JP3972996B2 - Method for purifying ferrous iron-containing solution - Google Patents
Method for purifying ferrous iron-containing solution Download PDFInfo
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- JP3972996B2 JP3972996B2 JP23753493A JP23753493A JP3972996B2 JP 3972996 B2 JP3972996 B2 JP 3972996B2 JP 23753493 A JP23753493 A JP 23753493A JP 23753493 A JP23753493 A JP 23753493A JP 3972996 B2 JP3972996 B2 JP 3972996B2
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- 238000000034 method Methods 0.000 title claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 9
- 239000002253 acid Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910001035 Soft ferrite Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 31
- 238000000746 purification Methods 0.000 description 15
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compounds Of Iron (AREA)
- Soft Magnetic Materials (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、金属塩溶液を噴霧焙焼してフェライト原料粉体を製造する際の原料の金属塩溶液の精製に関するものである。
【０００２】
【従来の技術】
従来の第１鉄含有溶液の精製方法としては特開平３−５３２４号公報に示されているように、塩化第１鉄水溶液を鉄または鉄化合物で遊離塩酸を中和してｐＨを２〜５に調整した後酸素もしくは酸素含有気体と接触させて溶液中の鉄分の０．５〜１５％を含水酸化第２鉄を主成分とする沈殿物に酸化させ、この沈殿物を分離し、精製塩化第１鉄水溶液とした後、高温焙焼するフェライト原料用酸化鉄の製造方法が知られている。
【０００３】
【発明が解決しようとする課題】
上述した特開平３−５３２４号公報にあっては、溶液中に金属鉄や鉄化合物を投入して溶液中の遊離酸を減少させて水酸化第２鉄を生成させ、不純物をこれに吸着させ沈殿除去する方法であるが、この方法は、金属塩や鉄化合物の溶解速度が大きくないため、溶液中の遊離酸を減少させるのに時間を要し、溶液中の塩酸量が多ければ多い程、本工程に要する時間が長くなり液製造の生産性を低下させていた。また、多成分溶液を製造する場合は、溶液を構成する金属（例えば金属Ｍｎ）で鉄よりも溶解速度の大きなものを投入して遊離酸の減少時間を短縮する方法があるが、その効果は数割程度のものでしかないため、ｐＨ調整に極めて時間を要するという問題がある。
【０００４】
【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るべく、発明者らは鋭意開発を進めた結果、遊離酸を減少させるために、初めに成品であり、しかも比表面積が５〜２５ｍ2 ／ｇと大きいソフトフェライト原料粉体を投入することにより短時間にてｐＨ１．０〜２．０に上げた後、再度ｐＨ調整する溶液の精製方法を提供せんとするものである。
その発明の要旨とするところは、溶液焙焼法によりＭｎＯ、ＺｎＯおよびＦｅ 2 Ｏ 3 を含むソフトフェライト原料粉体を製造する工程において、原料溶液となる第１鉄を含む多成分金属塩の酸溶液を精製するに際し、予め溶液中に比表面積５〜２５ｍ 2 ／ｇのソフトフェライト原料粉体を投入することで短時間で遊離酸を減少させてｐＨ１．０〜２．０に上げた後、Ｍｎ金属の投入により、更に遊離酸を減少させてｐＨ２．０〜５．０に調整すると共に、酸素含有気体と接触させることで生成する鉄の酸化物に不純物を吸着させ、これを濾過することで不純物を効率良く除去することを特徴とする第１鉄含有溶液の精製方法にある。
