JP5488098B2 - Treatment method for acid-resistant waste bricks - Google Patents
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Description
本発明は、乾式銅製錬において発生する製錬ガスから硫酸を製造する過程で使用されたレンガで、耐用年数後に更新されて廃棄物となる耐酸レンガを効率的に処分する方法に関するものである。 The present invention relates to a method for efficiently disposing of acid-resistant bricks that are used in the process of producing sulfuric acid from smelting gas generated in dry copper smelting and that are renewed after the service life and become waste.
銅製錬において硫化鉱石から金属銅を製造する工程は、銅品位が１〜２％程度の硫化鉱石を選鉱処理することによって銅品位が３０％程度の硫化銅精鉱を得て、産地ごとに異なる不純物組成をもつ硫化銅精鉱を、組成がなるべく均一となるように調合して得られる硫化銅精鉱（以下、単に銅精鉱という）に、珪酸鉱を主体とするフラックス等の装入物および重油、微粉炭またはコークス等の燃料を、予熱した酸素富化空気とともに銅製錬自溶炉（以下、単に自溶炉という）内に吹き込み、熱源の大半を占める銅精鉱中の硫黄の酸化による反応熱と燃料の燃焼熱とを加えて，銅精鉱を溶解するとともに酸化製錬を行い、硫化銅（Ｃｕ２Ｓ）および硫化鉄（ＦｅＳ）を主体とする溶体であるマットと、酸化鉄の珪酸塩を主体とする溶体であるカラミ（またはスラグ）を生成させる。ここで使用される珪酸鉱としては、通常硅石を用いている。
銅精鉱の主成分をＣｕＦｅＳ２とした例においては、酸化溶融製錬反応は以下のように進行すると考えられる。すなわち、先ず銅精鉱が（１）式に従って銅の硫化物と鉄の硫化物となる。
４ＣｕＦｅＳ２→ ２Ｃｕ２Ｓ＋２ＦｅＳ＋２ＦｅＳ２・・・・・（１）
鉄の硫化物のうち二硫化鉄（ＦｅＳ２）はさらに酸化されて（２）式に従って硫化鉄（ＦｅＳ）となる。
２ＦｅＳ２＋２Ｏ２→ ２ＦｅＳ ＋ ２ＳＯ２・・・・・（２）
こうしてできた硫化鉄（ＦｅＳ）は、（３）式に従ってさらに酸化されるとともにフラックス中の珪酸と結合して鉄珪酸塩となる。
４ＦｅＳ＋６Ｏ２＋４ＳｉＯ２→２Ｃｕ２Ｓ＋４ＦｅＯＳｉＯ２＋６ＳＯ２
・・・・・（３）
つまり上記（１）式から（３）式までの左右各編を加えると、銅精鉱の製錬反応は以下の（４）式で代表される。
４ＣｕＦｅＳ２＋４ＳｉＯ２＋８Ｏ２
→ ２Ｃｕ２Ｓ＋４ＦｅＯＳｉＯ２＋６ＳＯ２・・・・・・（４）
この際、炉内での反応に伴って発生する多量の亜硫酸ガス（ＳＯ２）は、硫酸工場へ導入して酸化して三酸化硫酸ガス（ＳＯ３）に転化した後、水に溶かして硫酸製造の原料とされる。銅精鉱の主成分が上記とは別の化学式形態をとる場合でも、製錬反応にともなってＳＯ２が多量に発生することは同様である。
The process of producing metallic copper from sulfide ore in copper smelting is different for each production area by obtaining copper sulfide concentrate with copper grade of about 30% by beneficiation treatment of sulfide ore with copper grade of about 1-2%. A copper sulfide concentrate with an impurity composition mixed as much as possible to a uniform composition (hereinafter simply referred to as “copper concentrate”) and a charge such as a flux mainly composed of silicate ore. In addition, fuel such as heavy oil, pulverized coal, or coke is blown into a copper smelting flash smelting furnace (hereinafter simply referred to as flash smelting furnace) together with preheated oxygen-enriched air to oxidize sulfur in copper concentrate that occupies most of the heat source. The reaction heat and fuel combustion heat are added to dissolve copper concentrate and oxidative smelting, and the mat is a solution mainly composed of copper sulfide (Cu 2 S) and iron sulfide (FeS), and oxidized. A solution consisting mainly of iron silicate. Mi (or slug) is produced. As the silicate ore used here, a meteorite is usually used.
