JP6694689B2 - Arsenic-containing copper mineral treatment method - Google Patents
Arsenic-containing copper mineral treatment method Download PDFInfo
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- JP6694689B2 JP6694689B2 JP2015197118A JP2015197118A JP6694689B2 JP 6694689 B2 JP6694689 B2 JP 6694689B2 JP 2015197118 A JP2015197118 A JP 2015197118A JP 2015197118 A JP2015197118 A JP 2015197118A JP 6694689 B2 JP6694689 B2 JP 6694689B2
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- 229910052785 arsenic Inorganic materials 0.000 title claims description 78
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 77
- 238000000034 method Methods 0.000 title claims description 52
- 229910001779 copper mineral Inorganic materials 0.000 title claims description 49
- 239000010949 copper Substances 0.000 claims description 88
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 84
- 229910052802 copper Inorganic materials 0.000 claims description 84
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 238000002386 leaching Methods 0.000 claims description 65
- 230000001590 oxidative effect Effects 0.000 claims description 12
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000638 solvent extraction Methods 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- -1 after neutralization Chemical compound 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000012141 concentrate Substances 0.000 description 14
- 229910052964 arsenopyrite Inorganic materials 0.000 description 7
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 3
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000218657 Picea Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052950 sphalerite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052969 tetrahedrite Inorganic materials 0.000 description 2
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment 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
Description
本発明は、砒素を含有する銅鉱物（硫砒銅鉱、砒四面銅鉱等）の処理方法に関する。 The present invention relates to a method of treating a copper mineral containing arsenic (arsenic spruce ore, arsenic tetrahedrite, etc.).
砒素を含有する銅鉱物（硫砒銅鉱、砒四面銅鉱等）から、銅と砒素とを分離する方法として、従来、以下に示すような乾式法及び湿式法に係る処理方法が報告されている。 As a method for separating copper and arsenic from a copper mineral containing arsenic (arsenic spruce ore, arsenic tetrahedrite, etc.), conventionally, the following processing methods relating to a dry method and a wet method have been reported.
−乾式法の例−
酸化雰囲気または非酸化雰囲気で銅精鉱を焙焼し、砒素を揮発除去する酸化焙焼法、非酸化焙焼法が知られている。得られた焙焼鉱は、乾式製錬原料にして、銅を回収する。
また、精鉱と硫酸を混錬して、炉で焙焼する硫酸焙焼法（硫酸塩に変換する処理方法）も報告されている（非特許文献１〜３）。銅鉱物中の砒素は、浸出液に溶解させて回収、または、高温焙焼によって揮発除去している。
-Example of dry method-
An oxidizing roasting method and a non-oxidizing roasting method are known in which copper concentrate is roasted in an oxidizing atmosphere or a non-oxidizing atmosphere to volatilize and remove arsenic. The roasted ore thus obtained is used as a raw material for dry smelting to recover copper.
In addition, a sulfuric acid roasting method (processing method of converting to sulfate) in which a concentrate and sulfuric acid are kneaded and roasted in a furnace is also reported (Non-patent documents 1 to 3). Arsenic in copper minerals is dissolved in the leachate and recovered, or volatilized and removed by high temperature roasting.
−湿式法の例−
硫化浴浸出等のアルカリ浸出法が知られている。
また、酸浸出では、オートクレーブによる加圧・空気吹き込みにより酸化浸出するＣＥＳＬプロセスが知られている（非特許文献４）。銅鉱物中の砒素は、浸出中に共存するＦｅとスコロダイトを形成し、残渣に沈殿させて除去している。
-Example of wet method-
Alkaline leaching methods such as sulfide bath leaching are known.
Further, in acid leaching, a CESL process is known in which oxidative leaching is performed by pressurizing and blowing air in an autoclave (Non-Patent Document 4). Arsenic in copper minerals forms scorodite with coexisting Fe during leaching, and is removed by precipitation in the residue.
しかしながら、上記従来の乾式法によれば、銅と砒素とを分離するには６５０℃以上の温度で焙焼する必要がある。また、酸化焙焼法では有毒な亜砒酸の形態で揮発し、非酸化焙焼では硫化砒素の形態で揮発するため、これら砒素の回収方法に問題が生じている。 However, according to the above conventional dry method, it is necessary to roast at a temperature of 650 ° C. or higher to separate copper and arsenic. Further, in the oxidative roasting method, it is volatilized in the form of toxic arsenous acid, and in the non-oxidative roasting method, it is volatilized in the form of arsenic sulfide, which causes a problem in the method of recovering these arsenic.
