoO66
A roasting furnace containing 1077.6 kg of a roasting solution consisting of 1.6 kg
As a result of roasting atTwoOThree71%, MnO 22%,
To obtain a ternary soft ferrite material with a composition of 7% ZnO
Was completed.
[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、７ 濃縮塔 ２ 脱硅装置 ３ 不純物除去装置 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] 1,7 Concentration tower 2 Silicon removal equipment 3 Impurity removal device 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 (1)
トを製造する溶液において、濃縮塔で濃縮した廃酸を濾
過・吸着して脱硅した後、脱硅廃酸に水を加えてＦｅＣ
ｌ2 換算濃度で３０〜３５％に濃度調整した後不純物除
去装置に移し、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て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・除去させ
ると共に、塩化第２鉄の還元を行い、引続き金属マンガ
ンと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。(57) [Claims] [Claim 1] In a solution for producing a ternary soft ferrite by a solution roasting method, a waste acid concentrated in a concentration tower is filtered and adsorbed, desiliconized, and then desiliconized. FeC by adding water to waste acid
After adjusting the concentration to 30 to 35% in terms of l 2 concentration, the mixture was transferred to an impurity removing device, and the metal manganese was reduced to 3 equivalents of the free acid equivalent in the waste acid.
10 to 10 times, and react with hydrochloric acid in waste acid to obtain pH 3.5
Adjusted to ~ 5.0, coprecipitated with the generated iron hydroxide to precipitate and remove heavy metals including phosphorus, silica and nickel, and reduced ferric chloride. And a method for producing a ternary roasting liquid, which comprises adjusting the ferrite composition to a predetermined ferrite composition by adding hydrochloric acid and hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25131993A JP3417615B2 (en) | 1993-10-07 | 1993-10-07 | Production method of ternary roasting liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25131993A JP3417615B2 (en) | 1993-10-07 | 1993-10-07 | Production method of ternary roasting liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07101729A JPH07101729A (en) | 1995-04-18 |
| JP3417615B2 true JP3417615B2 (en) | 2003-06-16 |
Family
ID=17221050
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25131993A Expired - Fee Related JP3417615B2 (en) | 1993-10-07 | 1993-10-07 | Production method of ternary roasting liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3417615B2 (en) |
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1993
- 1993-10-07 JP JP25131993A patent/JP3417615B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07101729A (en) | 1995-04-18 |
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