In the example in which the main component of the copper concentrate is CuFeS 2 , it is considered that the oxidation melting smelting reaction proceeds as follows. That is, first, the copper concentrate becomes copper sulfide and iron sulfide according to the formula (1).
4CuFeS 2 → 2Cu 2 S + 2FeS + 2FeS 2 (1)
Of the iron sulfides, iron disulfide (FeS 2 ) is further oxidized to iron sulfide (FeS) according to the equation (2).
2FeS 2 + 2O 2 → 2FeS + 2SO 2 (2)
The iron sulfide (FeS) thus produced is further oxidized according to the formula (3) and combined with silicic acid in the flux to form iron silicate.
4FeS + 6O 2 + 4SiO 2 → 2Cu 2 S + 4FeOSiO 2 + 6SO 2
(3)
That is, when the left and right knittings from the above formula (1) to the formula (3) are added, the smelting reaction of copper concentrate is represented by the following formula (4).
4CuFeS 2 + 4SiO 2 + 8O 2
→ 2Cu 2 S + 4FeOSiO 2 + 6SO 2 (4)
At this time, a large amount of sulfurous acid gas (SO 2 ) generated along with the reaction in the furnace is introduced into a sulfuric acid factory, oxidized and converted into sulfuric acid trioxide gas (SO 3 ), dissolved in water, and then sulfuric acid. Made as a raw material for manufacturing. Even when the main component of the copper concentrate takes a chemical formula different from the above, it is the same that SO 2 is generated in a large amount with the smelting reaction.
より詳しくは、上記硫酸製造工程には、ＳＯ２を主成分とする製錬ガスの洗浄工程、ＳＯ２をＳＯ３に転化する転化工程、ＳＯ３を水や希硫酸に吸収させて濃硫酸を製造する吸収工程などが含まれており、吸収工程において使用される吸収塔という設備には、その内張りとして耐酸レンガが使用されている。
吸収塔の内張りに使用されている耐酸レンガは、設備の更新時にレンガの張替え作業が行なわれるので、設備の状態にもよるが、更新されて廃棄物となった耐酸レンガ（以下、耐酸廃レンガという場合がある）は２０〜３０年に１回、約１００ｔ規模で発生する。
耐用年数経過後に更新されて廃棄物となった耐酸レンガを、産業廃棄物として処分すると高額な処理費用が必要となり経済的損失を招く。
More specifically, the above-mentioned sulfuric acid manufacturing process, cleaning process of smelting gas mainly composed of SO 2, the conversion step of converting the SO 2 to SO 3, concentrated sulfuric acid by absorption of SO 3 in water or dilute sulfuric acid The absorption process etc. to manufacture are included, and the acid-resistant brick is used as the lining in the equipment called the absorption tower used in an absorption process.
The acid-resistant bricks used for the lining of the absorption tower are replaced by bricks when the equipment is renewed, so depending on the state of the equipment, the acid-resistant bricks (hereinafter referred to as acid-resistant bricks) that have been renewed and become waste Sometimes occurs on a scale of about 100 t once every 20-30 years.
Disposing of acid-resistant bricks that have been renewed after the end of their useful life and become wastes as industrial wastes requires high processing costs and causes economic losses.
また、上記洗浄工程においては洗浄塔という設備が使用され、洗浄塔の中で製錬排ガスを工業用水のシャワーの中に通過させることにより、重金属を含むヒュームなどを洗い落とすことが行なわれる。洗浄塔において水分を含んだガスとなるので、洗浄後に一度乾燥させている。しかし、洗浄工程において、ＳＯ２の一部は工業用水に吸収され硫酸を形成するので、乾燥塔の内張りにも耐酸レンガが使用され、頻度の違いはあるが同様に耐酸廃レンガが発生する。 In the above washing step, equipment called a washing tower is used. By passing the smelting exhaust gas through a shower of industrial water in the washing tower, fumes containing heavy metals are washed off. Since it becomes a gas containing moisture in the washing tower, it is dried once after washing. However, in the washing process, part of SO 2 is absorbed into industrial water to form sulfuric acid, so acid-resistant bricks are also used for the lining of the drying tower, and acid-resistant waste bricks are generated although there is a difference in frequency.
