JPH04318125A - Method for reusing ferrous scrap - Google Patents
Method for reusing ferrous scrapInfo
- Publication number
- JPH04318125A JPH04318125A JP3086885A JP8688591A JPH04318125A JP H04318125 A JPH04318125 A JP H04318125A JP 3086885 A JP3086885 A JP 3086885A JP 8688591 A JP8688591 A JP 8688591A JP H04318125 A JPH04318125 A JP H04318125A
- Authority
- JP
- Japan
- Prior art keywords
- scrap
- iron
- slag
- ferrous
- iron oxide
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 67
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000002893 slag Substances 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 ferrous metals Chemical class 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910052718 tin Inorganic materials 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000000292 calcium oxide Substances 0.000 description 13
- 235000012255 calcium oxide Nutrition 0.000 description 11
- 239000002699 waste material Substances 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、自動車解体屑等の老廃
鉄系スクラップの再利用方法に関する。さらに詳述すれ
ば、直接再利用が困難な老廃鉄系スクラップを使用して
クリーンなエネルギーである水素を製造すると共に、生
成した酸化鉄と酸化されないＣｕ、Ｎｉ、Ｓｎ等の非鉄
金属とを溶融状態で分離し、両者をそれぞれ回収するこ
とにより資源の有効利用を図る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reusing old iron-based scraps such as automobile scraps. More specifically, we will produce hydrogen, which is a clean energy, using old iron-based scrap that is difficult to recycle directly, and melt the produced iron oxide and non-ferrous metals such as Cu, Ni, and Sn that will not be oxidized. This relates to a method for effectively utilizing resources by separating the two in the same state and recovering both.
【０００２】0002
【従来の技術】これまで、一般に老廃鉄系スクラップは
回収・仕分けされた後、ギロチンと呼ばれる切断処理や
シュレッダー処理等によりサイジングされ、またその際
、ある程度、ゴム・プラスチック等の非金属およびＣｕ
等の非鉄金属を分離除去し、製鋼用原料として再生され
ている。しかし、自動車や家電製品のスクラップに混入
しているＣｕ、Ｓｎ等を含む部品である小型モータ等を
このような処理方法で分離・除去するのは困難である。[Prior Art] Until now, waste iron scrap has generally been collected and sorted, and then sized by a cutting process called a guillotine or a shredding process.
Non-ferrous metals such as steel are separated and removed and recycled as raw materials for steelmaking. However, it is difficult to separate and remove small motors and the like, which are parts containing Cu, Sn, etc., mixed in scraps from automobiles and home appliances using such processing methods.
【０００３】このような老廃鉄系スクラップ（ 以下、
単に老廃スクラップともいう） は、一般に電気炉で溶
解され再利用され、製品化されているが、ほとんどの製
品はＣｕ、Ｓｎなどの不純物含有規制値の比較的緩やか
な棒鋼である。高炉メーカで製造されている薄板、厚板
、鋼管等の製品は、製造段階で熱間・冷間加工等を行う
際にスクラップ由来のＣｕ、Ｓｎ等の特殊な不純物 （
以下、トランプエレメントと称する） 含有量が問題と
なり、上記のような老廃スクラップは極く少量しか使用
されていない。[0003] Such old iron scrap (hereinafter referred to as
(also simply referred to as waste scrap) is generally melted in an electric furnace, reused, and made into products, but most of the products are steel bars with relatively loose regulation values for the content of impurities such as Cu and Sn. Products such as thin plates, thick plates, and steel pipes manufactured by blast furnace manufacturers are subject to special impurities such as Cu and Sn derived from scrap during hot and cold processing during the manufacturing stage.
(hereinafter referred to as playing card elements) content is a problem, and only a very small amount of the above-mentioned waste scrap is used.
【０００４】製鋼精錬ではＳ、Ｐ、Ｏ、Ｎ、Ｃ等の不純
物を除去する技術は確立されている。しかし、Ｃｕ、Ｓ
ｎ等のトランプエレメントを除去する精錬技術は確立さ
れておらず、超真空あるいは超高温で蒸発除去する方法
や硫黄化合物等の特殊なフラックスを用いる方法が実験
室規模で試みられているにすぎない。これらの方法は技
術的問題に加え、コスト的にも有望とは考え難い。また
、最近、欧米先進国と同様、日本においても老廃スクラ
ップ発生が増加傾向にあり、建材、機械、自動車、家電
等のスクラップを中心に現状約２２百万トン／年の発生
量が２０２０年には倍近くまで増加することが予測され
ている。In steelmaking and refining, techniques for removing impurities such as S, P, O, N, and C have been established. However, Cu, S
No refining technology has been established to remove Trump elements such as n, and only laboratory-scale attempts have been made to remove them by evaporation in an ultra-vacuum or ultra-high temperature, or to use special fluxes such as sulfur compounds. . In addition to technical problems, these methods are not considered promising in terms of cost. In addition, recently, the generation of obsolete scrap has been on the rise in Japan, similar to developed countries in Europe and the United States, and the current amount of generation, mainly scrap of building materials, machinery, automobiles, home appliances, etc., is expected to reach approximately 22 million tons/year in 2020. is predicted to nearly double.
