JPH04318124A - Method for reusing ferrous scrap - Google Patents
Method for reusing ferrous scrapInfo
- Publication number
- JPH04318124A JPH04318124A JP3085494A JP8549491A JPH04318124A JP H04318124 A JPH04318124 A JP H04318124A JP 3085494 A JP3085494 A JP 3085494A JP 8549491 A JP8549491 A JP 8549491A JP H04318124 A JPH04318124 A JP H04318124A
- Authority
- JP
- Japan
- Prior art keywords
- scrap
- iron
- steam
- gas
- oxidizing
- 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- Withdrawn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 description 23
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000009628 steelmaking Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- -1 ferrous metals Chemical class 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 238000007664 blowing Methods 0.000 abstract description 6
- 238000007885 magnetic separation Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000012360 testing method 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
- 239000004566 building material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects 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
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 150000003464 sulfur compounds Chemical class 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
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、鉄
を酸化させ、Ｃｕ、Ｎｉ、Ｓｎ等の非鉄金属との分離回
収を容易にすることにより資源の有効利用を図る方法に
関するものである。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, in addition to producing hydrogen, which is a clean energy source, by using old iron-based scrap that is difficult to recycle directly, we also oxidize the iron and separate and recover it from non-ferrous metals such as Cu, Ni, and Sn. This topic relates to a method for making effective use of resources by facilitating the use of resources.
【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・冷間加工性等を行う
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 called 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 impurities such as Cu and Sn. Thin plates, thick plates manufactured by blast furnace manufacturers,
Products such as steel pipes are subject to special impurities such as Cu and Sn derived from scrap during hot and cold workability 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はメリット
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, which changes iron to iron oxide, provides 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。すなわち[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 is converted into clean energy called H2. i.e.
【００１０】0010
【数１】[Math 1]
【００１１】上記反応は両者とも発熱反応であり、反応
器の設計により熱効率を向上させればその他の熱エネル
ギーの付与は不要または少量で済む。
（２） 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） は、水蒸気酸
化処理後のスクラップが酸化され、破砕され易くなって
いるため、それを破砕した後、磁選あるいは比重分離等
により容易に分離される。回収された酸化鉄はトランプ
エレメントをほとんど含まないため、問題なく製鋼用原
料として使用できる。[0011] Both of the above reactions are exothermic reactions, and if the thermal efficiency is improved by designing the reactor, it is unnecessary or only a small amount of other thermal energy needs to be applied. (2) Impurities such as Cu and Sn that are not oxidized by steam (introduced from small motors, etc.) are oxidized after steam oxidation treatment, making them more likely to be crushed. Alternatively, it can be easily separated by specific gravity separation or the like. Since the recovered iron oxide contains almost no tramp elements, it can be used as a raw material for steelmaking without any problems.
【００１２】本発明は、以上の知見に基づいてなされた
ものであり、その要旨とするところは、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水素ガスを製造するとともに
、水蒸気による酸化処理後のスクラップを回収する鉄系
スクラップの再利用方法である。本発明の好適態様によ
れば、シャフト炉等の向流移動層を反応器として使用し
て水蒸気による酸化を行ってもよい。また、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であってもよい。The present invention has been made based on the above findings, and its gist is to oxidize iron-based scrap such as automobile scraps with water vapor at a high temperature of 700°C or higher to produce hydrogen gas. This is a method for reusing iron-based scrap, in which scrap is produced and the scrap is recovered after oxidation treatment with steam. According to a preferred embodiment of the invention, the oxidation with steam may be carried out using a countercurrent moving bed, such as a shaft furnace, as the reactor. Further, the iron-based scrap may be sized and sorted by cutting using a shredder or the like.
