JPH01192729A - Method for dechlorinating iron oxide - Google Patents
Method for dechlorinating iron oxideInfo
- Publication number
- JPH01192729A JPH01192729A JP1418288A JP1418288A JPH01192729A JP H01192729 A JPH01192729 A JP H01192729A JP 1418288 A JP1418288 A JP 1418288A JP 1418288 A JP1418288 A JP 1418288A JP H01192729 A JPH01192729 A JP H01192729A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- furnace
- roasting
- waste liquor
- roasting furnace
- 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 16
- 230000000382 dechlorinating effect Effects 0.000 title claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007664 blowing Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 5
- 239000000567 combustion gas Substances 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 2
- 229910001035 Soft ferrite Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001047 Hard ferrite Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸化鉄、特にソフトフェライト用酸化鉄を製造
する際、得られる酸化鉄の塩素濃度を低減させる方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for reducing the chlorine concentration of iron oxide obtained when producing iron oxide, particularly iron oxide for soft ferrite.
一般に、フェライト用酸化鉄は、鋼材などの塩酸酸洗廃
酸液を噴霧焙焼または流動床焙焼方式で焙焼することに
よって、熱分解して塩酸を回収する際に副生ずる酸化鉄
を、その後適当な処理工程を経て得る方法を採っている
。In general, iron oxide for ferrite is made by roasting waste acid solution from hydrochloric acid pickling of steel materials using spray roasting or fluidized bed roasting to thermally decompose the iron oxide that is produced as a by-product when hydrochloric acid is recovered. A method is adopted in which the material is then obtained through appropriate processing steps.
上記の焙焼炉で副生した酸化鉄中には、塩素が１０００
〜４０００ ｐｐｍ、通常は１７００〜２４００ｐｐｍ
程度含有されている。この塩素は、Ｃ１分が酸化鉄に付
着した状態や、ＦｅＣ１ｚＯ形で存在する。The iron oxide produced as a by-product in the above roasting furnace contains 1,000 chlorine.
~4000 ppm, typically 1700-2400 ppm
Contains to some extent. This chlorine exists in the form of C1 attached to iron oxide or in the form of FeC1zO.
このような、高塩素骨の酸化鉄は、ハードフェライト用
には使用できるとしても、高透磁率が要求されるソフト
フェライト用には、このまま使用すると、錆の発生など
の問題を生じるため、通常、ソフトフェライト用途には
、１１０００ｐｐ以下であることが要請されている。Although iron oxide with a high chlorine content can be used for hard ferrite, it is usually not used for soft ferrite, which requires high magnetic permeability, because if it is used as it is, problems such as rust will occur. , for soft ferrite applications, it is required to be 11,000 pp or less.
そこで、この要請に答えるべく、従来は、焙焼炉で副生
じた酸化鉄を、純水などに投入して数時間ないし数十時
間攪拌して塩素骨を溶出させ、沈降分をフィルタープレ
スや遠心分離機などの固液分離機によって脱水した後、
乾燥し、必要により粉砕機を用いて所要の粒度に揃えて
ソフトフェライト用とする湿式法によって処理するのが
一般的な方法である。Therefore, in order to meet this demand, conventionally, the iron oxide by-produced in the roasting furnace was poured into pure water, etc., stirred for several hours to several tens of hours to elute the chlorine bones, and the sediment was removed using a filter press or the like. After dehydration using a solid-liquid separator such as a centrifuge,
The general method is to dry it, use a crusher if necessary to make it into the required particle size, and process it by a wet method to make soft ferrite.
近時は、副生酸化鉄をロータリーキルンや電気炉等によ
り約８５０℃以上の高温で再焙焼する乾式法も開発され
ている。この方法は、（１）式の反応を期待するものと
考えられる。Recently, a dry method has also been developed in which by-product iron oxide is reroasted at a high temperature of approximately 850° C. or higher using a rotary kiln, electric furnace, or the like. This method is considered to expect the reaction of formula (1).
４ＦｅＣ１１ｔ＋３０ｚ→２Ｆｅｚ０２＋４Ｃ１ｚ
・・・（１）〔発明が解決しようとする課題〕
上記の湿式法では、（１）（４分の除去率がさほど高く
なく、７００〜１０００ｐｐ■が下限である、（２）脱
水時に濾液側に酸化鉄の一部が移行したり、濾布からの
剥離が不十分であったり、さらに乾燥時に飛散するなど
してロス分が多く歩留りが大きい、（３）Ｃ１以外の磁
性特性を悪化させる不純物（ＳｉＯ□。4FeC11t+30z→2Fez02+4C1z
...(1) [Problems to be solved by the invention] In the above wet method, (1) (the removal rate in 4 minutes is not so high, the lower limit is 700 to 1000 pp), (2) the filtrate is removed during dehydration. (3) Magnetic properties other than C1 deteriorate due to a large amount of loss due to some of the iron oxide migrating to the side, insufficient peeling from the filter cloth, or scattering during drying, etc. impurities (SiO□.