このようにして発生した耐酸廃レンガは、通常産業廃棄物として処理され、処理費用が嵩むという問題点だけでなく、最終処分場の不足の問題もあり、産業廃棄物として産廃業者への委託処理ができなくなる可能性があるという問題点がある。このため別の処理方法が要請されている。ところがこれまでに熔錬炉に使用された廃レンガから有価金属を分離回収する既存技術はあるが、使用済み耐酸レンガの処理方法は見当らない。 The acid-resistant waste bricks generated in this way are usually treated as industrial waste, which increases the processing cost, and there is also a problem of shortage of final disposal sites. There is a problem that it may not be possible. For this reason, another processing method is required. However, there are existing techniques for separating and recovering valuable metals from waste bricks used in smelting furnaces, but there is no method for treating used acid-resistant bricks.
使用済み耐酸レンガの処理方法については、例えば廃レンガを粉砕する際に問題となる廃レンガに付着した銅メタルを感知して排除する方法が公開されており（例えば、特許文献１参照。）、また、熔錬炉に使用された廃レンガから銅を回収する方法が公開されている（例えば、特許文献２参照。）が、いずれの方法も熔錬炉に使用されたレンガの廃棄が前提であり、上記の使用済み耐酸レンガの処理方法の問題点の解決には馴染まない。
硫酸製造工程で使用された耐酸廃レンガは比重が小さく、上記先行文献にあるようにカラミ選鉱工程に混ぜて処理すると、比重差が大きく、スラリーにした際に分離し、配管を閉塞させたりシックナーにて比重の小さい耐酸廃レンガの沈降を阻害する問題がある。
About the processing method of a used acid-resistant brick, the method of detecting and removing the copper metal adhering to the waste brick which becomes a problem, for example when grind | pulverizing a waste brick is disclosed (for example, refer patent document 1). Moreover, although the method of collect | recovering copper from the waste brick used for the smelting furnace is open | released (for example, refer patent document 2), all methods presuppose disposal of the brick used for the smelting furnace. Yes, it is not familiar with the solution of the above-mentioned problem of the method for treating used acid-resistant bricks.
The acid-resistant waste bricks used in the sulfuric acid production process have a low specific gravity, and when mixed with the calami beneficiation process as described in the previous literature, the specific gravity difference is large, and when separated into slurries, the pipes are blocked or thickened. There is a problem that obstructs the sedimentation of acid-resistant waste bricks with low specific gravity.
本発明はこのような状況を解決するためになされたものであり、廃棄処分が必要な廃耐酸レンガを産業廃棄物として処分するのではなく、安価かつ効率的に処分することが可能な、処理方法を提供することを課題とする。 The present invention has been made to solve such a situation, and does not dispose of waste acid-resistant bricks that need to be disposed of as industrial waste, but can be disposed of inexpensively and efficiently. It is an object to provide a method.