【０００５】一方、将来ますます表面処理や複合鋼板等
の鉄鋼製品の高付加価値化が進むことが考えられる。こ
のような製品のスクラップは不純物を多く含むため、回
収しても直接製鉄用スクラップとして再利用するのは困
難と考えられる。さらに、地球温暖化問題の観点から、
精錬の際、ＣＯ２ 発生の少ないスクラップの利用が注
目されていくと考えられる。以上を総合すると、増加す
る老廃スクラップを使用して、棒鋼のみならず一般的な
鉄鋼製品を製造することは、将来の大きな課題と言える
。[0005] On the other hand, in the future, it is thought that surface treatments and higher value-added steel products such as composite steel plates will become more and more advanced. Scraps from such products contain many impurities, so even if they are recovered, it is considered difficult to reuse them directly as scraps for steelmaking. Furthermore, from the perspective of global warming,
It is thought that the use of scrap, which produces less CO2 during refining, will attract attention. Taking all the above into account, it can be said that using the increasing amount of old scrap to produce not only steel bars but also general steel products will be a major challenge in the future.
【０００６】[0006]
【発明が解決しようとする課題】このように、特にＣｕ
、Ｓｎ等のトランプエレメントを精錬除去することが困
難な理由は、それらのトランプエレメントがＦｅより酸
化され難い元素であるからである。逆に言えば、Ｆｅを
酸化してしまえば、酸化されないトランプエレメントは
分離し易くなる。しかし、単に空気や酸素でスクラップ
を酸化しても鉄から酸化鉄に変化するだけでメリットは
少ない。[Problem to be solved by the invention] In this way, especially Cu
The reason why it is difficult to refine and remove tramp elements such as , Sn, etc. is that these tramp elements are elements that are more difficult to oxidize than Fe. Conversely, if Fe is oxidized, the playing card elements that are not oxidized become easier to separate. However, simply oxidizing scrap with air or oxygen only changes iron to iron oxide, so there is little benefit.
【０００７】一方、Ｈ２はクリーンなエネルギーとして
石油精製およびアンモニア合成にその需要の拡大が見込
まれる。Ｈ２は、一般に、メタン、プロパン等の炭化水
素ガスを主成分とする天然ガスや石油ガスを水蒸気を用
いて改質し （ＣＯとＨ２にする） 、さらにウォータ
シフト反応によりＣＯ２ とＨ２に変換した後、ＣＯ２
を分離除去して製造されている。しかし、この方法で
は天然資源の節約、また地球温暖化対策としてのＣＯ２
の発生量を減少させるという面での効果が少なく、将
来的には問題がある。On the other hand, demand for H2 is expected to increase as a clean energy for petroleum refining and ammonia synthesis. H2 is generally produced by reforming natural gas or petroleum gas, whose main component is hydrocarbon gas such as methane or propane, using steam (to convert it into CO and H2), and then converting it into CO2 and H2 through a water shift reaction. After, CO2
Manufactured by separating and removing. However, this method saves natural resources and reduces CO2 emissions as a measure against global warming.
It is not very effective in reducing the amount of carbon dioxide generated, and there will be problems in the future.
【０００８】理想的な方法は、太陽エネルギー等のクリ
ーンエネルギーを用い、水を分解してＨ２を製造するこ
とであるが、少なくとも現状では技術的、コスト的に実
用化は困難である。ここに、本発明の目的は、老廃スク
ラップからトランプエレメントを除去するとともに、ク
リーンなエネルギーであるＨ２をＣＯ２ の副生を伴う
ことなく製造することができる方法を提供することであ
る。[0008] The ideal method would be to use clean energy such as solar energy to decompose water to produce H2, but at least at present it is difficult to put this into practical use due to technical and cost considerations. An object of the present invention is to provide a method that can remove playing card elements from waste scrap and produce H2, which is a clean energy, without producing CO2 as a by-product.