Ｃａ、 Ｍｇ等）が純水を使用しない場合には混入する
虞れがある、（４）設備費、ランニングコストが嵩む、
などの問題がある。(Ca, Mg, etc.) may be mixed in if pure water is not used. (4) Equipment costs and running costs will increase.
There are problems such as.
一方、乾式法においては、確かに８５０℃以上の高温で
あれば塩素を１１０００ｐｐ以下にすることができるこ
とを本発明者らも確認したが、（イ）焙焼炉以外に別途
処理設備が必要である、（ロ）高温処理なので、熱消費
が嵩む、（ハ）さらに根本的な難点として、変質し、黒
色化し、ソフトフェライト用としての磁性特性が悪化す
る、などの問題点がある。On the other hand, in the dry method, the present inventors have confirmed that it is possible to reduce chlorine to 11,000 pp or less at high temperatures of 850°C or higher; however, (a) separate processing equipment is required in addition to the roasting furnace; (b) Since it is a high-temperature treatment, heat consumption increases; (c) More fundamental problems include deterioration, blackening, and deterioration of magnetic properties for use in soft ferrite.
そこで、本発明の主たる目的は、上記各課題を一挙に解
決し、きわめて簡易かつ経済的な方法をもって、確実に
塩素の低減を図り得る方法を提要することにある。Therefore, the main purpose of the present invention is to provide a method that solves the above-mentioned problems all at once and can reliably reduce chlorine using an extremely simple and economical method.
前記課題を解決するための本発明は、鋼材の塩酸酸洗廃
液を焙焼して熱分解することによって酸化鉄を得るに当
り；
前記焙焼炉の中部〜下部に水分を添加することを特徴と
するものである。The present invention for solving the above problems is characterized in that when iron oxide is obtained by roasting and thermally decomposing waste liquid from hydrochloric acid pickling of steel materials; moisture is added to the middle to lower part of the roasting furnace. That is.
本発明では、焙焼炉の中部〜下部に水分を、たとえば水
蒸気や水を圧力空気に乗せた形で吹込むと、次記（２）
および（３）式の反応が生じ、塩素分をガス中に飛散さ
せることによって、酸化鉄として取り出したときにおけ
る塩素分を確実に低減できる。In the present invention, when moisture is blown into the middle to lower part of the roasting furnace, for example, in the form of steam or water carried on pressurized air, the following (2) can be achieved.
By causing the reaction of formula (3) and scattering the chlorine content into the gas, the chlorine content when extracted as iron oxide can be reliably reduced.
（Ｆｅｔｒｓ ＋ ＨＣｌ ） ＋ Ｈ２Ｏ＋ Ｏｘ−
Ｆｅ２Ｏ３＋ ＨＣＩｔ↑＋Ｈ，０↑ ・（２）
２ＦｅＣｊ！ｚ ＋２ＨｚＯ＋二〇。(Fetrs + HCl) + H2O+ Ox-
Fe2O3+ HCIt↑+H,0↑ ・(2)
2FeCj! z +2HzO+20.
” Ｆｅ、Ｏ，＋ ４ ＨＣｊ！ ↑
・（３）（上記〔〕は付着している状態を示す。）ま
た、本発明法では、水分吹込みという簡易な手段による
から、きわめて実用的である。” Fe, O, + 4 HCj! ↑
- (3) (The above [ ] indicates a state of adhesion.) Furthermore, the method of the present invention is extremely practical because it uses a simple method of blowing moisture.
〔発明の具体的構成〕。[Specific configuration of the invention].
以下本発明を図面を参照しながらさらに詳説する。The present invention will be explained in more detail below with reference to the drawings.
本発明に係る焙焼炉としては、ドラボーやルスナ等の噴
霧形式の焙焼炉のほか、ケミライト等の流動型焙焼炉を
使用できるが、以下は前者の例である。As the roasting furnace according to the present invention, in addition to a spray type roasting furnace such as Drabaud or Rusna, a fluidized type roasting furnace such as Chemilite can be used, and the following is an example of the former.
第１図中１は焙焼炉、２は副生ずる酸化鉄の成品ホッパ
ーである。焙焼炉１は円筒状胴部とその下部に円錐状の
ホッパ一部を有し、さらにその下部に一時貯留部ＩＡを
備えている。In FIG. 1, 1 is a roasting furnace, and 2 is a product hopper for iron oxide produced as a by-product. The roasting furnace 1 has a cylindrical body and a part of a conical hopper at the lower part thereof, and further includes a temporary storage part IA at the lower part.