本発明者らは上記課題を解決するために、銅製錬プラントの硫酸製造工程から発生する
耐酸廃レンガを処理する際に、耐酸廃レンガとフラックス用の珪酸鉱との混合割合が、その珪酸鉱に対して重量比で３％以下となるように耐酸廃レンガを珪酸鉱原料と混合し、湿式粉砕により、粉末状に粉砕して、銅製錬工程のフラックス原料として使用することとした。この方法によれば安価で産業廃棄物を出さずに効率的に処理できることを見出し、本発明を完成させた。
すなわち、耐酸廃レンガをフラックス用珪酸鉱原料と混ぜ、ジョークラッシャーなどで
粗破砕し、さらにボールミルによって粒径が５０〜１００μｍの粉末状になるように粉砕
することで、自熔炉でのフラックス用珪酸鉱原料として供給することができる。
本発明においては、耐酸廃レンガと珪酸鉱との混合割合は、重量比で珪酸鉱に対して３重量％以下の割合とするのが重要であり、１重量％以下の割合とするのがより好ましい。
前記珪酸鉱としては、硅石を使用することができる。
In order to solve the above-mentioned problems, the present inventors treated the acid-resistant waste brick generated from the sulfuric acid production process of the copper smelting plant, and the mixing ratio of the acid-resistant waste brick and the silicate ore for flux is the silicate ore. the acid waste bricks at 3% or less by weight is mixed with silicofluoride Sanko material against, by wet grinding, was ground to a powder, it was decided to use as a flux material for copper smelting process. This method has been found to be inexpensive and can be processed efficiently without producing industrial waste, and the present invention has been completed.
That is, acid-resistant waste bricks are mixed with silicate ore raw materials for flux, coarsely crushed with a jaw crusher, etc., and further pulverized into a powder with a particle size of 50 to 100 μm by a ball mill, thereby producing silicic acid for flux in a self-melting furnace It can be supplied as a mineral raw material.
In the present invention, the mixing ratio of the resistance Sanhai brick and silica ore is important to the proportion of 3% by weight or less based on silica ore in a weight ratio, is given to a ratio of 1 wt% or less More preferred.
As the silicate ore, meteorite can be used.
本発明の耐酸レンガの処理方法では、産業廃棄物として処理するのではなく、粉末状のフラックス原料として自熔炉で繰返し使用することで有効活用できるので、その工業的価値は極めて大きい。 In the method for treating acid-resistant brick according to the present invention, it is not treated as industrial waste, but it can be effectively used by repeatedly using it as a powdery flux material in a flash furnace, so its industrial value is extremely high.
硫酸製造工程の転化器補修で発生する耐酸廃レンガは、主たる耐熱成分であるＳｉＯ２ 、Ａｌ２Ｏ３、ＭｇＯ、ＣａＯを含んでいる。この耐酸廃レンガは銅精鉱の製錬反応で必要とされるＳｉＯ２を７４〜７６重量％程度含有しており、耐酸廃レンガを自熔炉操業用の珪酸鉱として使用できることが期待される。 The acid-resistant waste bricks generated by the repair of the converter in the sulfuric acid production process contain SiO 2 , Al 2 O 3 , MgO, and CaO that are the main heat-resistant components. This acid-resistant waste brick contains about 74 to 76% by weight of SiO 2 required for the smelting reaction of copper concentrate, and it is expected that the acid-resistant waste brick can be used as a silicate ore for flash furnace operation.
自熔炉操業用の珪酸鉱の原単位は、原料銅精鉱の品位に応じて前記（１）式で示される反応に従って決めなければならない。前記（１）式で示されるように銅精鉱の酸化反応で必要とされるのは、ＳｉＯ２成分である。耐酸廃レンガにはＳｉＯ２成分の他にＡｌ２Ｏ３、ＭｇＯ、ＣａＯ、Ｃｒ２Ｏ３等が含まれているので、これらの影響を考慮すると耐酸廃レンガの使用には当然限界がある。 The basic unit of the silicate ore for the operation of the self-melting furnace must be determined according to the reaction represented by the above formula (1) according to the quality of the raw copper concentrate. As shown by the formula (1), what is required in the oxidation reaction of copper concentrate is a SiO 2 component. Since the acid-resistant waste brick contains Al 2 O 3 , MgO, CaO, Cr 2 O 3 and the like in addition to the SiO 2 component, there is a limit to the use of the acid-resistant waste brick in consideration of these effects.