また、上記従来の湿式法によれば、加圧・空気吹き込みにより酸化浸出することで銅の高浸出率が実現されるが、加圧・空気吹き込みが必須であるため、オートクレーブのような耐圧、耐酸性の装置が必要となり、コスト等、処理効率の面で問題がある。 Further, according to the above conventional wet method, a high leaching rate of copper is realized by oxidizing and leaching by pressurizing and blowing air, but since pressurizing and air blowing are essential, pressure resistance such as in an autoclave, An acid-resistant device is required, and there is a problem in processing efficiency such as cost.
本発明は、上記問題に鑑み、砒素を含有する銅鉱物から、効率良く銅を浸出させ、且つ、容易に砒素を回収する砒素含有銅鉱物の処理方法を提供することを課題とする。 In view of the above problems, it is an object of the present invention to provide a method for treating an arsenic-containing copper mineral that efficiently leaches copper from an arsenic-containing copper mineral and easily recovers arsenic.
本発明者が鋭意検討を進めた結果、所定の温度の硫酸によって砒素含有銅鉱物から銅を浸出させることにより、砒素を含有する銅鉱物から、効率良く銅を浸出させ、且つ、容易に砒素を回収することができることを見出した。 As a result of intensive studies by the present inventors, by leaching copper from an arsenic-containing copper mineral with sulfuric acid at a predetermined temperature, copper is efficiently leached from an arsenic-containing copper mineral, and arsenic is easily extracted. It was found that it can be recovered.
以上の知見を基礎として完成された本発明は一側面において、砒素含有銅鉱物から、１００〜２９０℃の硫酸のみによって銅を浸出させる工程を含み、前記銅を浸出させる工程において、酸素含有ガスの吹き込みを行わずに銅を浸出させる砒素含有銅鉱物の処理方法である。 In the above findings the present invention in one aspect that is completed as a basis, the arsenic-containing copper minerals, saw including the step of leaching the copper only by sulfuric acid one hundred to two hundred and ninety ° C., in the step of leaching the copper-oxygen-containing gas This is a method of treating an arsenic-containing copper mineral in which copper is leached without performing the blowing of copper .
本発明の砒素含有銅鉱物の処理方法は一実施形態において、前記銅を浸出させる工程を大気圧下で行う。 In one embodiment of the method for treating an arsenic-containing copper mineral of the present invention, the step of leaching the copper is performed under atmospheric pressure.
本発明の砒素含有銅鉱物の処理方法は別の一実施形態において、前記銅を浸出させる工程において、１５０〜２００℃の硫酸によって銅を浸出させる。 In another embodiment of the method for treating an arsenic-containing copper mineral of the present invention, in the step of leaching copper, copper is leached with sulfuric acid at 150 to 200 ° C.
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記銅を浸出させる工程における銅の浸出率が５０％以上である。 In still another embodiment of the method for treating an arsenic-containing copper mineral of the present invention, the leaching rate of copper in the step of leaching the copper is 50% or more.
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記銅を浸出させる工程において、銅の浸出時間が１〜５時間である。 In still another embodiment of the method for treating an arsenic-containing copper mineral of the present invention, in the step of leaching the copper, the leaching time of copper is 1 to 5 hours.
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記銅を浸出させる工程における硫酸溶液のパルプ濃度が４０％以下である。 In still another embodiment of the method for treating an arsenic-containing copper mineral according to the present invention, the pulp concentration of the sulfuric acid solution in the step of leaching the copper is 40% or less.
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記銅を浸出させる工程で得られた浸出液を希釈し、中和した後、酸化しながら加温することによりスコロダイトを合成する工程をさらに含む。 In yet another embodiment of the method for treating an arsenic-containing copper mineral of the present invention, a scorodite is synthesized by diluting the leaching solution obtained in the step of leaching the copper, neutralizing it, and then heating it while oxidizing it. The method further includes:
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記スコロダイトを合成する工程で得られたスコロダイトを除去した後に残った液から溶媒抽出により銅を回収する工程をさらに含む。 In yet another embodiment, the method for treating an arsenic-containing copper mineral of the present invention further includes a step of recovering copper by solvent extraction from a liquid remaining after removing the scorodite obtained in the step of synthesizing the scorodite.