焙焼炉１の上部からは、廃酸液３が吹込口から液状、好
ましくは噴霧状で吹込むノズル４によって吹込まれる。A waste acid liquid 3 is blown into the upper part of the roasting furnace 1 through a nozzle 4 through which it is blown in liquid form, preferably in the form of a spray.
焙焼炉１の胴部の下端には、燃焼ガス５の吹込口６が接
線的に配置され、燃焼ガス５によって炉内を８００〜９
００℃程度に保ちつつ、廃酸液３を熱分解して、ＨＣｌ
をガスとして排出ロアから排出するとともに、副生ずる
酸化鉄Ｆｅは下部のホッパ一部から貯留部２へ移行され
る。At the lower end of the body of the roasting furnace 1, an inlet 6 for the combustion gas 5 is arranged tangentially, and the inside of the furnace is
The waste acid solution 3 is thermally decomposed while maintaining the temperature at around 00°C to produce HCl.
is discharged as a gas from the discharge lower, and iron oxide Fe, which is a by-product, is transferred from a part of the lower hopper to the storage section 2.
８は排出されたＨＣｌ１ガスを処理するための湿式集塵
機で、除塵後のＨＣｌは酸洗に再利用される。8 is a wet type dust collector for treating the discharged HCl1 gas, and the HCl after dust removal is reused for pickling.
上記の焙焼設備は基本的には公知のものであるが、本発
明では、酸化鉄化が進んだ、かつ第４図に炉内温度分布
例を示すように酸化鉄温度が４００℃以上の個所、すな
わち炉ｌの中部およびまたは下部において水分を添加す
る。この場合、第１図のように、燃焼ガス吹込口６の下
部（Ａ）、その上部（Ｂ）、下部から中心部まで延在さ
せて（Ｃ）、あるいは−時貯留部ＩＡ（Ｄ）など適宜の
位置から吹込むことができる。また、吹込みに当っては
、第２図および第３図のように、複数本の吹込ノズルＡ
Ｉ”’ Ａ ａによってもよい。The above-mentioned roasting equipment is basically known, but in the present invention, the iron oxide temperature is 400°C or higher, as shown in Fig. 4, which shows an example of the temperature distribution in the furnace. Moisture is added at points, ie in the middle and/or lower part of the furnace I. In this case, as shown in Fig. 1, the lower part (A) of the combustion gas inlet 6, the upper part (B), extending from the lower part to the center (C), or the storage part IA (D), etc. It can be injected from any suitable position. In addition, when blowing, as shown in FIGS. 2 and 3, multiple blow nozzles A are used.
I''' Aa may also be used.
水分添加の態様としては、水、水蒸気、あるいはこれら
を圧力空気と共に吹込むなどの態様がある。水分添加量
としては、生成する酸化鉄１トン当り１０１以上が好ま
しい。Examples of ways to add moisture include adding water, steam, or blowing these together with pressurized air. The amount of water added is preferably 101 or more per ton of iron oxide produced.
次に実施例によって本発明の効果を明らかにする。 Next, the effects of the present invention will be clarified by examples.
上述例のＡ位置から、スプレー元圧６ ｋｇ ／ ｃｉ
、ノズル径１．５鰭φの４つのノズルにより霧氷を全水
量として１００１／ｌｏｎ （酸化鉄）で吹込んだ。From position A in the above example, spray source pressure 6 kg/ci
Hoarfrost was injected at a total amount of water of 1001/lon (iron oxide) using four nozzles with a nozzle diameter of 1.5 fins.
また、水量を１Ｑｊ２／１ｏｎ（酸化鉄）に変えてみた
。さらに、霧氷の吹込みと、圧空の吹込みを併用した。I also tried changing the amount of water to 1Qj2/1on (iron oxide). Furthermore, a combination of blowing in hoarfrost and blowing in compressed air was used.
これらによって、副生する酸化鉄のＣＩ！濃度の変化を
調べたところ、第１表の結果を得た。By these, the CI of iron oxide produced as a by-product! When the change in concentration was investigated, the results shown in Table 1 were obtained.
第 １ 表
上記の結果から、本発明に従うと、Ｃ１分の低減を図る
ことができるとともに、霧水量が多いほど、圧空を併用
すると、脱ＣＩ！率が高いことが判る。Table 1 From the above results, according to the present invention, it is possible to reduce C1, and the greater the amount of mist water, the more compressed air is used, the more CI can be removed! It can be seen that the rate is high.
〔発明の効果］
以上の通り、本発明によれば、簡易な方法によって、確
実に塩素の低減を図ることができる。[Effects of the Invention] As described above, according to the present invention, chlorine can be reliably reduced by a simple method.
