JP2015105436A - Pretreatment method of copper-containing molybdenite - Google Patents

Pretreatment method of copper-containing molybdenite Download PDF

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JP2015105436A
JP2015105436A JP2013258499A JP2013258499A JP2015105436A JP 2015105436 A JP2015105436 A JP 2015105436A JP 2013258499 A JP2013258499 A JP 2013258499A JP 2013258499 A JP2013258499 A JP 2013258499A JP 2015105436 A JP2015105436 A JP 2015105436A
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copper
molybdenite
sulfuric acid
pretreatment method
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JP5833621B2 (en
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ヨンユン チョ
Young Yoon Choi
ヨンユン チョ
シュンミュン シン
Shun Myung Shin
シュンミュン シン
チュルウ ナム
Chul Woo Nam
チュルウ ナム
ヒョンソク キム
Hyung Suk Kim
ヒョンソク キム
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Korea Institute of Geoscience and Mineral Resources KIGAM
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes

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Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment method of copper-containing molybdenite that removes copper alone while minimizing oxidation of molybdenum in reacting low-grade molybdenite containing copper sulfide with sulfuric acid to produce ferromolybdenum for steel making.SOLUTION: Before pretreatment, molybdenite is subjected to ore flotation to separate minerals on the hydrophilic surface leaving the minerals in a solution, and further may be subjected to crushing and granulating to improve reactivity with sulfuric acid. The pretreatment includes a step for mixing the copper-containing molybdenite with sulfuric acid at an equivalence ratio of 0.9-1.8, a step for heating and subjecting the mixture to sulfation reaction at 180-240°C for 20-80 minutes, a step for water exudation by adding water and agitating after the sulfation reaction, a step for separating a solid from a liquid after the water exudation, and a step for drying the separated solid.

Description

本発明は、低品位の輝水鉛鉱に含有されている銅を除去する銅含有輝水鉛鉱の前処理方法に関する。   The present invention relates to a pretreatment method for copper-containing molybdenite, which removes copper contained in low-grade molybdenite.

モリブデンは、鉄鋼の熱間クリープ特性を改善し、浮上脆性を防止し、鋼の耐食性を増大する役目を果たして、耐熱鋼の製造や合金元素として耐食鋼製造に非常に重要な元素である。製鋼用フェロモリブデンにおいて銅含有量は、通常、０.５％以下に制限される。   Molybdenum is a very important element in the production of heat-resistant steel and as an alloying element in the production of corrosion-resistant steel by improving the hot creep characteristics of steel, preventing floating embrittlement, and increasing the corrosion resistance of steel. In ferromolybdenum for steel making, the copper content is usually limited to 0.5% or less.

輝水鉛鉱(molybdenite, MoS2)は、経済性のあるモリブデンの一次的な原料であって、原鉱においてモリブデンの濃度が、通常、約０.０５〜０.１質量％に過ぎないため濃度が低いが、硫化鉱の特性上、浮遊選別により、銅、鉄などと共に、硫化物を容易に回収濃縮することができる。 Molybdenite (MoS 2 ) is the primary raw material for economical molybdenum, and the concentration of molybdenum in the ore is usually only about 0.05 to 0.1% by mass. However, due to the characteristics of sulfide ore, sulfides can be easily recovered and concentrated together with copper, iron, etc. by floating selection.

選鉱工程だけで輝水鉛鉱中の銅含有量を０.５％以下に低くすることは、銅鉱石も硫化鉱であるため困難さがあり、モリブデンの回収率が低下することがあるため、銅含有量が高い輝水鉛鉱も、銅含有量を低くすることに困難さがあるが、それにもかかわらず、生産販売されている。   It is difficult to reduce the copper content in molybdenite to 0.5% or less only by the beneficiation process because copper ore is also a sulfide ore, and the recovery rate of molybdenum may decrease. Highly molybdenite has difficulty in reducing the copper content, but it is nevertheless produced and sold.

銅を含有する低品位の輝水鉛鉱から製鋼用フェロモリブデンは、輝水鉛鉱を焙焼して酸化物とした後、薄い硫酸溶液で浸出して、銅を除去し、ろ過及び乾燥後、熱還元工程を介して、フェロモリブデンを製造することができる。しかし、前記のような方法は、硫酸浸出に際して、水溶液にモリブデンが相当量溶けて損失するので、これを回収する工程が必要であり、浸出に際して、ＭｏＯ３が水と反応してモリブデン酸として存在するので、ろ過ケーキ(cake)の水分乾燥に多いエネルギーが消耗される。このような不都合を補うため、焙焼前、つまり、硫化物状態で浸出除去するための方法が開発されている。米国特許第1,895,811号(1933.01.31. 公開)は、鉱石の前処理方法(Process of treating ores)に関するものであって、高圧容器が不要であり、工程が簡単であるという利点があるが、モリブデン鉱に濃い硫酸を加えて高温で処理する場合、温度が高いほど銅硫化物との反応速度及び反応率が高くなり、輝水鉛鉱の表面も酸化されて、銅と共に水溶液で浸出される問題がある。そこで、銅の除去率は高くしながら、モリブデンの酸化は、最小化することができる工程の開発が必要な実情である。 Ferromolybdenum for steel making from low-grade molybdenite containing copper, after roasting molybdenite to an oxide, leaching with a thin sulfuric acid solution, removing copper, filtering and drying, heat Ferromolybdenum can be produced through a reduction process. However, in the above-described method, a considerable amount of molybdenum is dissolved and lost in the aqueous solution during sulfuric acid leaching, and thus a step for recovering this is necessary. During leaching, MoO 3 reacts with water and exists as molybdic acid. Therefore, a lot of energy is consumed for drying the moisture of the cake. In order to compensate for such inconvenience, a method for leaching and removing before roasting, that is, in a sulfide state, has been developed. US Pat. No. 1,895,811 (1933.01.31. Published) relates to a process of treating ores, which has the advantage that a high-pressure vessel is not required and the process is simple. When concentrated sulfuric acid is added to the ore and processed at a high temperature, the higher the temperature, the higher the reaction rate and reaction rate with copper sulfide, and the surface of molybdenite is oxidized and leached with an aqueous solution with copper. is there. Therefore, it is necessary to develop a process capable of minimizing the oxidation of molybdenum while the copper removal rate is high.