【００１３】本発明は、その別の態様によれば、上記方
法で処理後のスクラップを破砕後、酸化鉄は製鋼原料等
の鉄源として、酸化されないＣｕ、Ｎｉ、Ｓｎ等はそれ
ぞれの金属源としてそれぞれ分離回収する鉄系スクラッ
プの再利用方法である。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ことができる。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
をも包含するものであって、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
てはその利益が大きい。According to another aspect of the present invention, after crushing the scrap treated by the above method, iron oxide is used as an iron source such as a steelmaking raw material, and unoxidized Cu, Ni, Sn, etc. are used as respective metal sources. This is a method of reusing iron-based scrap that is separated and collected as Thus, according to the present invention,
By reacting old iron scrap with steam at high temperatures of over 700°C, hydrogen gas is produced, and Cu, Ni
, Sn, and other non-ferrous metals that are not oxidized can be easily separated and removed, and resources can be recycled. The obsolete scrap to be processed by the present invention includes not only automobile dismantling waste but also iron-based scrap from any field such as home appliances, building materials, machinery, etc., and is not limited to a specific type. The benefits of those containing playing card elements are large.
【００１４】従来にあっても鉄を水蒸気酸化して水素を
生成させる方法は水素の製造方法として知られていた。
しかし、それはあくまでも水素の製造方法であって、例
えばそれに用いられる鉄は鉄鉱石を還元したものであっ
て、酸化したものは再び還元して使用する。このような
従来法と比較してみると、本発明にあっては水蒸気酸化
処理して得た酸化鉄が破砕し易いことおよびマグネタイ
トに富むことにさらに着目し、それらの事実と鉄系スク
ラップの処理、特にトランプエレメント含有鉄系スクラ
ップの処理とを組合せることによりこれまで不可能と考
えられていた鉄系スクラップからの効率的脱銅が経済的
にも可能となることを見い出したのであって、従来何ら
注目されることがなかった事実に着目してなされた本発
明はその発想においてすでにユニークなものと云える。Conventionally, a method of producing hydrogen by steam oxidizing iron has been known as a method of producing hydrogen. However, this is just a method for producing hydrogen; for example, the iron used therein is reduced iron ore, and the oxidized product is reduced again before use. When compared with such conventional methods, the present invention focuses on the fact that iron oxide obtained by steam oxidation treatment is easy to fracture and is rich in magnetite, and combines these facts with iron-based scrap. We have discovered that by combining this process with the treatment of ferrous scrap containing tramp elements, it becomes economically possible to efficiently remove copper from ferrous scrap, which was previously thought to be impossible. The present invention, which was created by focusing on a fact that has not received any attention in the past, can be said to be unique in its idea.
【００１５】[0015]
【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 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 achieved by separately preheating the scrap to a predetermined temperature by 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.
【００１６】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
度にたいしてグラフで示す。緻密な酸化鉄層が生成され
るため、反応速度はかなり遅いが温度上昇により著しく
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０．７ｍｍ（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 oxidized layer after a 30 mm thick iron plate is reacted in a steam atmosphere for 20 hours as a function of the temperature at that time. Due to the formation of a dense iron oxide layer, the reaction rate is quite slow, but increases significantly with increasing temperature. Most scraps such as shredder waste 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. 0.7 mm of a 1 mm thick iron sheet (0.7 mm on one side)
．． As can be seen from the graph in FIG. 1, a temperature of 700° C. or higher is required to oxidize a material with a diameter of 35 mm or more. By the way, at 600°C, it takes 70 hours to oxidize 70% of the scrap.