本発明の砒素含有銅鉱物の処理方法は更に別の一実施形態において、前記溶媒抽出により銅を回収する工程で銅を溶媒抽出した後の抽出後液に、不純物除去処理を行った後、得られた液を、前記銅を浸出させる工程で得られた浸出液を希釈する際の希釈液として用いる工程をさらに含む。 In still another embodiment of the method for treating an arsenic-containing copper mineral of the present invention, after the impurity removal treatment is performed on the post-extraction liquid after solvent extraction of copper in the step of recovering copper by the solvent extraction, it is obtained. The method further includes the step of using the obtained liquid as a diluting liquid when diluting the leaching liquid obtained in the step of leaching the copper.
本発明によれば、砒素を含有する銅鉱物から、効率良く銅を浸出させ、且つ、容易に砒素を回収する砒素含有銅鉱物の処理方法を提供することができる。 According to the present invention, it is possible to provide a method for treating an arsenic-containing copper mineral that efficiently leaches copper from an arsenic-containing copper mineral and easily recovers arsenic.
本発明の砒素含有銅鉱物の処理方法について、図を用いて詳細に説明する。図１は、本発明の砒素含有銅鉱物の処理方法の一実施形態を示すフローチャートである。 The method for treating an arsenic-containing copper mineral of the present invention will be described in detail with reference to the drawings. FIG. 1 is a flowchart showing an embodiment of the method for treating an arsenic-containing copper mineral of the present invention.
本発明において処理対象とする砒素含有銅鉱物は、硫砒銅鉱（Ｃｕ3ＡｓＳ4）、砒四面銅鉱（Ｃｕ12Ａｓ4Ｓ13）、さらに、黄銅鉱（ＣｕＦｅＳ2）に硫砒鉄鉱（ＦｅＡｓＳ）や硫化砒素が混在した鉱物等の、砒素成分を含有する銅鉱物である。 The arsenic-containing copper minerals to be treated in the present invention include arsenopyrite (Cu 3 AsS 4 ), arsenopyrite (Cu 12 As 4 S 13 ), chalcopyrite (CuFeS 2 ) and arsenopyrite (FeAsS) and sulfide. It is a copper mineral containing an arsenic component, such as a mineral containing arsenic.
本発明の砒素含有銅鉱物の処理方法の一実施形態においては、砒素含有銅鉱物から、１００〜２９０℃の硫酸によって銅を浸出させる。このとき、下記式で示す反応が生じ、硫酸の酸化力によって例えば硫砒銅鉱を硫酸銅と亜砒酸とに酸化・分解することができる。
２Ｃｕ3ＡｓＳ4＋９Ｈ2ＳＯ4→６ＣｕＳＯ4＋Ａｓ2Ｏ3＋９Ｈ2Ｏ＋１１Ｓ
In one embodiment of the method for treating an arsenic-containing copper mineral of the present invention, copper is leached from an arsenic-containing copper mineral with sulfuric acid at 100 to 290 ° C. At this time, a reaction represented by the following formula occurs, and for example, arsenic sphalerite can be oxidized and decomposed into copper sulfate and arsenous acid by the oxidizing power of sulfuric acid.
2Cu 3 AsS 4 + 9H 2 SO 4 → 6CuSO 4 + As 2 O 3 + 9H 2 O + 11S
硫酸の温度が１００℃未満であると、上記反応が生じ難くなる。また、硫酸の温度が２９０℃を超えると硫酸の分解温度となるため銅の浸出を行うことが困難となる。また、硫酸の蒸気圧を考慮する継続的に浸出液を維持しながら行うためには２００℃以下が好ましい。一方、砒素含有銅鉱物から効率的に銅を浸出させる観点から浸出温度は１５０℃以上が好ましく、１８０℃以上がより好ましい。 If the temperature of sulfuric acid is less than 100 ° C., the above reaction becomes difficult to occur. Further, if the temperature of sulfuric acid exceeds 290 ° C., the decomposition temperature of sulfuric acid will be reached, and it will be difficult to leach copper. In order to continuously maintain the leachate while considering the vapor pressure of sulfuric acid, the temperature is preferably 200 ° C. or lower. On the other hand, the leaching temperature is preferably 150 ° C. or higher, and more preferably 180 ° C. or higher from the viewpoint of efficiently leaching copper from the arsenic-containing copper mineral.