【０００５】
【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は本発明に係る金属塩溶液の精製工程図である。図１に示すように、先ず塩化鉄溶液をｐＨ調整槽１内に投入し、引き続いてフェライト原料粉体を投入して、攪拌混合させ塩化鉄溶液中の遊離酸を減少させｐＨを１．０〜２．０に上げた後、精製槽２に溶液を移送し、そこにＭｎ金属を投入して、更に遊離酸を減少させてｐＨを２．０〜５．０に調整すると共に、精製槽２内に酸素含有気体を投入し、鉄の酸化物を生成させ、それに不純物を吸着し、引続き精製槽２より粗いフィルター３を通し、未溶解Ｍｎを除去した後、フィルタープレス４に送り、一方除去した未溶解Ｍｎは再度ｐＨ調整槽１に送り、Ｍｎ液として再使用する。また、フィルタープレス４内で不純物を除去して精製塩化鉄溶液として成分調整槽５へ送り込み、ＭｎやＺｎの多成分系溶液を構成する成分を投入して、原料溶液を製造し、その後焙焼炉６で溶液を噴霧焙焼して成品であるソフトフェライト原料粉体を製造する。一方、成品の一部はｐＨ調整槽１に送り、遊離酸を減少させてソフトフェライト原料粉体として使用する。
【０００６】
このように塩化鉄溶液中の遊離酸を減少させるために、初めに比表面積の大きい粉状成品のソフトフェライト原料粉体を使用することから、最初から溶液を構成する金属等を投入する方法に比べて、極めて短時間で溶解することが可能となり、精製時間を大幅に短縮することが出来るもので、これにより、短時間で第１鉄含有多成分金属塩溶液を精製することが出来るものである。
【０００７】
【実施例】
表１に示すような組成をもつ７０℃の精製前塩化鉄溶液に、同じく表１のような組成をもつ平均比表面積２０ｍ2 ／ｇのソフトフェライト原料粉体をＨＣｌモル濃度で３倍に当たる量をｐＨ調整槽内で投入し、攪拌してｐＨを１．６に調整した後、精製槽に移送し、次いでＭｎ（粗いフィルターより生ずる未溶解Ｍｎを含めたもの）をＨＣｌモル濃度の５倍に当たる量について投入してｐＨを４．０に調整すると共に、酸素含有気体と接触させ生成する鉄の酸化物に不純物を吸着させ、その後粗いフィルターに掛けて未溶解Ｍｎを除去し、引続きフィルタープレスに掛けて不純物を除去した精製後の塩化鉄含有溶液の成分組成は表２の通りであり、不純物が良く除去させていることが判る。一方、ソフトフェライト原料粉体によりｐＨを１．６にするまでに要した時間は２０分であり、次にＭｎによりｐＨを４．０にするまでに要した時間は５０分であり、ｐＨ調整に要した時間は計７０分であった。
【０００８】
【表１】
【表２】
【比較例】
実施例で述べた７０℃の精製前塩化鉄溶液に、Ｆｅ（製鉄所内で発生する冷延鋼板のスクラップ）をＨＣｌモル濃度で１０倍に当たる量を精製槽内で投入して、ｐＨを４．０に調整すると共に、酸素含有気体と接触させ生成する鉄の酸化物に不純物を共に吸着させ、その後粗いフィルター及びフィルタープレスに掛けて不純物を除去した精製後の塩化鉄含有溶液の成分組成は表２の比較例１の通りである。このときｐＨ調整には５００分を要した。またｐＨ調整を７０分で中断して精製したときの結果を比較例２に示したが未だ不純物が多く残っていることが判る。
【００１１】
これによって、従来塩化鉄溶液の遊離酸の多い場合には、約８ｈｒの溶解時間かかっていたものが、ソフトフェライト原料粉体を使用することによって、約１時間の短時間で遊離酸を減少させることが出来る第１鉄含有多成分金属溶液を精製することが出来た。
【００１２】
【発明の効果】
以上述べたように、本発明を実施することによって、従来のような初めから粒状の金属を大量に投入して遊離酸を減少させる方法に比べて、最初の大量の投入物は粉体であることから、極めて短時間で溶解することが可能となり、よって精製時間が大幅に短縮され、しかも、その後に粒状の金属を少量だけ投入すれば良いため投入及び溶解操作が容易となる等工業上極めて優れた効果を奏するものである。
【図面の簡単な説明】
【図１】本発明に係る金属塩溶液の精製工程図である。
【符号の説明】
１ ｐＨ調整槽
２ 精製槽
３ 粗フィルター
４ フィルタープレス
５ 成分調整槽
６ 焙焼炉
７ 集塵機[0001]
[Industrial application fields]
The present invention relates to purification of a raw metal salt solution when a ferrite raw material powder is produced by spray roasting of a metal salt solution.