【０００９】[0009]
【課題を解決するための手段】そこで、本発明者らはか
かる課題を解決すべく種々検討を重ね、次のような知見
を得た。
（１） 老廃スクラップを一種のエネルギー源と考え、
水蒸気と反応させることにより、Ｈ２というクリーンエ
ネルギーに変換することができる。すなわち
Ｆｅ＋ＸＨ２Ｏ ＝ ＦｅＯＸ ＋ ＸＨ２ ・
・・（１）（２） 生成した酸化鉄を石灰等の造滓剤と
反応させ、低融点 （１１００〜１３００℃） スラグ
として溶融させることにより、水蒸気により酸化されな
いＣｕ、Ｓｎ等の不純物 （小型モータ等から混入して
くる） から分離し、回収することができる。回収され
た酸化鉄主体のスラグはトランプエレメントをほとんど
含まないため、良質の製鋼用原料として再使用できる。
（３） 後述のように、スクラップの水蒸気による酸化
反応は、生成された緻密な酸化鉄層内ガス拡散が律速と
なり、反応速度が遅いが、生成酸化鉄を低融点スラグ中
に溶融させることにより、反応速度を著しく促進するこ
とができる。[Means for Solving the Problems] The present inventors have made various studies to solve the problems and have obtained the following knowledge. (1) Considering waste scrap as a kind of energy source,
By reacting with water vapor, it can be converted into clean energy called H2. That is, Fe+XH2O = FeOX + XH2 ・
...(1)(2) By reacting the generated iron oxide with a slag-forming agent such as lime and melting it as a low melting point (1100-1300℃) slag, impurities such as Cu and Sn that are not oxidized by water vapor (small size (contaminated from motors, etc.) and can be recovered. The recovered iron oxide-based slag contains almost no tramp elements, so it can be reused as a high-quality raw material for steelmaking. (3) As described below, the oxidation reaction of scrap with water vapor is rate-determined by gas diffusion within the formed dense iron oxide layer, and the reaction rate is slow. , can significantly accelerate the reaction rate.
【００１０】本発明は、自動車解体屑等の鉄系スクラッ
プを７００ ℃以上の高温状態で水蒸気により酸化する
ことにより生成した水素ガスを回収すると共に、生成し
た酸化鉄を、石灰等の造滓剤と反応させて低融点スラグ
として溶融させることにより、Ｃｕ、Ｎｉ、Ｓｎ等の酸
化され難い非鉄金属から分離し、酸化鉄主体のスラグは
鉄源として、また、溶融非鉄金属は非鉄金属源として、
それぞれ回収することを特徴とする鉄系スクラップの再
利用方法である。[0010] The present invention recovers the hydrogen gas produced by oxidizing iron-based scrap such as automobile scraps with steam at a high temperature of 700°C or higher, and also uses the produced iron oxide as a slag-forming agent such as lime. By reacting with the slag and melting it as a low-melting point slag, it is separated from non-ferrous metals that are difficult to oxidize such as Cu, Ni, Sn, etc. The slag mainly composed of iron oxide can be used as an iron source, and the molten non-ferrous metal can be used as a non-ferrous metal source.
This is a method of reusing iron-based scrap, which is characterized by recovering each type of scrap.
【００１１】本発明の好適態様によれば、前記酸化鉄の
溶解のための熱源として、酸素を使用してもよい。また
、シャフト炉等の向流移動層を反応器として使用して前
記鉄系スクラップの酸化、溶解を行ってもよい。さらに
、前記鉄系スクラップは、シュレッダー等の切断処理に
より、サイジングおよび選別を行ったものを使用しても
よい。According to a preferred embodiment of the invention, oxygen may be used as the heat source for melting the iron oxide. Further, the iron-based scrap may be oxidized and melted using a countercurrent moving bed such as a shaft furnace as a reactor. Further, the iron-based scrap may be sized and sorted by cutting using a shredder or the like.
【００１２】このように、本発明によれば、老廃鉄系ス
クラップを７００℃以上の高温状態で水蒸気と反応させ
、水素ガスを製造すると共に、Ｃｕ、Ｎｉ、Ｓｎ等の酸
化されない非鉄金属の分離除去を容易にし、資源の再利
用を図るものである。本発明が処理の対象とする老廃ス
クラップは、自動車解体屑ばかりでなく、家電、建材、
機械などいずれの分野の鉄系スクラップをも包含するの
であって、特定のものに制限されないが、いわゆるトラ
ンプエレメントを含有するものについてその利益が大き
い。As described above, according to the present invention, waste iron scrap is reacted with water vapor at a high temperature of 700° C. or higher to produce hydrogen gas, and at the same time, it is possible to separate non-ferrous metals such as Cu, Ni, and Sn that are not oxidized. This facilitates removal and reuses resources. The obsolete scrap that is the object of the present invention is not only automobile dismantling waste, but also home appliances, building materials, etc.
It includes iron-based scrap from any field such as machinery, and is not limited to any particular type, but it is of great benefit to those containing so-called tramp elements.
【００１３】[0013]
【作用】次に、本発明において処理条件などを上述のよ
うに限定した理由について詳述する。まず、水蒸気との
反応温度を７００ ℃以上に限定している理由は、水蒸
気との十分な反応速度を確保するためである。そのよう
な高温度は、予め別途スクラップを適宜手段で所定温度
にまで予熱してから反応容器にその予熱スクラップを装
入するか、あるいは高温不活性ガスを反応容器内に吹き
込んで予めスクラップを加熱するかして、確保する。[Operation] Next, the reason why the processing conditions etc. are limited as mentioned above in the present invention will be explained in detail. First, the reason why the reaction temperature with water vapor is limited to 700° C. or higher is to ensure a sufficient reaction rate with water vapor. Such high temperatures can be handled by preheating the scrap separately to a predetermined temperature using an appropriate means and then charging the preheated scrap into the reaction vessel, or by blowing high-temperature inert gas into the reaction vessel to heat the scrap in advance. and secure it.