第１図は本発明法の実施の態様を示す概要図、第２図お
よび第３図は水分吹込み位置例の縦断面図および横断面
図、第４図は炉内温度分布側図である。
１・・・焙焼炉、３・・・廃酸液、４・・・ノズル、５
〜燃焼ガス、Ａ−Ｄ・・・水分吹込位置、Ａ、〜Ａ４・
・・吹込ノズル。
特許出願人 住友金属工業株式会社
第１図
第２図
第３図Figure 1 is a schematic diagram showing an embodiment of the method of the present invention, Figures 2 and 3 are longitudinal and cross-sectional views of examples of moisture injection positions, and Figure 4 is a side view of temperature distribution in the furnace. . 1... Roasting furnace, 3... Waste acid liquid, 4... Nozzle, 5
~Combustion gas, A-D... Moisture injection position, A, ~A4・
...Blow nozzle. Patent applicant: Sumitomo Metal Industries, Ltd. Figure 1 Figure 2 Figure 3
Claims (1)
よって酸化鉄を得るに当り； 前記焙焼炉の中部〜下部に水分を添加することを特徴と
する酸化鉄の脱塩素方法。(1) In obtaining iron oxide by roasting and thermally decomposing waste liquid from hydrochloric acid pickling of steel materials; a method for dechlorinating iron oxide, which is characterized by adding moisture to the middle to lower part of the roasting furnace. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1418288A JPH01192729A (en) | 1988-01-25 | 1988-01-25 | Method for dechlorinating iron oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1418288A JPH01192729A (en) | 1988-01-25 | 1988-01-25 | Method for dechlorinating iron oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01192729A true JPH01192729A (en) | 1989-08-02 |
Family
ID=11853993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1418288A Pending JPH01192729A (en) | 1988-01-25 | 1988-01-25 | Method for dechlorinating iron oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01192729A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597547A (en) * | 1995-04-13 | 1997-01-28 | Shell Oil Company | Reduction of residual chloride in iron oxides |
| EP0850881A1 (en) * | 1996-12-27 | 1998-07-01 | Ruthner, Michael Johann, Dipl.Ing. Dr.mont. | Process and apparatus for the preparation of iron oxides from solutions containing hydrochloric acid iron oxide chloride |
| KR100373759B1 (en) * | 2000-05-09 | 2003-02-26 | 주식회사 이지 | Removal system remaining chlorine of iron oxide |
| AT501627A1 (en) * | 2005-04-06 | 2006-10-15 | Wolfgang Dipl Ing Dr Kladnig | Device for extraction of ferric oxide from chlorometallic salt solutions, comprises a spray dryer and a heat reactor zone for thermal decomposition of the metallic salt solution |
| WO2008070885A3 (en) * | 2006-12-12 | 2008-09-25 | Gerhard Frithum | Method for increasing the specific surface of iron oxides in spray roasting plants |
| CN103071648A (en) * | 2013-01-04 | 2013-05-01 | 中冶南方工程技术有限公司 | Washing method for acid gun in acid regeneration system with atomization roasting method |
-
1988
- 1988-01-25 JP JP1418288A patent/JPH01192729A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597547A (en) * | 1995-04-13 | 1997-01-28 | Shell Oil Company | Reduction of residual chloride in iron oxides |
| EP0850881A1 (en) * | 1996-12-27 | 1998-07-01 | Ruthner, Michael Johann, Dipl.Ing. Dr.mont. | Process and apparatus for the preparation of iron oxides from solutions containing hydrochloric acid iron oxide chloride |
| KR100373759B1 (en) * | 2000-05-09 | 2003-02-26 | 주식회사 이지 | Removal system remaining chlorine of iron oxide |
| AT501627A1 (en) * | 2005-04-06 | 2006-10-15 | Wolfgang Dipl Ing Dr Kladnig | Device for extraction of ferric oxide from chlorometallic salt solutions, comprises a spray dryer and a heat reactor zone for thermal decomposition of the metallic salt solution |
| AT501627B1 (en) * | 2005-04-06 | 2007-03-15 | Wolfgang Dipl Ing Dr Kladnig | Device for extraction of ferric oxide from chlorometallic salt solutions, comprises a spray dryer and a heat reactor zone for thermal decomposition of the metallic salt solution |
| WO2008070885A3 (en) * | 2006-12-12 | 2008-09-25 | Gerhard Frithum | Method for increasing the specific surface of iron oxides in spray roasting plants |
| CN103071648A (en) * | 2013-01-04 | 2013-05-01 | 中冶南方工程技术有限公司 | Washing method for acid gun in acid regeneration system with atomization roasting method |
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