それで、本発明は、硫化銅を含有する低品位の輝水鉛鉱の硫酸と反応するに際して、モリブデンの酸化は最小化しながら、銅のみを除去することができる銅含有輝水鉛鉱の前処理方法を提供することにある。   Therefore, the present invention provides a pretreatment method for copper-containing molybdenite that can remove only copper while minimizing oxidation of molybdenum when reacting with sulfuric acid of low-grade molybdenite containing copper sulfide. It is to provide.

本発明が解決しようとする課題は、以上で言及した課題に制限することなく、触れていない他の課題は、以下の記載から、当業者にとって明確に理解されるだろう。   The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

前記課題を解決するため、本発明は、銅含有輝水鉛鉱と硫酸を混合する段階と、前記混合後、加熱して硫酸化反応させる段階と、前記硫酸化反応後、水を入れて撹拌して、水浸出させる段階と、前記水浸出後、固体と液体を分離する段階と、前記分離した固体を乾燥させる段階とを含む銅含有輝水鉛鉱の前処理方法を提供する。   In order to solve the above-mentioned problems, the present invention includes a step of mixing copper-containing molybdenite and sulfuric acid, a step of heating and then performing a sulfation reaction after the mixing, and a step of adding water and stirring after the sulfation reaction. A pretreatment method for copper-containing molybdenite comprising the steps of leaching with water, separating the solid and liquid after the leaching, and drying the separated solid.

ここで、前記硫酸化反応は、１８０−２４０℃で２０−８０分間、行われることを特徴とする。   Here, the sulfation reaction is performed at 180-240 ° C. for 20-80 minutes.

前記硫酸は、輝水鉛鉱に対して、０.９ −１.８の当量比で混合されることを特徴とする。   The sulfuric acid is mixed in an equivalent ratio of 0.9 to 1.8 with respect to the hydropyrite.

また、前記硫酸化反応は、２１０−２４０℃で４０−８０分間、行われることを特徴とする。   The sulfation reaction may be performed at 210-240 ° C. for 40-80 minutes.

前記水は、蒸留水、脱イオン水、軽水、及び重水からなる群から選ばれる１種以上であることを特徴とする。   The water is one or more selected from the group consisting of distilled water, deionized water, light water, and heavy water.

また、本発明による銅含有輝水鉛鉱の前処理方法は、輝水鉛鉱を硫酸と混合する前に、浮遊選鉱する段階を更に含むことができる。   The pretreatment method for copper-containing molybdenite according to the present invention may further include a step of flotation before mixing the molybdenite with sulfuric acid.

本発明によると、銅を含有した低品位の輝水鉛鉱から製鋼用フェロモリブデンを製造するため、輝水鉛鉱の処理に際して、硫酸化反応温度及び時間を調節することで、従来、モリブデンが水溶液で浸出されるという問題を防止することができ、銅の除去率を向上することができる。   According to the present invention, in order to produce ferromolybdenum for steel making from low-grade molybdenite containing copper, by adjusting the sulfation reaction temperature and time during treatment of molybdenite, The problem of leaching can be prevented and the copper removal rate can be improved.

また、硫化銅のみを硫酸銅で形成し、水に浸出させて除去するので、従来、焙焼後、硫酸浸出に比べて固液分離が容易であり、廃酸からモリブデンを回収するコストを低減することができる。   In addition, only copper sulfide is formed with copper sulfate and leached into water to remove it. Conventionally, after roasting, solid-liquid separation is easier than sulfuric acid leaching, and the cost of recovering molybdenum from waste acid is reduced. can do.

図１は、本発明による銅含有輝水鉛鉱の前処理方法を示すシーケンス図である。FIG. 1 is a sequence diagram showing a pretreatment method for copper-containing molybdenite according to the present invention. 図２は、水−硫酸系での硫酸濃度による沸点を示すグラフである。FIG. 2 is a graph showing the boiling point depending on the sulfuric acid concentration in the water-sulfuric acid system. 図３は、本発明による銅含有輝水鉛鉱の前処理方法において、硫酸添加量による銅の除去率を示すグラフである。FIG. 3 is a graph showing the copper removal rate depending on the amount of sulfuric acid added in the pretreatment method for copper-containing molybdenite according to the present invention. 図４は、本発明による銅含有輝水鉛鉱の前処理方法において、硫酸添加量による輝水鉛鉱のＸ線回折分析結果を示す図である。FIG. 4 is a diagram showing an X-ray diffraction analysis result of molybdenite by the amount of sulfuric acid added in the pretreatment method for copper-containing molybdenite according to the present invention. 図５は、本発明による銅含有輝水鉛鉱の前処理方法において、硫酸化反応温度及び反応時間による輝水鉛鉱における銅の濃度変化を示すグラフである。FIG. 5 is a graph showing a change in the copper concentration in the molybdenite according to the sulfation reaction temperature and reaction time in the pretreatment method for copper-containing molybdenite according to the present invention. 図６は、本発明による銅含有輝水鉛鉱の前処理方法において、硫酸化反応温度及び時間によるモリブデンの溶解率変化を示すグラフである。FIG. 6 is a graph showing changes in molybdenum dissolution rate with sulfation reaction temperature and time in the pretreatment method for copper-containing molybdenite according to the present invention.