【００１４】図１に厚さ３０ｍｍの鉄板を水蒸気雰囲気
下で２０時間反応させた後の酸化層厚さをそのときの温
度に対してグラフで示す。緻密な酸化鉄層が生成される
ため、反応速度は遅いが、温度上昇により反応速度は著
しく増大する。シュレッダー屑のようなスクラップは、
厚さ１ｍｍ程度の薄板を軽くプレスしたような状態にな
っているものが大部分である。したがって、酸化反応が
薄板の両面から進むこと、ならびに反応器内の滞留時間
を最大２０時間と仮定し、スクラップの７０％以上を酸
化させる、すなわち、１ｍｍ厚の鉄板の場合、０．７ｍ
ｍ（片側０．３５ｍｍ） 以上を酸化させるためには、
図１のグラフからも判るように７００ ℃以上の温度が
必要である。ちなみに６００ ℃ではスクラップの７０
％を酸化するのに７０時間必要となる。FIG. 1 is a graph showing the thickness of an oxide layer after a 30 mm thick iron plate is reacted in a steam atmosphere for 20 hours, versus the temperature at that time. The reaction rate is slow due to the formation of a dense iron oxide layer, but the reaction rate increases significantly as the temperature increases. Scraps such as shredder waste are
Most of them are in the state of lightly pressed thin plates with a thickness of about 1 mm. Therefore, assuming that the oxidation reaction proceeds from both sides of the sheet and that the residence time in the reactor is at most 20 hours, more than 70% of the scrap will be oxidized, i.e., for a 1 mm thick iron sheet, 0.7 m
In order to oxidize more than m (0.35 mm on one side),
As can be seen from the graph in Figure 1, a temperature of 700°C or higher is required. By the way, at 600℃, the scrap temperature is 70℃.
It takes 70 hours to oxidize %.
【００１５】次に、内径７０ｍｍ、外径１００ ｍｍ、
高さ２００ ｍｍの鉄ルツボ中にＦｅＯ：８０％、Ｃａ
Ｏ：２０％の混合フラックス１２００ｇを入れ、１２５
０℃まで昇温し同フラックスを溶解した後、粒径５〜１
０ｍｍの生石灰２００ｇを添加し、溶融スラグ上から鉄
製パイプを通して水蒸気を９．０ Ｎｌ／ｍｉｎの流量
で６０分間スラグ上面に向かって吹きつけ、鉄ルツボの
酸化・損耗状況を調査した。ルツボは底面と側壁部で底
より約８０ｍｍの部分が損耗しており、測定した結果、
平均約３．１ ｍｍ損耗されていることが判明した。こ
れらの結果より、スラグ中の鉄イオンが２価、３価の形
態をとることにより酸素媒体の役目をし、鉄ルツボを酸
化させること、ならびに、酸化により生成した酸化鉄を
スラグに溶解することにより酸化反応が促進されること
が判明した。Next, the inner diameter is 70 mm, the outer diameter is 100 mm,
FeO: 80%, Ca in an iron crucible with a height of 200 mm
O: Add 1200g of 20% mixed flux, 125
After heating up to 0℃ and melting the same flux, the particle size is 5 to 1.
200 g of quicklime with a thickness of 0 mm was added, and steam was blown onto the molten slag through an iron pipe toward the top of the slag at a flow rate of 9.0 Nl/min for 60 minutes, and the oxidation and wear conditions of the iron crucible were investigated. The bottom and side walls of the crucible were worn about 80mm from the bottom, and as a result of measurement,
It was found that the average wear was about 3.1 mm. These results show that iron ions in slag take the divalent or trivalent form and act as an oxygen medium to oxidize the iron crucible, and that the iron oxide produced by oxidation is dissolved in the slag. It was found that the oxidation reaction was promoted by
【００１６】図１に示す固体状態での鉄の酸化速度に比
べ、溶融スラグの存在下では約３倍の反応速度であり、
著しい反応速度向上効果があることが判明した。したが
って、本発明の好適態様によれば、生石灰などの造滓剤
との共存下でスクラップの水蒸気酸化を行えば特に速や
かに酸化が起こり、それに伴って水素生成も促進される
。本発明の好適態様にあって、向流移動層を反応容器と
して使用するのは、後述の実施例で示すように固体 （
スクラップ） −ガス間の熱交換および反応を良好にし
、熱効率を高めるためである。向流移動層としては例え
ば高炉のようなシャフト炉タイプ等が挙げられる。但し
、効率は低下するもののバッチ型反応器を用いることも
可能である。Compared to the oxidation rate of iron in the solid state shown in FIG. 1, the reaction rate is approximately three times as high in the presence of molten slag.