[0002]
[Prior art]
As a conventional method for purifying a ferrous iron-containing solution, as disclosed in Japanese Patent Laid-Open No. 3-5324, an aqueous ferrous chloride solution is neutralized with free hydrochloric acid with iron or an iron compound to adjust the pH to 2-5. After being adjusted to 0, it is brought into contact with oxygen or an oxygen-containing gas to oxidize 0.5 to 15% of iron in the solution to a precipitate containing hydrous ferric oxide as a main component. There is known a method for producing iron oxide for ferrite raw material which is made into a ferrous aqueous solution and then roasted at a high temperature.
[0003]
[Problems to be solved by the invention]
In the above-mentioned Japanese Patent Laid-Open No. 3-5324, metallic iron or an iron compound is introduced into a solution to reduce the free acid in the solution to produce ferric hydroxide, and the impurities are adsorbed thereto. This is a method of removing precipitates, but this method does not have a high dissolution rate of metal salts and iron compounds, so it takes time to reduce the free acid in the solution. The more hydrochloric acid in the solution, the more As a result, the time required for this step is increased and the productivity of the liquid production is reduced. In the case of producing a multi-component solution, there is a method of shortening the reduction time of free acid by introducing a metal constituting the solution (for example, metal Mn) having a dissolution rate larger than that of iron. Since it is only about a few percent, there is a problem that it takes a very long time to adjust the pH.
[0004]
[Means for Solving the Problems]
To solve the problems described above, inventors have conducted intensive result of developing, in order to reduce the free acid, a finished product initially, yet soft large specific surface area and 5~25m 2 / g starting ferrite It is intended to provide a method for purifying a solution in which the pH is adjusted to 1.0 to 2.0 in a short time by adding powder and then the pH is adjusted again.
The gist of the invention is that an acid of a multicomponent metal salt containing ferrous iron that becomes a raw material solution in a process of producing a soft ferrite raw material powder containing MnO, ZnO and Fe 2 O 3 by a solution roasting method. In refining the solution, the soft acid raw material powder having a specific surface area of 5 to 25 m 2 / g was previously introduced into the solution to reduce the free acid in a short time and raise the pH to 1.0 to 2.0. By adding Mn metal, the free acid is further reduced to adjust the pH to 2.0 to 5.0, and impurities are adsorbed on the iron oxide produced by contacting with oxygen-containing gas, and this is filtered. The method for purifying a ferrous iron-containing solution is characterized in that impurities are efficiently removed.
[0005]
[Action]
Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a purification process diagram of a metal salt solution according to the present invention. As shown in FIG. 1, first, an iron chloride solution is introduced into the pH adjusting tank 1, and subsequently, ferrite raw material powder is introduced and mixed by stirring to reduce the free acid in the iron chloride solution to a pH of 1.0. After raising the pH to ~ 2.0, the solution is transferred to the purification tank 2, Mn metal is added thereto, the free acid is further reduced to adjust the pH to 2.0 to 5.0, and the purification tank 2, an oxygen-containing gas is introduced to produce iron oxide, and impurities are adsorbed thereto, and after passing through a coarse filter 3 from the purification tank 2 to remove undissolved Mn, it is sent to the filter press 4. The removed undissolved Mn is sent again to the pH adjusting tank 1 and reused as a Mn solution. Moreover, impurities are removed in the filter press 4 and sent to the component adjustment tank 5 as a purified iron chloride solution, and components constituting a multicomponent solution of Mn and Zn are introduced to produce a raw material solution, followed by roasting The solution is spray roasted in a furnace 6 to produce a soft ferrite raw material powder as a product. On the other hand, a part of the product is sent to the pH adjusting tank 1 to reduce the free acid and used as a soft ferrite raw material powder.