【００１７】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
しては例えばシャフト炉、ロータリーキルン、グレート
キルン等が挙げられる。但し、効率は低下するものの固
定層型反応器を用いることも可能である。また、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ク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。In a preferred embodiment of the present invention, the use of a countercurrent moving bed as a reaction vessel improves heat exchange and reaction between solid (scrap) and gas, and improves thermal efficiency, as shown in the examples below. This is to increase the Examples of the countercurrent moving bed include a shaft furnace, rotary kiln, and grate kiln. However, it is also possible to use a fixed bed reactor, although the efficiency will be lower. In addition, it is desirable to use waste scrap that has been sized by a shredding process 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】鉄が酸化して酸化物になると、弾性、延性
が非常に小さくなり、強度も著しく低下するため、小さ
な力で破砕が容易になる。また生成したマグネタイト（
Ｆｅ３Ｏ４） は磁性があり、また比重は約５．２ で
ある。一方、酸化され難い非鉄金属であるＣｕ、Ｎｉ、
Ｓｎの比重はそれぞれ８．９６、８．９ 、７．３０で
ある。Ｃｕ、Ｎｉ、Ｓｎ等は酸化されずメタルのまま残
っているが、磁性がなく比重も酸化鉄に比べ軽いため磁
選や比重分離による分離回収が容易である。すなわち、
本発明における上述のような水蒸気酸化処理を行って酸
化鉄を得た後、その酸化鉄とＣｕ等の非鉄金属が分かれ
るような程度にまで細かく破砕し、次いで磁選、比重分
離等による選別処理を行うことにより、酸化鉄はトラン
プエレメント含有量の少ない良好な鉄源として、酸化さ
れないＣｕ、Ｎｉ、Ｓｎ等の金属はそれぞれ金属源とし
て回収することができる。[0018] When iron is oxidized and becomes an oxide, its elasticity and ductility become extremely low, and its strength is also significantly reduced, making it easy to crush with a small force. Also generated magnetite (
Fe3O4) is magnetic and has a specific gravity of about 5.2. On the other hand, Cu, Ni, which are non-ferrous metals that are difficult to oxidize,
The specific gravity of Sn is 8.96, 8.9, and 7.30, respectively. Cu, Ni, Sn, etc. are not oxidized and remain as metals, but they are not magnetic and have a lighter specific gravity than iron oxide, so they can be easily separated and recovered by magnetic separation or specific gravity separation. That is,
After obtaining iron oxide by performing the above-mentioned steam oxidation treatment in the present invention, the iron oxide is crushed finely to such an extent that non-ferrous metals such as Cu are separated, and then a sorting treatment such as magnetic separation and specific gravity separation is carried out. By doing so, iron oxide can be recovered as a good iron source with a low content of Trump elements, and metals such as Cu, Ni, and Sn that are not oxidized can be recovered as metal sources.
【００１９】[0019]
【実施例１】本例では、図２に示す小型固定層型反応器
を用いて本発明にかかる方法にて老廃スクラップを水蒸
気で酸化し、生成した水素を回収した。図２に示すよう
に、内径４００ ｍｍ、高さ１５００ｍｍのＡｌ２０３
系耐火物５を内張し、高周波コイル６による加熱機能
のある反応炉内に、粒径５０〜１００ ｍｍの１５０ｋ
ｇ のシュレッダースクラップ１を充填した。２本の羽
口４よりＮ２ガスを吹込みながら、所定の温度（９００
℃または１０００℃） に加熱した後、吹込みガスを水
蒸気２に切替えた。水蒸気の流量は１２０ Ｎｍ３／ｈ
ｒとし、９００ ℃の場合３ｈｒ、１０００℃の場合２
ｈｒテストを継続した。[Example 1] In this example, waste scrap was oxidized with steam using the method according to the present invention using a small fixed bed reactor shown in FIG. 2, and the generated hydrogen was recovered. As shown in Fig. 2, the Al203 material has an inner diameter of 400 mm and a height of 1500 mm.
In a reactor lined with a refractory 5 and equipped with a heating function using a high-frequency coil 6, 150 kg of grain size 50 to 100 mm was placed.
g of shredder scrap 1 was filled. While blowing N2 gas through the two tuyeres 4, the temperature is maintained at a predetermined temperature (900
After heating to 1000° C. or 1000° C., the blowing gas was switched to steam 2. The flow rate of water vapor is 120 Nm3/h
r, 3 hours at 900℃, 2 hours at 1000℃
Continued hr test.
【００２０】生成した水蒸気とＨ２の混合ガス３は冷却
・除塵後、流量測定ならびに組成分析に供した。また終
了後は羽口よりＮ２ガスを吹込みながら冷却してから炉
内よりスクラップを取出し、分析に供した。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
発生ガス量 （積算） は１０００℃の場合約約７６Ｎ
ｍ３ 、９００ ℃の場合５４Ｎｍ３ であった。The generated mixed gas 3 of water vapor and H2 was cooled and dust removed, and then subjected to flow rate measurement and composition analysis. After completion, the reactor was cooled while blowing N2 gas through the tuyeres, and scraps were taken out from the furnace and subjected to analysis. When the generated gas was analyzed after cooling (water vapor becomes water and is separated during cooling), it was found that almost 100% was H2. H2
The amount of gas generated (integrated) is approximately 76N at 1000℃
m3 at 900°C was 54Nm3.