以下、添付の図面を参照して、本発明による好適な実施例を詳しく説明する。   Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

本発明の利点及び特徴、そして、それを達成する方法は、添付の図面と共に詳しく後述されている実施例を参照すると、明確になるだろう。   Advantages and features of the present invention, and methods for achieving the same, will become apparent with reference to the embodiments described in detail below in conjunction with the accompanying drawings.

しかし、本発明は、以下に開示される実施例により限定されるものではなく、互いに様々な形態で具現され、単に、本実施例は、本発明の開示が完全になるようにし、発明が属する技術の分野における通常の知識を有する者にとって、発明の範疇を完全に知らせるために提供されるものであり、本発明は、請求項の範疇によって定義されるだけである。   However, the present invention is not limited to the embodiments disclosed below, and may be embodied in various forms. The embodiments merely serve to complete the disclosure of the present invention and to which the invention belongs. It is provided to provide a general knowledge of the scope of the invention to those skilled in the art and the invention is only defined by the scope of the claims.

また、本発明を説明することに当たり、関連する公知技術などが本発明の要旨を濁ごすと判断される場合、それに関する詳しい説明は、省略することにする。   Further, in describing the present invention, when it is determined that related known technology or the like disturbs the gist of the present invention, a detailed description thereof will be omitted.

本発明は、銅含有輝水鉛鉱と硫酸を混合する段階と、前記混合後、加熱して硫酸化反応させる段階と、前記硫酸化反応後、水を入れて撹拌して水浸出させる段階と、前記水浸出後、固体と液体を分離する段階と、前記分離した固体を乾燥させる段階とを含む銅含有輝水鉛鉱の前処理方法を提供する。   The present invention includes a step of mixing copper-containing molybdenite and sulfuric acid, a step of heating and sulfating after the mixing, a step of adding water and stirring and leaching water after the sulfating reaction, Provided is a pretreatment method for copper-containing molybdenite comprising the steps of separating a solid and a liquid after the water leaching and drying the separated solid.

本発明による銅含有輝水鉛鉱の前処理方法は、硫化銅を含む低品位の輝水鉛鉱を硫酸と反応させて、輝水鉛鉱に含有した銅を硫酸銅として製造した後、水で浸出させて除去することができ、硫酸と反応に際して、温度及び時間を調節することで、銅除去率は高く、且つ、モリブデンの酸化は、最小化することができる。   The pretreatment method for copper-containing molybdenite according to the present invention is a method of reacting low-grade molybdenite containing copper sulfide with sulfuric acid to produce copper contained in molybdenite as copper sulfate, and then leaching it with water. By adjusting the temperature and time during the reaction with sulfuric acid, the copper removal rate is high, and the oxidation of molybdenum can be minimized.

図１は、本発明による銅含有輝水鉛鉱の前処理方法を示すシーケンス図である。以下、図１を参照して、本発明を詳しく説明する。   FIG. 1 is a sequence diagram showing a pretreatment method for copper-containing molybdenite according to the present invention. Hereinafter, the present invention will be described in detail with reference to FIG.

本発明による銅含有輝水鉛鉱の前処理方法は、銅含有輝水鉛鉱と硫酸とを混合する段階(Ｓ１００)を含む。   The pretreatment method for copper-containing molybdenite according to the present invention includes a step of mixing copper-containing molybdenite and sulfuric acid (S100).

本発明による銅含有輝水鉛鉱の前処理方法において、前記銅含有輝水鉛鉱は、黄銅鉱(chalcopyrite、CuFeS2)、輝銅鉱(chalcocite、Cu2S)、及び斑銅鉱(bornite、Cu5FeS4)などが含まれており、これらの鉱物を硫酸と反応させて硫酸銅とすることができる。この際、輝水鉛鉱は、硫酸と混合する前に、浮遊選鉱工程を行う段階を更に含み、輝水鉛鉱粒子中で疎水性表面を有する鉱物は、気泡の表面に取り付けて溶液の表面に浮上することになり、親水性表面の鉱物は、溶液中に残るようにして、分離することができる。また、輝水鉛鉱は、破砕及び粉砕する段階を更に含み、硫酸との反応性をより向上することができる。 In the pretreatment method of copper-containing molybdenite according to the present invention, the copper-containing molybdenite is chalcopyrite, CuFeS 2 , chalcocite, Cu 2 S, and porphyry (bornite, Cu 5 FeS). 4 ) and the like, and these minerals can be reacted with sulfuric acid to form copper sulfate. In this case, the hydropyrite ore further includes a step of a flotation process before mixing with sulfuric acid. Thus, the hydrophilic surface mineral can be separated so that it remains in solution. In addition, the hydropyrite ore further includes a step of crushing and pulverizing, and can further improve the reactivity with sulfuric acid.

また、輝水鉛鉱と硫酸とを均一に混合するために、硫酸で全体の輝水鉛鉱が十分濡れない場合は、水を添加して均一に混合することができる。   In addition, in order to uniformly mix the hydropyrite and sulfuric acid, when the entire molybdenite is not sufficiently wet with sulfuric acid, water can be added and mixed uniformly.