このように、本発明の砒素含有銅鉱物の処理方法によれば、従来の乾式法に比べて低温での処理が可能となり、砒素を揮発させることなく浸出液に溶解させて容易に回収することができる。また、従来の湿式法では、上述のように加圧・空気吹き込みが必須であるため、オートクレーブのような耐圧、耐酸性の装置が必要であったが、本発明によれば、加圧・空気吹き込み（または、酸素含有ガスの吹き込み）は不要であり、大気圧下でも良好に砒素含有銅鉱物の処理が可能となる。そのため、本願発明によれば、砒素を含有する銅鉱物から、効率良く銅と砒素とを分離して回収することができる。 Thus, according to the method for treating an arsenic-containing copper mineral of the present invention, it is possible to treat at a lower temperature than the conventional dry method, and arsenic can be dissolved in the leachate without volatilizing and easily recovered. it can. Further, in the conventional wet method, since pressurization and air blowing are essential as described above, a pressure-resistant and acid-resistant device such as an autoclave was required. Blowing (or blowing of oxygen-containing gas) is not necessary, and the arsenic-containing copper mineral can be satisfactorily treated even under atmospheric pressure. Therefore, according to the present invention, copper and arsenic can be efficiently separated and recovered from the copper mineral containing arsenic.
本発明において用いる硫酸は、濃度が９５％以上の濃硫酸であることが好ましく、濃度が９８％以上の濃硫酸であることがより好ましい。すなわち、本発明において用いる硫酸は、温度：１００〜２９０℃で、濃度：９５％以上の熱濃硫酸であることが好ましい。このような熱濃硫酸を用いることで、より良好に上記式で示される反応が進み、硫砒銅鉱を、より良好に硫酸銅と亜砒酸とに酸化・分解することができる。 The sulfuric acid used in the present invention is preferably concentrated sulfuric acid having a concentration of 95% or more, and more preferably concentrated sulfuric acid having a concentration of 98% or more. That is, the sulfuric acid used in the present invention is preferably hot concentrated sulfuric acid having a temperature of 100 to 290 ° C. and a concentration of 95% or more. By using such hot concentrated sulfuric acid, the reaction represented by the above formula proceeds more favorably, and arsenic sphalerite can be oxidized and decomposed into copper sulfate and arsenous acid more favorably.
このようにして砒素含有銅鉱物から銅が浸出されるが、このとき、本発明の砒素含有銅鉱物の処理方法によれば、銅を５０％以上の浸出率で浸出することができる。また、本発明の砒素含有銅鉱物の処理方法によれば、さらに、銅を６０％以上、７０％以上、８０％以上、または、９０％以上の浸出率で浸出することができる。 In this way, copper is leached from the arsenic-containing copper mineral. At this time, according to the method for treating an arsenic-containing copper mineral of the present invention, copper can be leached at a leaching rate of 50% or more. Further, according to the method for treating an arsenic-containing copper mineral of the present invention, copper can be further leached at a leaching rate of 60% or more, 70% or more, 80% or more, or 90% or more.
銅を浸出させる工程において、銅の浸出時間は１〜１０時間とすることができ、１〜６時間としてもよく、さらに１〜５時間としてもよい。 In the step of leaching copper, the leaching time of copper may be 1 to 10 hours, may be 1 to 6 hours, and may be 1 to 5 hours.
銅を浸出させる工程における硫酸溶液のパルプ濃度が４０％以下であるのが好ましい。硫酸溶液のパルプ濃度が４０％以下であると、より銅の浸出率が向上する。また、硫酸溶液のパルプ濃度が４０％を超えると、反応で硫酸が消費されることもあり、硫酸が枯渇して浸出ではなく焙焼処理の形態となってしまうおそれがある。「パルプ濃度」は、以下の式で算出される：
パルプ濃度＝精鉱質量（ｇ）÷（精鉱質量＋濃硫酸質量（ｇ））×１００（％）
なお、上記「濃硫酸質量」は、濃硫酸液量（ｍＬ）×濃硫酸比重（ｇ／ｃｍ3）で算出される。
The pulp concentration of the sulfuric acid solution in the step of leaching copper is preferably 40% or less. When the pulp concentration of the sulfuric acid solution is 40% or less, the leaching rate of copper is further improved. Further, when the pulp concentration of the sulfuric acid solution exceeds 40%, the sulfuric acid may be consumed in the reaction, and the sulfuric acid may be depleted and the form of roasting treatment may be used instead of leaching. "Pulp density" is calculated by the following formula:
Pulp concentration = concentrate mass (g) / (concentrate mass + concentrated sulfuric acid mass (g)) x 100 (%)
Incidentally, the "concentrated sulfuric acid mass" is calculated by the concentrated sulfuric acid solution volume (mL) × concentrated sulfuric acid specific gravity (g / cm 3).