自熔炉操業で大切なのは、マットへの銅成分の移行を促進させるとともに、カラミ中への銅の捕捉を押さえて銅の回収効率を高めることである。
好ましい操業状態では、マット中のＣｕ分は６４〜６９重量％、Ｆｅ分は１０〜１５重量％、Ｓは１８〜２２重量％程度である。また、好ましいカラミとは、Ｃｕ含有量が０．６５〜０．９０重量％、Ｆｅ含有量が４０〜４４重量％、ＳｉＯ２ 含有量が２６〜３０重量％で、Ｆｅ／ＳｉＯ２ （モル比 ）が１．０〜１．４程度である。
このようなカラミの好ましい組成は、ＳｉＯ２：２６〜２８重量％、 Ａｌ２Ｏ３：４〜８重量％、ＭｇＯ：２４〜２８重量％、ＣａＯ：２〜５重量％程度である。ＦｅはＦｅ３Ｏ４を生成するとカラミ融点が高くなり、半溶融状態のまま炉内に残留するので、Ｃｕの巻き込みが多くなったり操業上の支障を来すようになるので、表面に粉炭を供給したり銑鉄を添加してＦｅ３Ｏ４をＦｅＯに還元するのが有効である。また、カラミ中のＭｇＯやＣａＯもカラミの融点を高めて流動性を悪化させる。Ａｌ２Ｏ３は中性成分として作用する。カラミ中にはこの他に金、銀、鉛、亜鉛、アンチモン、ビスマス等の有用金属を含むので、さらに精製工程に移して回収する。
What is important in the operation of the self-melting furnace is to promote the transfer of the copper component to the mat and to increase the copper recovery efficiency by suppressing the capture of copper in the calami.
In a preferable operation state, the Cu content in the mat is 64 to 69% by weight, the Fe content is 10 to 15% by weight, and S is about 18 to 22% by weight. Further, preferable calami has a Cu content of 0.65 to 0.90% by weight, an Fe content of 40 to 44% by weight, an SiO 2 content of 26 to 30% by weight, and Fe / SiO 2 (molar ratio). ) Is about 1.0 to 1.4.
A preferred composition of such Karami is, SiO 2: 26 to 28 wt%, Al 2 O 3: 4~8 wt%, MgO: 24 to 28 wt%, CaO: is about 2-5 wt%. When Fe forms Fe 3 O 4 , the melting point of calami increases, and it remains in the furnace in a semi-molten state, so that Cu entrainment increases and troubles in operation occur. It is effective to supply Fe or add pig iron to reduce Fe 3 O 4 to FeO. Further, MgO and CaO in the calami also increase the melting point of the calami and deteriorate the fluidity. Al 2 O 3 acts as a neutral component. Since calami contains other useful metals such as gold, silver, lead, zinc, antimony, bismuth, etc., it is further transferred to a purification process and recovered.
このような条件下で耐酸廃レンガの珪酸（ＳｉＯ２）分を利用するには、使用する銅精鉱と目標とするマット組成とカラミ組成を設定し、前述の反応式（４）に基づいて配合計算をして決定する。
カラミ中のＭｇＯ、ＣａＯやＡｌ２Ｏ３、Ｃｒ２Ｏ３を目標値に抑えるためには、耐酸廃レンガの配合量は多くとも硅石鉱原料の３重量％以下とするのが限度である。耐酸廃レンガの配合量が３重量％を越えるとＭｇＯ、ＣａＯやＡｌ２Ｏ３等の脈石成分が多くなり、カラミの融点や粘度が上昇し、操業に支障を来す恐れがある。耐酸廃レンガの発生が十数年に一度であるため、この程度の耐酸廃レンガの使用量でも再利用しながら処分可能な量である。尚、前記耐酸レンガの代表的な組成は、ＳｉＯ２：７４重量％以上、Ａｌ２Ｏ３：１４重量％以上、ＭｇＯ・ＣａＯ：２重量％程度である。廃レンガとなっても、この組成に大きな変動はない。
To use the silicic acid (SiO 2 ) content of acid-resistant waste bricks under such conditions, set the copper concentrate to be used, the target mat composition and the calami composition, and based on the above reaction formula (4) Determine by blending calculation.