本発明による銅含有輝水鉛鉱の前処理方法は、前記混合後、加熱して硫酸化反応させる段階(Ｓ２００)を含む。   The pretreatment method for copper-containing molybdenite according to the present invention includes a step of heating and performing a sulfation reaction after the mixing (S200).

ここで、添加される硫酸量は、硫化物として存在するCu、Fe、Znなどは勿論のこと、低品位の輝水鉛鉱に含まれているアルカリ金属又はアルカリ土金属酸化物のように、硫酸と反応が可能な全ての元素を反応させることができる量が必要であるが、蒸発して損失される硫酸と不純物の種類により、反応性が様々であるため、原料や反応装置により、加減することができる。本発明による前処理方法では、輝水鉛鉱に対して、硫酸を０.９−１.８の当量比で混合することが望ましい。前記硫酸が、０.９当量比未満に混合する場合は、輝水鉛鉱に含まれた銅の除去率が低いという問題があり、１.８の当量比を超える場合は、輝水鉛鉱に含まれたモリブデンが浸出されるという問題がある。   Here, the amount of sulfuric acid added is not only Cu, Fe, Zn, etc. present as sulfide, but also sulfuric acid such as alkali metal or alkaline earth metal oxide contained in low-grade molybdenite. The amount that can react with all the elements that can react with is necessary, but depending on the type of sulfuric acid and impurities that are lost by evaporation, the reactivity varies, so it depends on the raw materials and reactor be able to. In the pretreatment method according to the present invention, it is desirable to mix sulfuric acid with an equivalence ratio of 0.9 to 1.8 with respect to the molybdenite. When the sulfuric acid is mixed to less than 0.9 equivalent ratio, there is a problem that the removal rate of copper contained in the molybdenite is low, and when it exceeds 1.8, it is contained in the molybdenite. There is a problem that the leached molybdenum is leached.

図２は、水−硫酸系における硫酸濃度による沸点(boiling point)を示すグラフである。図２に示しているように、大気圧において硫酸で処理可能な最高温度は、９８.３質量％付近の硫酸と水の共沸点(eutectic point)である３３０℃であることが分かり、参照として、９０質量％の硫酸の沸点は、２５５ ℃である。   FIG. 2 is a graph showing the boiling point depending on the sulfuric acid concentration in the water-sulfuric acid system. As shown in FIG. 2, it can be seen that the maximum temperature that can be treated with sulfuric acid at atmospheric pressure is 330 ° C., which is the eutectic point of sulfuric acid and water in the vicinity of 98.3% by mass. The boiling point of 90% by weight sulfuric acid is 255 ° C.

輝水鉛鉱を硫酸と硫酸化反応させると、下記の反応式１、２及び３に示しているように、輝水鉛鉱に含まれた銅が、硫酸銅で形成される。   When the hydrous lead ore is subjected to a sulfation reaction with sulfuric acid, the copper contained in the hydrous lead ore is formed with copper sulfate as shown in the following reaction formulas 1, 2 and 3.

［式１］
1/2CuFeS2+ 2H2SO4 → 1/2CuSO4 + 1/2FeSO4 + S + 2H2O + SO2↑ [Formula 1]
1 / 2CuFeS 2 + 2H 2 SO 4 → 1 / 2CuSO 4 + 1 / 2FeSO 4 + S + 2H 2 O + SO 2 ↑

［式２］
1/2CuS2+ 2H2SO4 → CuSO4 + 1/2S + 2H2O + SO2↑ [Formula 2]
1 / 2CuS 2 + 2H 2 SO 4 → CuSO 4 + 1 / 2S + 2H 2 O + SO 2 ↑

［式３］
1/4Cu5FeS4+ 3H2SO4 → 5/4CuSO4 + 1/4FeSO4 + S + 3H2O + 3/2SO2↑ [Formula 3]
1 / 4Cu 5 FeS 4 + 3H 2 SO 4 → 5/4 CuSO 4 + 1 / 4FeSO 4 + S + 3H 2 O + 3 / 2SO 2 ↑

下記の表１は、前記輝水鉛鉱に含まれたCuFeS2、Cu2S、及びCu5FeS4が硫酸と反応するに際して発生する反応熱(△Ｈ)、ギブス自由エネルギー(△Ｇ)、及び平衡定数(Ｋ)を示すものである。表１に示しているように、温度が高くなるほど、反応率(平衡定数)が増加し、反応熱は、弱い吸熱反応(△Ｈが正数)であることを分かる。 Table 1 below shows reaction heat (ΔH), Gibbs free energy (ΔG) generated when CuFeS 2 , Cu 2 S, and Cu 5 FeS 4 contained in the molybdenite react with sulfuric acid, and This shows the equilibrium constant (K). As shown in Table 1, the higher the temperature, the higher the reaction rate (equilibrium constant), and the reaction heat is a weak endothermic reaction (ΔH is a positive number).

輝水鉛鉱も、硫酸と反応させると、式４又は式５により表面が酸化されることができ、酸化された輝水鉛鉱は、水に相当量溶解される。   When hydrous lead ore is also reacted with sulfuric acid, the surface can be oxidized according to Formula 4 or 5, and the oxidized molybdenite is dissolved in a considerable amount in water.