【００２１】また、処理後のスクラップを分析したとこ
ろ、１０００℃の場合、全鉄中の約９５％が、９００
℃の場合、約７０％がマグネタイトにまで酸化されてい
ることが判明した。さらにスクラップ中には小型モータ
が混入していたがモータで使用されている銅は金属状態
のまま残っていた。本例の結果から、スクラップを水蒸
気で酸化させ、Ｈ２を製造することが可能であり、シュ
レッダー屑のような薄板をプレスしたような形状のもの
では、比較的短時間で処理が可能であることが判明した
。[0021] Further, when the scrap after processing was analyzed, at 1000°C, about 95% of the total iron was 900°C.
℃, approximately 70% was found to be oxidized to magnetite. Furthermore, a small motor was found in the scrap, but the copper used in the motor remained in its metallic state. The results of this example show that it is possible to produce H2 by oxidizing scrap with steam, and that it is possible to process scraps in a relatively short time if they are shaped like pressed thin plates, such as shredder scraps. There was found.
【００２２】[0022]
【実施例２】本例では、図３に示すシャフト炉型向流反
応器での連続操業テストを実施した。すなわち、Ａｌ２
０３ 系耐火物５を内張りした内径約８００ｍｍ 、高
さ約３０００ｍｍのシャフト炉内に約１．６ トンのシ
ュレッダースクラップ１を充填した後、約１０００℃の
Ｎ２ガスを羽口４より吹込み、スクラップ層内を約８０
０ ℃に予熱した。その後、吹込みガスを水蒸気２に切
替えると共に、スクレパー７を動かすことによりスクラ
ップを炉下部排出口８より切出しながら、炉上部よりス
クラップ１を装入する連続操業をスタートした。操業は
約４ｈｒでほぼ定常状態となりその後約２０ｈｒのテス
トを継続した。[Example 2] In this example, a continuous operation test was conducted in a shaft furnace type countercurrent reactor shown in FIG. 3. That is, Al2
After filling about 1.6 tons of shredder scrap 1 into a shaft furnace lined with 03 series refractory 5 and having an inner diameter of about 800 mm and a height of about 3000 mm, N2 gas at about 1000°C was blown into the tuyere 4 to remove the scrap. Approximately 80 within the layer
Preheated to 0°C. Thereafter, the blown gas was switched to steam 2, and continuous operation was started in which scrap 1 was charged from the upper part of the furnace while scrap was cut out from the lower furnace outlet 8 by moving the scraper 7. The operation reached a nearly steady state after about 4 hours, and then the test continued for about 20 hours.
【００２３】なお、スクラップの排出速度は約０．４
トン／ｈｒ 、水蒸気の吹込み速度は約４３０Ｎｍ３／
ｈｒとした。炉上から排出されるガス３の流量は約４３
０Ｎｍ３／ｈｒ 、その組成は、平均でＨ２約４８％、
Ｈ２Ｏ 約５２％であり、温度は約３００ ℃であった
。排出された処理後スクラップを分析したところ、全鉄
中の約９５％がマグネタイトに酸化されていることが判
明した。また排出されたスクラップの温度は約４００℃
であった。[0023] The scrap discharge rate is approximately 0.4
ton/hr, the steam injection rate is approximately 430Nm3/
It was set as hr. The flow rate of gas 3 discharged from the top of the furnace is approximately 43
0Nm3/hr, its composition is about 48% H2 on average,
H2O was about 52% and the temperature was about 300°C. Analysis of the discharged scrap after treatment revealed that about 95% of the total iron had been oxidized to magnetite. The temperature of the discharged scrap is approximately 400℃.
Met.