It was found that the reaction rate was significantly improved. Therefore, according to a preferred embodiment of the present invention, if the scrap is subjected to steam oxidation in the presence of a slag-forming agent such as quicklime, oxidation occurs particularly quickly, and hydrogen production is also promoted accordingly. In a preferred embodiment of the present invention, a countercurrent moving bed is used as a reaction vessel, as shown in the examples below.
scrap) - This is to improve heat exchange and reaction between gases and increase thermal efficiency. Examples of the countercurrent moving bed include a shaft furnace type such as a blast furnace. However, it is also possible to use a batch type reactor, although the efficiency is reduced.
【００１７】さらに、使用する老廃スクラップとしては
、ハンドリング上、また反応器内のガス流れ分布を比較
的均一にするため、シュレッダー処理等によってサイジ
ングしたものを用いることが望ましい。シュレッダー処
理の際、磁選等により大まかな選別を行ったものを使用
することが望ましい。ゴムやプラスチック等が混入する
とＣＯやＣＯ２ 、Ｎ２といったＨ２、Ｈ２Ｏ 以外の
ガスが発生するため、後にガスの精製が煩雑になるため
である。[0017] Furthermore, it is desirable to use waste scrap that has been sized by shredding or the like for handling reasons and to make the gas flow distribution within the reactor relatively uniform. When shredding, it is desirable to use materials that have been roughly sorted by magnetic separation or the like. This is because when rubber, plastic, etc. are mixed in, gases other than H2 and H2O, such as CO, CO2, and N2, are generated, which makes purification of the gas complicated later.
【００１８】なお、（１） 式で示した反応は発熱反応
であるが、発熱量は小さく生成した酸化鉄を溶解するに
は何らかの形で他のエネルギーを加える必要がある。電
力等の加熱エネルギーを加えることも可能であるが、ロ
スも多く反応器の設計も難しくなる。また、石油等の化
石燃料を燃焼させる方法もあるが、このような燃料は炭
素を含んでいるため生成ガス中にＣＯやＣＯ２ ガスが
含有されることになり、Ｈ２ガスの純度が低下する。Although the reaction shown in equation (1) is an exothermic reaction, the calorific value is small and it is necessary to add some form of other energy to dissolve the produced iron oxide. Although it is possible to add heating energy such as electricity, there is a lot of loss and it becomes difficult to design the reactor. There is also a method of burning fossil fuels such as petroleum, but since such fuels contain carbon, the generated gas will contain CO and CO2 gas, reducing the purity of H2 gas.
【００１９】したがって、本発明の好適態様にあっては
、水蒸気とともに少量の酸素を吹込んでスクラップ中の
鉄を酸化させる際の発熱により酸化鉄を溶解する。この
方法によれば、熱ロスも非常に少なく反応器の設計も容
易であり、かつ生成ガスにも問題を及ぼさない。空気を
用いることも可能であるが、生成ガス中にＮ２が混入す
るので純度低下の問題がある。Therefore, in a preferred embodiment of the present invention, a small amount of oxygen is blown in together with water vapor to melt the iron oxide by the heat generated when the iron in the scrap is oxidized. According to this method, there is very little heat loss, the design of the reactor is easy, and there is no problem with the produced gas. Although it is possible to use air, there is a problem of a decrease in purity since N2 is mixed into the generated gas.
【００２０】鉄が酸化し、生成した酸化鉄と石灰等の造
滓剤と反応すると低融点スラグが生成する。例としてＦ
ｅＯ −ＣａＯ 系を例にとると１００ ％ＦｅＯ で
は融点は約１３９０℃であるのに対し、９０％ＦｅＯ
−１０％ＣａＯ 、８０％ＦｅＯ −２０％ＣａＯ 、
７５％ＦｅＯ −２５％ＣａＯ スラグの融点はそれぞ
れ約１３００℃、１２００℃、１１５０℃である。でき
るだけ低温で処理した方が、熱効率面および耐火物の損
耗抑制面で有利であることは明らかである。When iron is oxidized and the produced iron oxide reacts with a slag-forming agent such as lime, low melting point slag is produced. For example, F
Taking the eO -CaO system as an example, 100% FeO has a melting point of approximately 1390°C, while 90% FeO
-10%CaO, 80%FeO -20%CaO,
The melting points of the 75%FeO-25%CaO slag are approximately 1300°C, 1200°C, and 1150°C, respectively. It is clear that treatment at as low a temperature as possible is advantageous in terms of thermal efficiency and suppression of wear and tear on the refractory.