［式４］
MoS2 + 2H2SO4 → MoO2+ 2S + 2H2O + 2SO2↑ [Formula 4]
MoS 2 + 2H 2 SO 4 → MoO 2 + 2S + 2H 2 O + 2SO 2 ↑

［式５］
MoS2 + 3H2SO4 → MoO3+ 2S + 3H2O + 3SO2↑ [Formula 5]
MoS 2 + 3H 2 SO 4 → MoO 3 + 2S + 3H 2 O + 3SO 2 ↑

下記の表２は、輝水鉛鉱と硫酸の酸化反応に対する反応熱(△Ｈ)、ギブス自由エネルギー(△Ｇ)、及び平衡定数(Ｋ)を示すものである。輝水鉛鉱と硫酸の酸化反応も、温度が増加することにつれ、反応率が増加することが分かる。   Table 2 below shows the heat of reaction (ΔH), Gibbs free energy (ΔG), and equilibrium constant (K) for the oxidation reaction of molybdenite and sulfuric acid. It can also be seen that the oxidation rate of hydropyrite and sulfuric acid increases as the temperature increases.

前述したように、銅硫化物と輝水鉛鉱とはいずれも、温度が増加することにより、反応率が高くなることが分かる。しかし、ＣｕとＭｏは、濃い硫酸と反応性において差がある。すなわち、Ｃｕ、Ｆｅなどの酸化物は塩基性酸化物で、硫酸と反応が容易である。これに対して、Ｍｏの酸化物は酸性酸化物で、硫酸とよく反応しない。これと類似に、硫化物も、ＣｕがＭｏの硫化物よりも容易に硫酸と反応する。それで、硫酸との反応条件を適切に調節すると、多くの銅硫化物は硫酸銅で形成され、ＭｏＳ２は反応しないことができる。それで、前記硫酸化反応は、１８０−２４０℃で、２０−８０分間、行われることが望ましい。前記硫酸化反応が１８０℃未満の場合は、銅除去率が低下するという問題があり、２４０℃を超える場合は、モリブデンの浸出率が増加して、浸出溶液からモリブデンを回収しなければならないという問題がある。また、前記硫酸化反応時間が２０分未満の場合は、輝水鉛鉱に含まれている銅が十分除去しないという問題があり、８０分を超える場合は、モリブデンが浸出されるという問題がある。 As described above, it can be seen that the reaction rate of both the copper sulfide and the molybdenite increases as the temperature increases. However, Cu and Mo have a difference in reactivity with concentrated sulfuric acid. That is, oxides such as Cu and Fe are basic oxides and can easily react with sulfuric acid. On the other hand, the oxide of Mo is an acidic oxide and does not react well with sulfuric acid. Analogous to this, sulfides also react with sulfuric acid more easily than sulfides with Cu being Mo. Therefore, if the reaction conditions with sulfuric acid are appropriately adjusted, many copper sulfides can be formed with copper sulfate and MoS 2 cannot react. Therefore, the sulfation reaction is preferably performed at 180-240 ° C. for 20-80 minutes. When the sulfation reaction is less than 180 ° C., there is a problem that the copper removal rate decreases, and when it exceeds 240 ° C., the leaching rate of molybdenum increases, and molybdenum must be recovered from the leaching solution. There's a problem. In addition, when the sulfation reaction time is less than 20 minutes, there is a problem that copper contained in the molybdenite is not sufficiently removed, and when it exceeds 80 minutes, molybdenum is leached.

硫酸化反応装置は、回分式又は連続式のいずれもが可能であるが、回分式反応装置の場合、反応物層を薄くして、反応物全体が均一な温度に維持されるようにする。連続式の場合も、反応器の全体温度が均一になるようにし、反応器内の反応物の滞留時間が同一であるように、反応物の流れを層流(plug flow)に維持する。硫酸化反応が終了した反応物は排出され、１００℃ 以下に冷却させることが望ましい。   The sulfation reactor can be either batch-wise or continuous, but in the case of a batch-type reactor, the reactant layer is made thin so that the entire reactant is maintained at a uniform temperature. Even in the continuous mode, the reactant flow is maintained in a laminar flow so that the overall temperature of the reactor is uniform and the residence time of the reactants in the reactor is the same. It is desirable that the reaction product after the sulfation reaction is discharged and cooled to 100 ° C. or lower.

本発明による銅含有輝水鉛鉱の前処理方法は、前記硫酸化反応後、水を入れて撹拌して水浸出させる段階(Ｓ３００)を含む。   The pretreatment method for copper-containing molybdenite according to the present invention includes a step (S300) of adding water and stirring and leaching the water after the sulfation reaction.

本発明による銅含有輝水鉛鉱の前処理方法において、硫酸化反応が終了した輝水鉛鉱は、撹拌器が備えられた浸出槽で回分式又は連続式で、硫酸銅及び他の不純物などを水で浸出させて除去することができる。前記水は、蒸留水、脱イオン水、軽水、及び重水からなる群から選ればれる１種以上を使用することができる。   In the pretreatment method of copper-containing molybdenite according to the present invention, the molybdenite after the sulfation reaction is completed in a batch or continuous manner in a leaching tank equipped with a stirrer, and copper sulfate and other impurities are watered. Can be leached and removed. As the water, one or more selected from the group consisting of distilled water, deionized water, light water, and heavy water can be used.

ついで、本発明による銅含有輝水鉛鉱の前処理方法は、前記水浸出後、固体と液体を分離する段階(Ｓ４００)を含む。   Next, the pretreatment method for copper-containing molybdenite according to the present invention includes a step (S400) of separating solid and liquid after the water leaching.

本発明による銅含有輝水鉛鉱の前処理方法において、前記水浸出後、溶液に存在する固体と液体を分離する固液分離が行われる。ここで、固液分離は、ベルトフィルター(belt filter)、又はドラムフィルター(drum filter) などといったろ過装置で行われることができる。   In the pretreatment method for copper-containing molybdenite according to the present invention, after the water leaching, solid-liquid separation for separating solid and liquid present in the solution is performed. Here, the solid-liquid separation can be performed by a filtration device such as a belt filter or a drum filter.