In order to keep MgO, CaO, Al 2 O 3 , and Cr 2 O 3 in the calami to the target values, the amount of acid-resistant waste bricks is limited to 3% by weight or less of the meteorite ore raw material at most. If the blending amount of acid-resistant waste bricks exceeds 3% by weight, gangue components such as MgO, CaO, and Al 2 O 3 increase, and the melting point and viscosity of the calami rise, which may hinder the operation. Since the generation of acid-resistant waste bricks occurs once every ten or so years, even this amount of acid-resistant waste bricks can be disposed of while being reused. Incidentally, a typical composition of the acid brick, SiO 2: 74 wt% or more, Al 2 O 3: 14 wt% or more, MgO · CaO: about 2 wt%. Even if it becomes waste brick, there is no big change in this composition.
硫酸製造工程の転化器補修で発生した耐酸廃レンガは、フラックス用原料である珪酸鉱に３重量％以下の割合で添加して混合した後、クラッシャーによる破砕工程で１５ｍｍ程度に破砕し、さらにボールミルを使って湿式粉砕を行い、７５μｍの篩目を６０〜８０重量％が通過できるように粉砕する。粉砕後のスラリーをシックナーにて粗粒を沈降させ、濃縮してセラミックフィルター等の脱水機にて脱水する。
珪酸鉱は自溶炉で銅精鉱とともに酸素付加空気で炉内に吹き込み、基本的には燃料を使用しないで溶解させねばならないので、５０〜１００μｍと充分細かい粒径にしておく必要がある。この粒径の粉末を得るには、上記したとおり、７５μｍの篩目を６０〜８０重量％が通過できるように粉砕すれば良い。
The acid-resistant waste bricks generated during the repair of the converter in the sulfuric acid production process are added to and mixed with silicate ore, which is a raw material for flux, in a proportion of 3% by weight or less, and then crushed to about 15 mm in a crusher crushing process. Is used to perform wet pulverization and pulverize so that 60 to 80% by weight of a 75 μm sieve can pass through. The crushed slurry is allowed to settle coarse particles with a thickener, concentrated and dehydrated with a dehydrator such as a ceramic filter.
Silicate ore is blown into the furnace with oxygen concentrate air together with copper concentrate in the flash smelting furnace, and basically must be dissolved without using fuel, so it is necessary to make the particle diameter as sufficiently fine as 50 to 100 μm. In order to obtain a powder having this particle size, as described above, it may be pulverized so that 60 to 80% by weight of a 75 μm sieve can pass through.
耐酸廃レンガは比重が２．３ｇ／ｃｍ３で、珪酸鉱は比重が２．８ｇ／ｃｍ３であるので、特定の混合割合であれば、破砕や粉砕工程を流す間に互いに均一に混合することができる。異種原料の比重差が大きいと、湿式粉砕した際に、スラリーが２層に分かれ、配管径が変わる箇所や角でスムーズに流れなくなることによる配管詰まりや、シックナーでは比重の小さい成分が沈降しにくくなるといった問題が発生するが、耐酸廃レンガと珪酸鉱の比重差は小さいのでこれらの問題は発生しない。
珪酸鉱としては、一般に硅石を使用する。
尚、破砕や粉砕工程のうち、前記均一な混合状態を維持するのがもっとも困難なのは、ボールミルを使用した湿式粉砕が工程である。通常操業においては、連続式のボールミルが使用されており、内容物が均一な混合状態であることを前提に操業されている。このため、ボールミルの回転によって比重の小さな粉末と比重の大きな粉末とが、２層にわかれると、比重の小さな粉末は、所定の湿式粉砕を受けずにボールミルから排出され、その結果ボールミルから排出される粉末に、０．５〜１．５ｍｍ程度の粗粒が目視でも判別できる程度に混入する。
このため、前記耐酸廃レンガと珪酸鉱との混合割合は、珪酸鉱に対して重量比で３％以下とすることが重要である。この重量比が３％を超えると、前記均一な混合状態を維持することが困難となり、粗粒が多量に発生し、７５μｍの篩目で６０重量％以上を通過させることができなくなるからである。
発明者らは、耐酸廃レンガの配合量は多くとも硅石鉱原料の３重量％以下とすることによって、組成上の要請と、粒径の要請の両方を満たすことができるので、本発明の効果が発現するものと考えている。
以上説明したとおり、本発明によれば、廃棄処分が必要な廃耐酸レンガを産業廃棄物として処分するのではなく、安価かつ効率的に処分することができる。
The acid-resistant waste brick has a specific gravity of 2.3 g / cm 3 and the silicate ore has a specific gravity of 2.8 g / cm 3 , so if the mixing ratio is a specific ratio, they are mixed evenly during the crushing and crushing process. be able to. If the difference in specific gravity of different types of raw materials is large, the slurry will be divided into two layers when wet pulverized, clogging of pipes due to the fact that the pipe diameter will change and corners will not flow smoothly, and thickeners will not settle easily. However, since the difference in specific gravity between acid-resistant waste brick and silicate ore is small, these problems do not occur.