【００２１】一方、Ｃｕ、Ｎｉ、Ｓｎ等のトランプエレ
メントは酸化されず、メタルのまま残るが、主体となる
成分であるＣｕの融点は１０８３℃である。従って、１
２００〜１３００℃といった温度では、Ｃｕは溶解し、
またＮｉ、Ｓｎ等の比較的少量の成分も溶融Ｃｕ中に溶
解し、溶融メタルを形成する。
従って、鉄を酸化し、スラグとして溶解する際、Ｃｕを
主体とするトランプエレメントは溶融メタルを形成する
ことから、この２相の溶体を一定時間保持すれば、自然
と比重分離されることになる。つまり、スクラップ中の
トランプエレメントを分離し、酸化鉄主体のスラグとＣ
ｕ主体のメタルをそれぞれ別に回収することが可能とな
る。On the other hand, playing card elements such as Cu, Ni, and Sn are not oxidized and remain as metals, but the melting point of Cu, which is the main component, is 1083°C. Therefore, 1
At temperatures such as 200 to 1300°C, Cu dissolves,
In addition, relatively small amounts of components such as Ni and Sn are also dissolved in the molten Cu to form molten metal. Therefore, when iron is oxidized and melted as slag, the tramp element mainly composed of Cu forms molten metal, and if this two-phase solution is maintained for a certain period of time, it will naturally separate by specific gravity. . In other words, the tramp elements in the scrap are separated, and the slag mainly composed of iron oxide and C
It becomes possible to collect the u-based metals separately.
【００２２】[0022]
【実施例１】本例では、本発明方法にて老廃スクラップ
を水蒸気で酸化し、水素を製造すると共に生成した酸化
鉄を生石灰と反応させ低融点スラグとして溶融させるこ
とにより、Ｃｕを主体とするトランプエレメントと分離
し、酸化鉄主体のスラグとＣｕ主体の溶融金属の両者を
回収した。本例で使用した反応容器は図２に示すバッチ
型反応器であった。図２（ａ） に示すように、内径４
００ ｍｍ、高さ１０００ｍｍの耐火物７を内張した炉
内に、予め約１０００℃に予熱した １００ｋｇのスク
ラップ１と １５ｋｇ の生石灰２を混合して充填した
。スクラップとしては粒径５０〜１００ ｍｍのシュレ
ッダースクラップを用いた。[Example 1] In this example, waste scrap is oxidized with steam using the method of the present invention to produce hydrogen, and the produced iron oxide is reacted with quicklime and melted as a low melting point slag to produce a material mainly composed of Cu. Separated from the tramp element, both slag mainly composed of iron oxide and molten metal mainly composed of Cu were recovered. The reaction vessel used in this example was a batch type reactor shown in FIG. As shown in Figure 2(a), the inner diameter is 4
100 kg of scrap 1 and 15 kg of quicklime 2, which had been preheated to about 1000° C., were mixed and filled into a furnace lined with a refractory material 7 having a diameter of 0.00 mm and a height of 1000 mm. Shredder scrap with a particle size of 50 to 100 mm was used as scrap.
【００２３】次に２本の羽口６より水蒸気３と酸素４の
混合ガスを吹込んだ。水蒸気および酸素の流量はそれぞ
れ４０Ｎｍ３／ｈｒ、１０Ｎｍ３／ｈｒとした。この状
態で約１時間処理を行ったところ、図２（ｂ） に示す
ようにスクラップは全て酸化され生石灰と反応して溶解
した。溶融スラグ８の温度は約１３００℃であった。生
成した水蒸気とＨ２の混合ガス５は冷却・除塵後、流量
測定ならびに組成分析に供した。またテスト終了後は羽
口よりＮ２ガスを吹込みながら冷却してから、炉内を解
体調査した。Next, a mixed gas of water vapor 3 and oxygen 4 was blown through two tuyeres 6. The flow rates of water vapor and oxygen were 40 Nm3/hr and 10 Nm3/hr, respectively. When the treatment was carried out in this state for about 1 hour, all the scraps were oxidized, reacted with quicklime, and dissolved, as shown in Figure 2(b). The temperature of molten slag 8 was about 1300°C. The generated mixed gas 5 of water vapor and H2 was cooled and dust removed, and then subjected to flow rate measurement and composition analysis. After the test was completed, the reactor was cooled while blowing N2 gas through the tuyere, and the inside of the reactor was dismantled and investigated.
【００２４】発生したガスを冷却後分析したところ （
冷却時に水蒸気は水となり分離される） ほぼ１００
％がＨ２であった。Ｈ２ガスの積算発生量は約１９Ｎｍ
３ であった。また、処理後の炉内を解体調査したとこ
ろ、図２（ｂ） に示すように、ＦｅＯ −ＣａＯ 系
のスラグの下に部分的にＣｕ主体のメタル粒９が存在し
ていた。使用したスクラップ中のＣｕ、Ｎｉ、Ｓｎの含
有量は平均でそれぞれ、０．３５、０．０９、０．０２
０ ％であったが、上記処理後に生成したＦｅＯ −Ｃ
ａＯ 系スラグ中にはＣｕ、Ｎｉ、Ｓｎがそれぞれ０．
０１２ ％、０．００５ ％、０．００２ ％しか含ま
れていなかった。When the generated gas was analyzed after cooling, it was found that (
During cooling, water vapor becomes water and is separated) Approximately 100
% was H2. The cumulative amount of H2 gas generated is approximately 19Nm
It was 3. Further, when the inside of the furnace was dismantled and inspected after the treatment, as shown in FIG. 2(b), metal grains 9 mainly composed of Cu were partially present under the FeO - CaO 2 slag. The average content of Cu, Ni, and Sn in the scrap used was 0.35, 0.09, and 0.02, respectively.