本発明による銅含有輝水鉛鉱の前処理方法は、前記分離した固体を乾燥させる段階(Ｓ５００)を含む。   The pretreatment method for copper-containing molybdenite according to the present invention includes a step (S500) of drying the separated solid.

前記分離した固体(cake)は、固体に存在する水分を乾燥するために、乾燥工程が行われることができる。   The separated solid may be subjected to a drying process in order to dry moisture present in the solid.

また、本発明は、銅含有輝水鉛鉱と硫酸とを混合する段階と、前記混合後、２１０−２４０℃で加熱して、硫酸化反応させる段階と、前記硫酸化反応後、水を入れて撹拌して、水浸出させる段階と、前記水浸出後、固体と液体を分離する段階と、前記分離した固体を乾燥させる段階とを含む銅含有輝水鉛鉱の前処理方法を提供する。   The present invention also includes a step of mixing copper-containing molybdenite and sulfuric acid, a step of heating at 210-240 ° C. after the mixing, and a sulfation reaction, and adding water after the sulfation reaction. Provided is a pretreatment method for copper-containing molybdenite comprising the steps of stirring and water leaching, separating the solid and liquid after the water leaching, and drying the separated solid.

本発明による銅含有輝水鉛鉱の前処理方法において、前記硫酸化反応を２１０−２４０℃で４０−８０分間行い、銅を９９％以上除去することができ、モリブデンは、９９.７％以上回収することができる(実験例２及び３参照)。ここで、前記硫酸は、輝水鉛鉱に対して、０.９−１.８の当量比で混合されることが望ましく、前記限定理由は、前述した通りである。   In the pretreatment method for copper-containing molybdenite according to the present invention, the sulfation reaction is carried out at 210-240 ° C. for 40-80 minutes to remove 99% or more of copper, and molybdenum is recovered to 99.7% or more. (See Experimental Examples 2 and 3). Here, it is desirable that the sulfuric acid is mixed in an equivalent ratio of 0.9 to 1.8 with respect to the molybdenite, and the reason for the limitation is as described above.

実施例１: 銅含有輝水鉛鉱の前処理   Example 1: Pretreatment of copper-containing molybdenite

下記の表３は、慶尚北道蔚珍郡金音鉱山で採取した輝水鉛鉱を、浮遊選鉱した精鉱の構成元素及び含有量を示すものである。下記の表３の輝水鉛鉱２０ｇと、硫酸が溶解した濃い硫酸溶液を５０ml資材るつぼに入れて、硝子棒でよく混合した後、マッフル炉(muffle furnace)を用いて、硫酸化反応させた。硫酸化反応後、試料を取出して冷却した後、１０００mlフラスコで蒸留水２００mlを入れ、９０℃で６０分間、３００rpmで撹拌して浸出させた。このように用意した試料を、ガラス繊維ろ過紙を用いてろ過した後、１１２℃で２４時間の間、乾燥させた。   Table 3 below shows the constituent elements and content of concentrates obtained by flotation of pyroxenite from the Kinon Mine, Uljin-gun, Gyeongsangbuk-do. 20 g of molybdenite ore in Table 3 below and a concentrated sulfuric acid solution in which sulfuric acid was dissolved were placed in a 50-ml material crucible, mixed well with a glass rod, and then subjected to a sulfation reaction using a muffle furnace. After the sulfation reaction, the sample was taken out and cooled, and then 200 ml of distilled water was put in a 1000 ml flask, and the mixture was leached by stirring at 90 ° C. for 60 minutes at 300 rpm. The sample thus prepared was filtered using glass fiber filter paper and then dried at 112 ° C. for 24 hours.

実験例１: 硫酸添加量による銅の濃度及び除去率分析 Experimental example 1: Analysis of copper concentration and removal rate by the amount of sulfuric acid added

本発明による銅含有輝水鉛鉱の前処理方法において、硫酸添加量による銅の濃度及び除去率を分析し、その結果を下記の表４、図３、及び図４に示している。   In the pretreatment method for copper-containing molybdenite according to the present invention, the concentration and removal rate of copper according to the amount of sulfuric acid added were analyzed, and the results are shown in Table 4, FIG. 3, and FIG.

前記表４及び図３に示しているように、硫酸化反応温度１８０℃と２２５ ℃のいずれにおいても、硫酸の添加量が増加するほど、銅の除去率は増加した(硫酸化反応時間: ４０分)。硫酸化反応温度が２２５ ℃の場合は、硫酸添加量が１６gであるとき、９７％の銅除去率を示し、硫酸添加量が増加するほど、銅除去率は増加した。また、硫酸添加量が同一であるにもかかわらず、硫酸化反応温度が２２５℃の場合、銅除去率が硫酸化反応温度１８０ ℃よりも高いことが分かる。   As shown in Table 4 and FIG. 3, at any of the sulfation reaction temperatures of 180 ° C. and 225 ° C., the copper removal rate increased as the addition amount of sulfuric acid increased (sulfation reaction time: 40 Min). When the sulfation reaction temperature was 225 ° C., the copper removal rate was 97% when the sulfuric acid addition amount was 16 g, and the copper removal rate increased as the sulfuric acid addition amount increased. Further, it can be seen that when the sulfation reaction temperature is 225 ° C., the copper removal rate is higher than the sulfation reaction temperature 180 ° C. even though the addition amount of sulfuric acid is the same.