【００２４】炉内のスクラップは （スクラップ層の高
さ２．８ｍ）、中央の約０．７ｍ〜約２．４ｍの部分は
、９５０ 〜１０５０℃に加熱されていた。すなわち、
先述のように鉄が水蒸気によって酸化される際の発熱に
より加熱されたのである。このように他に燃料を加える
必要なく、高い熱効率でスクラップを水蒸気にて酸化し
、水素を製造できることが判明した。また、混入された
不純物としての銅は、水蒸気酸化処理後のスクラップ中
にメタル状態のまま残存していた。[0024] The scrap in the furnace (the height of the scrap layer was 2.8 m) was heated to a temperature of 950 to 1050°C in the central portion of about 0.7 m to about 2.4 m. That is,
As mentioned earlier, iron was heated by the heat generated when it was oxidized by steam. In this way, it has been found that hydrogen can be produced by oxidizing scrap with steam with high thermal efficiency without the need to add any other fuel. In addition, copper as an impurity mixed in remained in the scrap after the steam oxidation treatment in a metal state.
【００２５】[0025]
【実施例３】実施例２で水蒸気酸化処理後のスクラップ
をクラシャーで５〜３０ｍｍサイズに破砕し、遠心力を
利用した比重分離を行った後、磁選を行いマグネタイト
主体の部分とＣｕ、Ｎｉ、Ｓｎ等非鉄金属主体の部分に
分離した。
なお、大部分がマグネタイトに酸化されているため破砕
は容易であった。処理前のスクラップ中のトランプエレ
メントの含有量は平均でＣｕ：０．３０ ％、Ｎｉ：０
．０７ ％、Ｓｎ：０．０１８％であったが、上記処理
後の分離回収したマグネタイト主体回収物中にはＣｕ、
Ｎｉ、Ｓｎがそれぞれ０．０２％、０．０１％、０．０
０５ ％しか含まれていなかった。以上のように、本発
明により処理したスクラップを破砕後、選別することに
よりトランプエレメント含有量が少ない製鋼用原料等の
鉄源として回収できる。[Example 3] The scrap after the steam oxidation treatment in Example 2 was crushed into 5-30 mm size pieces using a crusher, and after specific gravity separation using centrifugal force, magnetic separation was performed to separate the mainly magnetite part from Cu, Ni, It was separated into parts consisting mainly of non-ferrous metals such as Sn. Note that crushing was easy because most of it was oxidized to magnetite. The average content of playing card elements in scrap before processing is Cu: 0.30%, Ni: 0
．． 0.07%, Sn: 0.018%, but in the magnetite-based recovered material separated and recovered after the above treatment, Cu,
Ni and Sn are 0.02%, 0.01%, and 0.0, respectively.
It contained only 0.5%. As described above, by crushing and sorting the scrap treated according to the present invention, it can be recovered as an iron source such as a raw material for steelmaking with a low content of tramp elements.
【００２６】[0026]
【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、水蒸気酸化処理後の
スクラップ （酸化鉄） を粉砕、選別処理することに
より、酸化鉄はトランプエレメント含有量の少ない良質
な鉄源として、酸化されないＣｕ、Ｎｉ、Ｓｎ等の非鉄
金属はそれぞれの金属源としてそれぞれ回収できるので
あって、産業上の意義は大きい。Effects of the Invention According to the present invention, H2 gas, which is clean energy, can be produced by using old scrap that contains a lot of impurities such as Cu (tramp elements) and is difficult to reuse as a direct source of iron. By crushing and sorting the scrap (iron oxide) after processing, iron oxide can be used as a high-quality iron source with low tramp element content, and non-ferrous metals such as Cu, Ni, and Sn, which cannot be oxidized, can be used as sources of each metal. Since it can be recovered, it has great industrial significance.
【図１】鉄板を２０時間水蒸気酸化した後の酸化層厚さ
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】本発明の実施例に用いた固定層型反応器の概略
説明図である。FIG. 2 is a schematic explanatory diagram of a fixed bed reactor used in an example of the present invention.
【図３】本発明の実施例に用いたシャフト炉型反応器の
概略説明図である。FIG. 3 is a schematic explanatory diagram of a shaft furnace type reactor used in an example of the present invention.
Claims (4)
００ ℃以上の高温状態で水蒸気により酸化して水素ガ
スを製造するとともに、水蒸気による酸化処理後のスク
ラップを回収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
A method for reusing iron-based scrap, which involves producing hydrogen gas by oxidizing it with steam at a high temperature of 00°C or higher, and recovering the scrap after the oxidation treatment with steam.