[0006]
In this way, in order to reduce the free acid in the iron chloride solution, since the powdered soft ferrite raw material powder having a large specific surface area is first used, the metal constituting the solution is introduced from the beginning. In comparison, it can be dissolved in a very short time, and the purification time can be greatly shortened. By this, a ferrous iron-containing multicomponent metal salt solution can be purified in a short time. is there.
[0007]
【Example】
The amount of soft ferrite raw material powder having an average specific surface area of 20 m 2 / g having the composition as shown in Table 1 and the molar ratio of HCl being tripled in a 70 ° C. pre-purification iron chloride solution having the composition shown in Table 1. Was added to the pH adjustment tank, stirred to adjust the pH to 1.6, transferred to the purification tank, and then Mn (including undissolved Mn produced from the coarse filter) was 5 times the HCl molar concentration. In addition, the pH is adjusted to 4.0 by contacting with an oxygen-containing gas and impurities are adsorbed to the generated iron oxide, and then applied to a coarse filter to remove undissolved Mn. The component composition of the iron chloride-containing solution after purification after removing impurities by applying is as shown in Table 2, and it can be seen that the impurities are well removed. On the other hand, the time required to set the pH to 1.6 with the soft ferrite raw material powder is 20 minutes, and the time required to set the pH to 4.0 with Mn is 50 minutes. It took 70 minutes in total.
[0008]
[Table 1]
[Table 2]
[Comparative example]
An amount equivalent to 10 times the HCl molar concentration of Fe (scrap of cold-rolled steel sheet generated in the steelworks) was added to the pre-purification iron chloride solution at 70 ° C. described in the examples in the purification tank to adjust the pH to 4. The composition of the iron chloride-containing solution after purification was adjusted to 0, adsorbed together with the iron oxide produced by contacting with an oxygen-containing gas, and then subjected to a coarse filter and filter press to remove the impurities. 2 as Comparative Example 1. At this time, pH adjustment took 500 minutes. Moreover, although the result when it refine | purifies by interrupting pH adjustment in 70 minutes was shown in the comparative example 2, it turns out that many impurities still remain.
[0011]
As a result, when the amount of free acid in the conventional iron chloride solution is large, the amount of free acid can be reduced in a short time of about 1 hour by using soft ferrite raw material powder, which took about 8 hours of dissolution time. It was possible to purify a ferrous iron-containing multicomponent metal solution.
[0012]
【The invention's effect】
As described above, by carrying out the present invention, compared with the conventional method in which a large amount of granular metal is added from the beginning to reduce free acid, the first large amount of input is a powder. Therefore, it is possible to dissolve in an extremely short time, and thus the purification time is greatly shortened. Moreover, since only a small amount of granular metal needs to be added thereafter, the charging and dissolving operation is facilitated. It has an excellent effect.
[Brief description of the drawings]
FIG. 1 is a purification process diagram of a metal salt solution according to the present invention.
[Explanation of symbols]
1 pH adjustment tank 2 Purification tank 3 Coarse filter 4 Filter press 5 Component adjustment tank 6 Roasting furnace 7 Dust collector
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23753493A JP3972996B2 (en) | 1993-09-24 | 1993-09-24 | Method for purifying ferrous iron-containing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23753493A JP3972996B2 (en) | 1993-09-24 | 1993-09-24 | Method for purifying ferrous iron-containing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0789731A JPH0789731A (en) | 1995-04-04 |
| JP3972996B2 true JP3972996B2 (en) | 2007-09-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23753493A Expired - Fee Related JP3972996B2 (en) | 1993-09-24 | 1993-09-24 | Method for purifying ferrous iron-containing solution |
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| Country | Link |
|---|---|
| JP (1) | JP3972996B2 (en) |
-
1993
- 1993-09-24 JP JP23753493A patent/JP3972996B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH0789731A (en) | 1995-04-04 |
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