0%, but FeO-C generated after the above treatment
Cu, Ni, and Sn are each contained in the aO-based slag.
It contained only 0.012%, 0.005%, and 0.002%.
【００２５】[0025]
【実施例２】本例では、図３に示す高炉に類似したシャ
フト炉型反応器での連続操業テストを実施した。耐火物
７を内張りした内径８００ｍｍ 、高さ３０００ｍｍの
炉内に実施例１で用いたものと同様の約１．６ トンの
スクラップ１および０．２４トンの生石灰２を充填した
後、羽口６より約１０００℃のＮ２ガスを吹込み、スク
ラップ層内を約８００ ℃に予熱した。その後、吹込み
ガスをＯ２ ５０ ％、Ｎ２ ５０ ％の混合ガスに切
替え、炉下部のスクラップを一部溶解した。[Example 2] In this example, a continuous operation test was carried out in a shaft furnace type reactor similar to the blast furnace shown in Fig. 3. After filling a furnace with an inner diameter of 800 mm and a height of 3000 mm lined with refractory material 7 with approximately 1.6 tons of scrap 1 and 0.24 tons of quicklime 2 similar to those used in Example 1, the tuyeres 6 N2 gas at about 1000°C was blown into the scrap layer to preheat the inside of the scrap layer to about 800°C. Thereafter, the blown gas was changed to a mixed gas of 50% O2 and 50% N2, and a portion of the scrap in the lower part of the furnace was melted.
【００２６】その後、吹込みガスを水蒸気３と酸素４の
混合ガスに切替え、水蒸気酸化をスタートした。流量は
、それぞれ水蒸気２８０ Ｎｍ３／ｈｒ、酸素３０Ｎｍ
３／ｈｒであった。スクラップが溶解すると空隙がなく
なるため、その分体積が小さくなりスクラップ層の高さ
が低くなる。その溶解分だけ炉上部よりスクラップ１を
追加装入し、常に一定高さになるよう操業した。スクラ
ップの装入速度は平均で約０．５ トン／ｈｒ であっ
た。水蒸気吹込み地点でのスクラップ温度はほゞ１３０
０℃であった。Thereafter, the blown gas was changed to a mixed gas of 3 steam and 4 oxygen, and steam oxidation was started. The flow rates are 280 Nm3/hr of water vapor and 30 Nm of oxygen.
It was 3/hr. When the scrap is melted, there are no voids, so the volume becomes smaller and the height of the scrap layer becomes lower. Additional scrap 1 was charged from the upper part of the furnace to account for the melted amount, and the furnace was operated so that the height was always constant. The scrap charging rate averaged about 0.5 ton/hr. The scrap temperature at the steam injection point is approximately 130
It was 0°C.
【００２７】１時間後に排出口１０を開孔し、炉内より
溶融スラグ８と溶融メタル１１を排出した。操業は約６
ｈｒでほぼ定常状態となり、その後約２４時間の操業を
継続した。炉上から排出されるガス５の流量は２８０Ｎ
ｍ３／ｈｒ 、その組成は平均でＨ２約５１％、Ｈ２Ｏ
約４９％であり、温度は約２００ ℃であった。排出
された溶融物を鍋に受け、冷却後調査したところ、Ｆｅ
Ｏ −ＣａＯ 系スラグとＣｕを主体とするメタルに分
離されていることが判明した。スラグを分析したところ
、Ｃｕ、Ｎｉ、Ｓｎの含有量はそれぞれ０．０１０ ％
、０．００４ ％、０．００２ ％であり、トランプエ
レメント除去効果が確認できた。このように向流型反応
器での処理では、熱効率がよく、水蒸気を主に少量の酸
素添加で溶解が可能である。After one hour, the discharge port 10 was opened and the molten slag 8 and molten metal 11 were discharged from the furnace. The operation is about 6
The system reached a steady state after approximately 24 hours, and the operation continued for about 24 hours. The flow rate of gas 5 discharged from the top of the furnace is 280N
m3/hr, its composition is on average about 51% H2, H2O
It was about 49% and the temperature was about 200°C. When the discharged melt was collected in a pot and investigated after cooling, it was found that Fe
It was found that the slag was separated into O -CaO -based slag and metal mainly composed of Cu. When the slag was analyzed, the content of Cu, Ni, and Sn was 0.010% each.
, 0.004%, and 0.002%, and the effect of removing playing card elements was confirmed. As described above, treatment in a countercurrent reactor has good thermal efficiency, and water vapor can be dissolved mainly by adding a small amount of oxygen.