浸出処理中に発生したガスは、図１に示すように、排ガス処理を経てＳＯ2とされ、硫酸プラントから、再度銅の浸出のための硫酸原料として用いてもよい。 As shown in FIG. 1, the gas generated during the leaching process is converted into SO 2 through exhaust gas treatment, and may be used again as a sulfuric acid raw material for leaching copper from a sulfuric acid plant.
本発明の砒素含有銅鉱物の処理方法の一実施形態においては、銅を浸出させる工程で得られた浸出液を水等で希釈し、Ｃａ（ＯＨ）2またはＮａＯＨを用いたｐＨ調整（例えばｐＨ＝１．５）によって中和した後、酸化しながら加温することにより、砒素を含有するスコロダイトを合成する。これにより、浸出液からの脱Ｆｅ、Ａｓ処理を行うことができる。 In one embodiment of the method for treating an arsenic-containing copper mineral of the present invention, the leachate obtained in the step of leaching copper is diluted with water or the like, and pH is adjusted using Ca (OH) 2 or NaOH (for example, pH = After neutralizing with 1.5), the scorodite containing arsenic is synthesized by heating while oxidizing. Thereby, Fe removal from the leachate and As treatment can be performed.
次に、スコロダイトを合成する工程で得られたスコロダイトを固液分離により除去した後に残った液（浸出液）に溶媒抽出を行うことで銅を回収することができる。このとき、例えば電解採取を行うことで銅（電気銅）を回収することができる。一方、残渣には、スコロダイトの他、例えば、脈石や石膏等が含まれている。 Next, the scorodite obtained in the step of synthesizing scorodite is removed by solid-liquid separation, and the liquid (leaching solution) remaining after the solvent extraction is performed to recover copper. At this time, copper (electrolytic copper) can be recovered by performing electrowinning, for example. On the other hand, the residue contains, for example, gangue, gypsum and the like in addition to scorodite.
次に、溶媒抽出により銅を回収する工程で銅を溶媒抽出した後の抽出後液（希硫酸）に、不純物除去処理（排水処理等）を行った後、得られた液を、銅を浸出させる工程で得られた浸出液を希釈する際の希釈液として用いてもよい。これにより、砒素含有銅鉱物の処理コストが良好となる。 Next, after the solvent is extracted in the step of recovering copper by solvent extraction, the solution after extraction (dilute sulfuric acid) is subjected to impurity removal treatment (wastewater treatment, etc.), and then the obtained liquid is leached with copper. You may use it as a diluting liquid when diluting the leachate obtained in the step. This improves the processing cost of the arsenic-containing copper mineral.
以下に、本発明について、実施例を用いて詳細に説明するが、本発明はこれら実施例に限定されることはない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
（試験例１）
砒素を含有する銅鉱物を含む銅精鉱２５０ｇを５００ｍｌの硫酸（濃度９８％）に溶解させて３時間の浸出処理を行った。銅精鉱の化学分析値は、Ｃｕ品位が２１％、Ａｓが７％であった。また、銅精鉱中の銅の形態を鉱物解析システム（ＭＬＡ：ＦＥＩ社製ＭＬＡ６５０Ｆ）で解析したところ、８５ｍａｓｓ％以上が硫砒銅鉱の形態であった。当該硫酸溶液のパルプ濃度は２０％であった。浸出温度は１２０℃、１５０℃、１８０℃の３種類とした。また、当該浸出処理は、大気圧下で、酸素含有ガスの吹き込みを行わずに行った。得られた銅の浸出液から銅、砒素を回収し、それらの浸出率を測定した。試験結果を表１及び図２に示す。
(Test Example 1)
250 g of copper concentrate containing a copper mineral containing arsenic was dissolved in 500 ml of sulfuric acid (concentration 98%), and leaching treatment was performed for 3 hours. The chemical analysis values of the copper concentrate were 21% for Cu grade and 7% for As. Further, when the morphology of copper in the copper concentrate was analyzed by a mineral analysis system (MLA: MLA650F manufactured by FEI), it was found that 85 mass% or more was the form of arsenopyrite. The pulp concentration of the sulfuric acid solution was 20%. The leaching temperature was set to three types of 120 ° C, 150 ° C, and 180 ° C. In addition, the leaching process was performed under atmospheric pressure without blowing the oxygen-containing gas. Copper and arsenic were recovered from the obtained copper leaching solution, and their leaching rates were measured. The test results are shown in Table 1 and FIG.