また、図４は、本発明による銅含有輝水鉛鉱の前処理方法において、硫酸添加量による輝水鉛鉱のＸ線回折分析結果である。図4を参考すると、硫酸化反応前の輝水鉛鉱には、輝水鉛鉱及び石英(quartz)が認められたが、硫酸化反応後、輝水鉛鉱、硫黄(sulfur)、及び石英などが存在していることが確認できた。   FIG. 4 is a result of X-ray diffraction analysis of molybdenite by the amount of sulfuric acid added in the pretreatment method for copper-containing molybdenite according to the present invention. Referring to Fig. 4, molybdenite and quartz were observed in the hydropyrite prior to the sulfation reaction, but after sulfation reaction, molybdenite, sulfur, and quartz existed. I was able to confirm.

実験例２: 硫酸化反応温度及び時間による銅の濃度分析 Example 2: Copper concentration analysis by sulfation reaction temperature and time

本発明による銅含有輝水鉛鉱の前処理方法において、硫酸化反応温度及び反応時間による輝水鉛鉱における銅の濃度を分析し、その結果を、表５及び図５に示している。   In the pretreatment method of copper-containing molybdenite according to the present invention, the concentration of copper in molybdenite according to the sulfation reaction temperature and reaction time was analyzed, and the results are shown in Table 5 and FIG.

前記表５及び図５に示しているように、硫酸化反応温度が２１０℃であるとき、硫酸化反応時間を８０分行うと、０.０６質量％の銅が残ることが分かり、２２５ ℃では、３０分で０.３３質量％の銅のみが残ることが分かり、２４０ ℃では、２０分で０.３４質量％の銅が残り、２７０℃及び３００ ℃では、反応時間を１０分で行うと、それぞれ、０.２２質量％、０.１４質量％のみが残ることが分かる(H2SO4の添加量: ３２g)。それで、反応温度２１０℃では、８０分で硫酸化反応を進行して、輝水鉛鉱中の銅含有量を０.５質量％以下に低くすることができ、 ２２５℃では３０分、２４０℃では２０分、２７０℃及び３００℃では１０分の反応時間でも、輝水鉛鉱中の銅含有量を０.５質量％以下に除去することができる。 As shown in Table 5 and FIG. 5, when the sulfation reaction temperature is 210 ° C., it can be seen that 0.06% by mass of copper remains when the sulfation reaction time is performed for 80 minutes, at 225 ° C. It can be seen that only 0.33% by mass of copper remains in 30 minutes, and at 240 ° C., 0.34% by mass of copper remains in 20 minutes, and at 270 ° C. and 300 ° C., the reaction time is 10 minutes. Only 0.22% by mass and 0.14% by mass remain, respectively (addition amount of H 2 SO 4 : 32 g). Therefore, at a reaction temperature of 210 ° C., the sulfation reaction can proceed in 80 minutes, and the copper content in the molybdenite can be lowered to 0.5% by mass or less, at 225 ° C. for 30 minutes, and at 240 ° C. Even at a reaction time of 20 minutes, 270 ° C. and 300 ° C. for 10 minutes, the copper content in the molybdenite can be removed to 0.5 mass% or less.

実験例３: 硫酸化反応温度及び時間によるモリブデンの溶解率分析 Experimental Example 3: Molybdenum solubility analysis by sulfation reaction temperature and time

本発明による銅含有輝水鉛鉱の前処理方法において、硫酸化反応温度及び時間によるモリブデンの溶解率を分析し、その結果を表６及び図６に示している。   In the pretreatment method for copper-containing molybdenite according to the present invention, the molybdenum dissolution rate according to the sulfation reaction temperature and time was analyzed, and the results are shown in Table 6 and FIG.

前記表６及び図６に示しているように、硫酸化反応温度が高く、且つ、時間が長くなるほど、モリブデンの溶解率が増加することが分かる(H2SO4: ３２g、輝水鉛鉱: ２０g)。つまり、２４０℃で８０分以上、２７０℃では３０分以上反応させると、輝水鉛鉱の表面で酸化が発生することが分かる。それで、２１０−２４０℃の硫酸化温度範囲で硫酸化反応時間を調節すると、モリブデンを損失することなく、銅を完壁に除去することができると判断される。つまり、硫酸化反応温度２１０−２４０℃で反応時間４０−８０分間行うと、銅を９９％以上除去することができ、モリブデンを９９.７％以上回収することができることが分かる。 As shown in Table 6 and FIG. 6, it can be seen that the higher the sulfation reaction temperature and the longer the time, the higher the molybdenum dissolution rate (H 2 SO 4 : 32 g, molybdenite: 20 g. ). In other words, it can be seen that oxidation occurs on the surface of molybdenite when reacted at 240 ° C. for 80 minutes or longer and at 270 ° C. for 30 minutes or longer. Therefore, when the sulfation reaction time is adjusted in the sulfation temperature range of 210 to 240 ° C., it is judged that copper can be completely removed without losing molybdenum. That is, when the reaction time is 210 to 240 ° C. and the reaction time is 40 to 80 minutes, 99% or more of copper can be removed and 99.7% or more of molybdenum can be recovered.

今まで本発明による銅含有輝水鉛鉱の前処理方法に関する具体的な実施例について説明したが、本発明の範囲から逸脱しない限度内では、様々な実施変形が可能であることは自明である。   Although the specific Example regarding the pre-processing method of the copper containing molybdenite ore by this invention was described until now, it is obvious that various implementation deformation | transformation is possible within the limit which does not deviate from the scope of the present invention.

そこで、本発明の範囲には前記実施例に限ってはいけなく、後述する特許請求の範囲だけでなく、この特許請求の範囲と均等なものなどによって決められるべきである。   Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined not only by the claims described later, but also by the equivalents of the claims.