As the silicate ore, meteorite is generally used.
Of the crushing and crushing processes, the most difficult to maintain the uniform mixed state is a wet crushing process using a ball mill. In normal operation, a continuous ball mill is used, and it is operated on the assumption that the contents are in a uniform mixed state. For this reason, when a powder having a small specific gravity and a powder having a large specific gravity are separated into two layers by the rotation of the ball mill, the powder having a small specific gravity is discharged from the ball mill without being subjected to a predetermined wet pulverization, and as a result, discharged from the ball mill. In the powder, coarse particles of about 0.5 to 1.5 mm are mixed so that they can be visually discerned.
For this reason, it is important that the mixing ratio of the acid-resistant waste brick and the silicate ore is 3% or less by weight with respect to the silicate ore. When this weight ratio exceeds 3%, it becomes difficult to maintain the uniform mixed state, and a large amount of coarse particles are generated, and it becomes impossible to pass 60% by weight or more through a 75 μm sieve mesh. .
The inventors can satisfy both the compositional requirement and the particle size requirement by setting the blending amount of acid-resistant waste brick to 3% by weight or less of the meteorite ore raw material at most. Is believed to develop.
As described above, according to the present invention, waste acid-resistant bricks that need to be disposed of can be disposed of at low cost and efficiently, rather than as industrial waste.
耐酸廃レンガ１．５トンに対して珪石３００トンの割合で混合（混合割合０．５重量％）して、ジョークラッシャーとコーンクラッシャーで１２ｍｍのスクリーンを通過するまで粗破砕を行い、さらにボールミルにて湿式粉砕をおこなった。湿式粉砕後のスラリーは７５μｍの篩目を７０〜７５重量％が通過するまで細かく粉砕した。その後は、スラリーをシックナーに入れて粗粒を沈降させ、濃度を５０〜６０％にまで濃縮したスラリーをセラミックフィルターにて脱水して、水分率を１５〜１８％とし、フラックス用原料として銅精鉱１トン当たり１５０キログラムの割合で配合して自熔炉へ供給した。 Mixing 1.5 tons of acid-resistant waste bricks at a rate of 300 tons of silica (mixing ratio 0.5% by weight), roughly crushing with a jaw crusher and cone crusher until it passes through a 12 mm screen, And wet pulverized. The slurry after wet pulverization was finely pulverized until 70 to 75% by weight of a 75 μm sieve was passed. After that, the slurry is put into a thickener to settle coarse particles, and the slurry concentrated to 50 to 60% is dehydrated with a ceramic filter to a moisture content of 15 to 18%. It was blended at a rate of 150 kilograms per ton of ore and supplied to the flash furnace.
その結果、ボールミルによる湿式粉砕において、均一な混合状態は保たれており、粉砕後の粉末に０．５〜１．５ｍｍといった粗粒の発生は見られなかった。また、自溶炉におけるマット中のＣｕ分は６７重量％、Ｆｅ分は１３重量％、Ｓは１９重量％であった。また、カラミ中のＣｕ分は０．７重量％、Ｆｅ分は４２重量％、ＳｉＯ２ 分は２８重量％あった。
以上のように、実施例１においては、極めて安定した良好な操業を維持しつつ、耐酸廃レンガをフラックス用原料として利用することができた。
As a result, in the wet pulverization by the ball mill, a uniform mixed state was maintained, and generation of coarse particles such as 0.5 to 1.5 mm was not observed in the pulverized powder. Further, the Cu content in the mat in the flash furnace was 67% by weight, the Fe content was 13% by weight, and S was 19% by weight. Further, the Cu content in the calami was 0.7% by weight, the Fe content was 42% by weight, and the SiO 2 content was 28% by weight.