【００２８】[0028]
【発明の効果】本発明によれば、Ｃｕ等不純物 （トラ
ンプエレメント） を多く含み直接鉄源として再利用が
困難な老廃スクラップを使用して、クリーンエネルギー
であるＨ２ガスを製造すると共に、生成した酸化鉄を石
灰等の造滓剤と反応させ低融点スラグとして溶融させる
ことによりＣｕ、Ｎｉ、Ｓｎ等の酸化され難い非鉄金属
と分離した後、酸化鉄主体のスラグは鉄源として、溶融
非鉄金属は非鉄金属源として回収することが可能となる
。このことにより老廃スクラップの有効利用が可能とな
る。[Effects of the Invention] According to the present invention, H2 gas, which is clean energy, is produced by using old scrap that contains a lot of impurities such as Cu (tramp elements) and is difficult to reuse as a direct iron source. After separating iron oxide from non-ferrous metals that are difficult to oxidize, such as Cu, Ni, and Sn, by reacting with a slag-forming agent such as lime and melting it as a low-melting slag, the iron oxide-based slag is used as an iron source for molten non-ferrous metals. can be recovered as a source of non-ferrous metals. This allows effective use of old scrap.
【図１】鉄板を２０時間水蒸気酸化した後の酸化層厚の
温度依存性を示すグラフである。FIG. 1 is a graph showing the temperature dependence of the oxidized layer thickness after steam oxidizing an iron plate for 20 hours.
【図２】本発明の実施例で使用したバッチ型反応器の略
式説明図であり、図２（ａ） は初期程度および図２（
ｂ） は処理後の段階の様子を示す。FIG. 2 is a schematic explanatory diagram of the batch reactor used in the examples of the present invention, and FIG. 2(a) shows the initial state and FIG.
b) shows the state after processing.
【図３】本発明の実施例で使用した流移動層型反応器の
略式説明図である。FIG. 3 is a schematic illustration of a fluidized moving bed reactor used in Examples of the present invention.
１ ： スクラップ ２ ：
生石灰３ ： 水蒸気
４ ： 酸素５ ： 生成ガス
６ ： 羽口７ ： 耐火物
８ ： 溶融スラグ９ ： メタル粒
１０ ： 排出口１１ ：
溶融メタル1: Scrap 2:
Quicklime 3: Steam
4: Oxygen 5: Produced gas
6: Tuyere 7: Refractory
8: Molten slag 9: Metal particles 10: Discharge port 11:
molten metal
Claims (4)
００ ℃以上の高温状態で水蒸気により酸化することに
より生成した水素ガスを回収すると共に、生成した酸化
鉄を、石灰等の造滓剤と反応させて低融点スラグとして
溶融させることにより、Ｃｕ、Ｎｉ、Ｓｎ等の酸化され
難い非鉄金属から分離し、酸化鉄主体のスラグは鉄源と
して、また、溶融非鉄金属は非鉄金属源として、それぞ
れ回収することを特徴とする鉄系スクラップの再利用方
法。[Claim 1] Iron-based scrap such as automobile dismantling debris
By recovering the hydrogen gas generated by oxidizing with steam at a high temperature of 00°C or higher, and melting the generated iron oxide as a low-melting slag by reacting with a slag-forming agent such as lime, Cu, Ni , Sn, and other non-ferrous metals that are difficult to oxidize, the slag mainly consisting of iron oxide is recovered as an iron source, and the molten non-ferrous metal is recovered as a non-ferrous metal source.
、酸素を使用する請求項１記載の方法。2. A method according to claim 1, wherein oxygen is used as a heat source for melting the iron oxide.
して使用して前記鉄系スクラップの酸化、溶解を行うこ
とを特徴とする請求項１記載の方法。3. The method according to claim 1, wherein the ferrous scrap is oxidized and melted using a countercurrent moving bed such as a shaft furnace as a reactor.
等の切断処理により、サイジングおよび選別を行ったも
のであることを特徴とする請求項１記載の方法。4. The method according to claim 1, wherein the iron-based scrap is sized and sorted by cutting using a shredder or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3086885A JPH04318125A (en) | 1991-04-18 | 1991-04-18 | Method for reusing ferrous scrap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3086885A JPH04318125A (en) | 1991-04-18 | 1991-04-18 | Method for reusing ferrous scrap |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04318125A true JPH04318125A (en) | 1992-11-09 |
Family
ID=13899289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3086885A Withdrawn JPH04318125A (en) | 1991-04-18 | 1991-04-18 | Method for reusing ferrous scrap |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04318125A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237559A (en) * | 1997-02-20 | 1998-09-08 | Mitsubishi Materials Corp | Recovery of valuable metal in municipal garbage incineration ash |
-
1991
- 1991-04-18 JP JP3086885A patent/JPH04318125A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237559A (en) * | 1997-02-20 | 1998-09-08 | Mitsubishi Materials Corp | Recovery of valuable metal in municipal garbage incineration ash |
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| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980711 |