（試験例２）
試験例１と同様の砒素を含有する銅精鉱２５ｇを、２００℃にて、空気中で酸化焙焼したところ、銅の水への浸出率は４〜６％であった。また、４００℃にて、空気中で酸化焙焼したところ、銅の水への浸出率は２２％であった。また、試験例１と同様の砒素を含有する銅精鉱２５ｇを非酸化焙焼したところ、５５０℃以上でなければ砒素の揮発反応が進行しなかった。
試験例１及び２からわかるように、本発明によれば、乾式法に比べて低温での銅の浸出処理が可能となる。
(Test Example 2)
When 25 g of the same arsenic-containing copper concentrate as in Test Example 1 was oxidized and roasted in air at 200 ° C., the leaching rate of copper to water was 4 to 6%. Further, when oxidatively roasted in air at 400 ° C., the leaching rate of copper to water was 22%. Further, when 25 g of copper concentrate containing arsenic similar to that in Test Example 1 was non-oxidized and roasted, the arsenic volatilization reaction did not proceed unless the temperature was 550 ° C. or higher.
As can be seen from Test Examples 1 and 2, according to the present invention, the leaching treatment of copper at a lower temperature can be performed as compared with the dry method.
（試験例３）
砒素を含有する銅鉱物を含む銅精鉱２５０ｇを５００ｍｌの硫酸（濃度９８％）に溶解させて１時間、３時間の浸出処理を行った。銅精鉱の化学分析値は、Ｃｕ品位が２０％、Ａｓが７．２％であった。また、銅精鉱中の銅の形態を鉱物解析システム（ＭＬＡ：ＦＥＩ社製ＭＬＡ６５０Ｆ）で解析したところ、８５ｍａｓｓ％以上が硫砒銅鉱の形態であった。当該硫酸溶液のパルプ濃度は２０％であった。浸出温度は１８０℃とした。また、当該浸出処理は、大気圧下で、酸素含有ガスの吹き込みを行わずに行った。得られた銅の浸出液から銅、砒素を回収し、それらの浸出率を測定した。試験結果を表２及び図３に示す。
(Test Example 3)
250 g of a copper concentrate containing a copper mineral containing arsenic was dissolved in 500 ml of sulfuric acid (concentration 98%), and leaching treatment was performed for 1 hour and 3 hours. Regarding the chemical analysis values of the copper concentrate, Cu grade was 20% and As was 7.2%. Further, when the form of copper in the copper concentrate was analyzed by a mineral analysis system (MLA: MLA650F manufactured by FEI Co.), 85 mass% or more was the form of arsenopyrite. The pulp concentration of the sulfuric acid solution was 20%. The leaching temperature was 180 ° C. Further, the leaching process was performed under atmospheric pressure without blowing the oxygen-containing gas. Copper and arsenic were recovered from the obtained copper leaching solution, and their leaching rates were measured. The test results are shown in Table 2 and FIG.
表２及び図３に示すように、銅と砒素との挙動が同様である。浸出前の銅精鉱中の銅及び砒素は、ほぼ硫砒銅鉱の形態で存在しており、銅と砒素の浸出挙動に差が無いことから、砒素が浸出中にガス化せず、浸出液に溶解して回収されることがわかる。 As shown in Table 2 and FIG. 3, the behaviors of copper and arsenic are similar. The copper and arsenic in the copper concentrate before leaching are almost in the form of arsenopyrite, and since there is no difference in the leaching behavior of copper and arsenic, arsenic does not gasify during leaching and dissolves in the leachate. It turns out that it is recovered.
（試験例４）
試験例１で得られた銅の浸出液をＣａ（ＯＨ）2によってｐＨ１．５に制御し、コグニスジャパン株式会社製の２０ｖｏｌ％−ＬＩＸ９８４Ｎによる溶媒抽出を行ったところ、銅が抽出されたことを確認した。
(Test Example 4)
When the copper leachate obtained in Test Example 1 was adjusted to pH 1.5 with Ca (OH) 2 and subjected to solvent extraction with 20 vol% -LIX984N manufactured by Cognis Japan KK, it was confirmed that copper was extracted. did.
Claims (9)
前記銅を浸出させる工程において、酸素含有ガスの吹き込みを行わずに銅を浸出させる砒素含有銅鉱物の処理方法。 Arsenic-containing copper minerals, saw including the step of leaching the copper only by sulfuric acid one hundred to two hundred ninety ° C.,
In the step of leaching copper, a method for treating an arsenic-containing copper mineral in which copper is leached without blowing oxygen-containing gas .
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