As described above, in Example 1, acid-resistant waste bricks could be used as a raw material for flux while maintaining a very stable and good operation.
耐酸廃レンガ３．０トンに対して硅石３００トンの割合で混合（混合割合１．０重量％）した以外は、実施例１と同様の操業を行った。
その結果、ボールミルによる湿式粉砕において、均一な混合状態は保たれており、粉砕後の粉末に０．５〜１．５ｍｍといった粗粒の発生は見られなかった。尚、７５μｍの篩目を６５〜７０重量％が通過した。
その結果、実施例１と同様、安定した操業を維持しつつ、耐酸廃レンガをフラックス用原料として利用することができた。
The same operation as in Example 1 was performed except that 3.0 tons of acid-resistant waste bricks were mixed at a ratio of 300 tons of meteorite (mixing ratio: 1.0% by weight).
As a result, in the wet pulverization by the ball mill, a uniform mixed state was maintained, and generation of coarse particles such as 0.5 to 1.5 mm was not observed in the pulverized powder. In addition, 65-70 weight% of 75-micrometer sieves passed.
As a result, as in Example 1, acid-resistant waste bricks could be used as a flux raw material while maintaining a stable operation.
耐酸廃レンガ９．０トンに対して硅石３００トンの割合で混合（混合割合２．９重量％）した以外は、実施例１と同様の操業を行った。
その結果、ボールミルによる湿式粉砕において、ほぼ均一な混合状態は保たれていた。粉砕後の粉末に０．５〜１．５ｍｍといった粗粒の発生が見られたが、ごく僅かであり、７５μｍの篩目を６０〜６５重量％が通過した。
また、マット成分やカラミ成分は実施例１と同様、安定した操業を維持しつつ、耐酸廃レンガをフラックス用原料として利用することができた。
The same operation as in Example 1 was carried out except that 9.0 tons of acid-resistant waste bricks were mixed at a ratio of 300 tons of meteorite (mixing ratio of 2.9% by weight).
As a result, a substantially uniform mixed state was maintained in the wet pulverization by the ball mill. Coarse particles such as 0.5 to 1.5 mm were observed in the pulverized powder, but the amount was very small, and 60 to 65% by weight of a 75 μm sieve passed through.
Moreover, the mat | matte component and the calami component were able to utilize the acid-resistant waste brick as a raw material for flux, maintaining the stable operation similarly to Example 1.
(比較例１）
耐酸廃レンガ１０．０トンに対して硅石３００トンの割合で混合（混合割合３．３重量％）した以外は、実施例１と同様の操業を行った。
その結果、ボールミルによる湿式粉砕において、均一な混合状態の維持が困難で、粉砕後の粉末に０．５〜１．５ｍｍといった粗粒が多く発生し、７５μｍの篩目を５０〜６５重量％しか通過させることが出来なかった。
また、前記した粉砕後の粉末から粗粒を取り除いて、引き続き操業をおこなった。その結果、マット成分は安定状態の範囲内であったが、カラミ成分のうち、例えばカラミ中のＣｕ分は１．０重量％を超えており、目標成績を達成した安定操業を維持することができなかった。
(Comparative Example 1)
The same operation as in Example 1 was carried out except that 10.0 tons of acid-resistant waste bricks were mixed at a ratio of 300 tons of meteorite (mixing ratio: 3.3% by weight).
As a result, in the wet pulverization by the ball mill, it is difficult to maintain a uniform mixed state, and a lot of coarse particles such as 0.5 to 1.5 mm are generated in the pulverized powder, and the mesh size of 75 μm is only 50 to 65% by weight. I couldn't pass it.
Further, the coarse particles were removed from the powder after pulverization, and the operation was continued. As a result, the mat component was within the range of the stable state, but among the calami components, for example, the Cu content in the calami exceeds 1.0% by weight, and the stable operation that achieves the target results can be maintained. could not.
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