して使用することを特徴とする請求項１記載の方法。2. Process according to claim 1, characterized in that a countercurrent moving bed, such as a shaft furnace, is used as the reactor.
ダー等の切断処理により、サイジングおよび選別を行っ
たものを用いる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 iron-based scrap is sized and sorted by cutting using a shredder or the like.
クラップを破砕後、酸化鉄は製鋼原料等の鉄源として、
酸化されないＣｕ、Ｎｉ、Ｓｎ等はそれぞれの金属源と
してそれぞれ分離回収する鉄系スクラップの再利用方法
。4. After crushing the scrap treated by the method according to claim 1, the iron oxide is used as an iron source for steelmaking raw materials, etc.
A method of recycling iron-based scrap in which unoxidized Cu, Ni, Sn, etc. are separated and recovered as their respective metal sources.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3085494A JPH04318124A (en) | 1991-04-17 | 1991-04-17 | Method for reusing ferrous scrap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3085494A JPH04318124A (en) | 1991-04-17 | 1991-04-17 | Method for reusing ferrous scrap |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04318124A true JPH04318124A (en) | 1992-11-09 |
Family
ID=13860490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3085494A Withdrawn JPH04318124A (en) | 1991-04-17 | 1991-04-17 | Method for reusing ferrous scrap |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04318124A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620398B2 (en) | 2001-03-06 | 2003-09-16 | Alchemix Corporation | Method for the production of ammonia |
| US6663681B2 (en) | 2001-03-06 | 2003-12-16 | Alchemix Corporation | Method for the production of hydrogen and applications thereof |
| EP1373131A1 (en) * | 2001-03-06 | 2004-01-02 | Alchemix Corporation | Method for the production of hydrogen and applications thereof |
| US6682714B2 (en) | 2001-03-06 | 2004-01-27 | Alchemix Corporation | Method for the production of hydrogen gas |
| US6685754B2 (en) | 2001-03-06 | 2004-02-03 | Alchemix Corporation | Method for the production of hydrogen-containing gaseous mixtures |
| US7232472B2 (en) | 2001-03-06 | 2007-06-19 | Alchemix Corporation | Method for the treatment of coal |
| WO2008151367A1 (en) * | 2007-06-12 | 2008-12-18 | Alternative Energy International Ltd | A system for production of hydrogen |
| JP2019212849A (en) * | 2018-06-08 | 2019-12-12 | パナソニックＩｐマネジメント株式会社 | Method for recycling magnetic substance material |
| WO2020174573A1 (en) * | 2019-02-26 | 2020-09-03 | 日揮グローバル株式会社 | Residue processing method and sulfatizing roasting method |
-
1991
- 1991-04-17 JP JP3085494A patent/JPH04318124A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620398B2 (en) | 2001-03-06 | 2003-09-16 | Alchemix Corporation | Method for the production of ammonia |
| US6663681B2 (en) | 2001-03-06 | 2003-12-16 | Alchemix Corporation | Method for the production of hydrogen and applications thereof |
| EP1373131A1 (en) * | 2001-03-06 | 2004-01-02 | Alchemix Corporation | Method for the production of hydrogen and applications thereof |
| US6682714B2 (en) | 2001-03-06 | 2004-01-27 | Alchemix Corporation | Method for the production of hydrogen gas |
| US6685754B2 (en) | 2001-03-06 | 2004-02-03 | Alchemix Corporation | Method for the production of hydrogen-containing gaseous mixtures |
| US7232472B2 (en) | 2001-03-06 | 2007-06-19 | Alchemix Corporation | Method for the treatment of coal |
| EP1373131A4 (en) * | 2001-03-06 | 2007-10-03 | Alchemix Corp | Method for the production of hydrogen and applications thereof |
| WO2008151367A1 (en) * | 2007-06-12 | 2008-12-18 | Alternative Energy International Ltd | A system for production of hydrogen |
| JP2019212849A (en) * | 2018-06-08 | 2019-12-12 | パナソニックＩｐマネジメント株式会社 | Method for recycling magnetic substance material |
| WO2020174573A1 (en) * | 2019-02-26 | 2020-09-03 | 日揮グローバル株式会社 | Residue processing method and sulfatizing roasting method |
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