つまり、前述した実施例は全ての面で例示に過ぎず、限定的なものではないことと理解されるべきであり、本発明の範囲は、詳細な説明よりは、後述する特許請求の範囲により示され、その特許請求の範囲の意味及び範囲、そして、その等価概念から導出される全ての変更又は変形した形態が、本発明の範囲に含まれることと解析されるべきである。   In other words, it should be understood that the above-described embodiment is merely illustrative in all aspects and not limiting, and the scope of the present invention is defined by the scope of the claims described below rather than by the detailed description. All changes or variations shown and derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention.

前記課題を解決するため、本発明は、銅含有輝水鉛鉱と硫酸を混合する段階と、前記混合後、加熱して硫酸化反応させる段階と、前記硫酸化反応後、水を入れて撹拌して、水浸出させる段階と、前記水浸出後、固体と液体を分離する段階と、前記分離した固体を乾燥させる段階とを含み、前記硫酸は、銅含有輝水鉛鉱に対して、０．９〜１．８の当量比で混合され、前記加熱は、２１０〜２４０℃で３０〜４０分間行われ、前記銅含有輝水鉛鉱に含まれた銅を９９％以上除去し、モリブデンを９９％以上回収する銅含有輝水鉛鉱の前処理方法を提供する。 In order to solve the above-mentioned problems, the present invention includes a step of mixing copper-containing molybdenite and sulfuric acid, a step of heating and then performing a sulfation reaction after the mixing, and a step of adding water and stirring after the sulfation reaction. Te, a step of water leaching, after the water leaching, and separating the solid and liquid, seen including a step of drying the separated solid, wherein the sulfuric acid, the copper-containing molybdenite ore, 0. It is mixed at an equivalent ratio of 9 to 1.8, and the heating is performed at 210 to 240 ° C. for 30 to 40 minutes, removing 99% or more of copper contained in the copper-containing molybdenite and 99% of molybdenum. Provided is a pretreatment method for copper-containing molybdenite to be recovered .

Claims (11)

銅含有輝水鉛鉱と硫酸とを混合する段階と、
前記混合後、加熱して硫酸化反応させる段階と、
前記硫酸化反応後、水を入れて撹拌して、水浸出させる段階と、
前記水浸出後、固体と液体を分離する段階と、
前記分離した固体を乾燥させる段階とを含むことを特徴とする銅含有輝水鉛鉱の前処理方法。 Mixing copper-containing molybdenite and sulfuric acid;
After the mixing, heating to cause a sulfation reaction;
After the sulfation reaction, adding water and stirring to leaching the water;
Separating the solid and liquid after the water leaching;
And a step of drying the separated solid. A pretreatment method for copper-containing molybdenite. 前記硫酸化反応は、１８０−２４０℃で行われることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   The pretreatment method for copper-containing molybdenite according to claim 1, wherein the sulfation reaction is performed at 180 to 240 ° C. 前記硫酸化反応は、２０−８０分間、行われることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   The pretreatment method for copper-containing molybdenite according to claim 1, wherein the sulfation reaction is performed for 20 to 80 minutes. 前記硫酸は、輝水鉛鉱に対して、０.９−１.８の当量比で混合されることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   2. The pretreatment method for copper-containing molybdenite according to claim 1, wherein the sulfuric acid is mixed in an equivalence ratio of 0.9 to 1.8 with respect to the hydropyrite ore. 前記硫酸化反応は、硫酸を０.９−１.８の当量比で混合して、１８０−２４０℃で２０−８０分間、行われることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   2. The copper-containing bright water lead according to claim 1, wherein the sulfation reaction is performed by mixing sulfuric acid at an equivalent ratio of 0.9-1.8 at 180-240 ° C. for 20-80 minutes. Pretreatment method for ore. 前記硫酸化反応は、２１０−２４０℃で行われることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   The pretreatment method for copper-containing molybdenite according to claim 1, wherein the sulfation reaction is performed at 210 to 240 ° C. 前記硫酸化反応は、４０−８０分間、行われることを特徴とする請求項６に記載の銅含有輝水鉛鉱の前処理方法。   The pretreatment method for copper-containing molybdenite according to claim 6, wherein the sulfation reaction is performed for 40-80 minutes. 前記硫酸は、輝水鉛鉱に対して、０.９−１.８の当量比で混合されることを特徴とする請求項６に記載の銅含有輝水鉛鉱の前処理方法。   The said sulfuric acid is mixed by the equivalence ratio of 0.9-1.8 with respect to a dolomite ore, The pre-processing method of the copper containing arsenite ore of Claim 6 characterized by the above-mentioned. 前記硫酸化反応は、硫酸を０.９−１.８の当量比で混合して、２１０−２４０℃で４０−８０分間、行われることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   2. The copper-containing bright water lead according to claim 1, wherein the sulfation reaction is performed by mixing sulfuric acid at an equivalent ratio of 0.9-1.8 at 210-240 ° C. for 40-80 minutes. Pretreatment method for ore. 前記水は、蒸留水、脱イオン水、軽水、及び重水からなる群から選ばれる１種以上であることを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   The said water is 1 or more types chosen from the group which consists of distilled water, deionized water, light water, and heavy water, The pretreatment method of the copper containing molybdenite ore of Claim 1 characterized by the above-mentioned. 更に、前記輝水鉛鉱は、硫酸と混合する前に、浮遊選鉱する段階を含むことを特徴とする請求項１に記載の銅含有輝水鉛鉱の前処理方法。   The pretreatment method for copper-containing molybdenite according to claim 1, further comprising a step of flotation before mixing with sulfuric acid.
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