JP2012241249A - Method for separating arsenic mineral from copper-containing material containing the arsenic mineral - Google Patents
Method for separating arsenic mineral from copper-containing material containing the arsenic mineral Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 162
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 161
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 107
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 62
- 239000011707 mineral Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000005188 flotation Methods 0.000 claims abstract description 30
- 239000002738 chelating agent Substances 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 description 75
- 235000010755 mineral Nutrition 0.000 description 51
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 8
- 229910052683 pyrite Inorganic materials 0.000 description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 8
- 239000011028 pyrite Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 229910001779 copper mineral Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 3
- 229910052951 chalcopyrite Inorganic materials 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- -1 bisulfite ions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
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Abstract
Description
本発明は、砒素を含有鉱物する含銅物から砒素鉱物を分離して高品位の銅精鉱を得る選鉱方法に関する。 The present invention relates to a beneficiation method for obtaining a high-grade copper concentrate by separating an arsenic mineral from a copper-containing material containing an arsenic-containing mineral.
銅精錬の分野では、銅を含有する銅鉱石や銅精鉱などの処理対象物(以降、含銅物と称する)から銅を回収する様々な方法が提案されている。例えば、含銅物の一形態である硫化銅鉱石中から銅を回収するには、一般的に以下の各段階を経た処理が行われる。 In the field of copper refining, various methods for recovering copper from processing objects (hereinafter referred to as copper-containing materials) such as copper ore and copper concentrate containing copper have been proposed. For example, in order to recover copper from copper sulfide ore which is one form of copper-containing material, generally, the following steps are performed.
(1)選鉱工程
選鉱工程では、鉱山で採掘された銅鉱石を粉砕した後、水を加えてスラリーとし、浮遊選鉱(浮選とも称する)を行う。この浮遊選鉱では、スラリーに抑制剤、起泡剤、捕収剤などで構成される浮選剤を添加し、空気を吹き込んで銅を含む鉱物を浮遊させつつ、脈石を沈降させて分離を行う。これにより銅品位30%前後の銅精鉱が得られる。得られた銅精鉱は次工程の乾式製錬工程に送られる。
(1) Mining process In the beneficiation process, after the copper ore mined in the mine is crushed, water is added to form a slurry, and flotation (also referred to as flotation) is performed. In this flotation, a flotation agent composed of an inhibitor, a foaming agent, a collection agent, etc. is added to the slurry, and air is blown to float minerals containing copper, while the gangue is allowed to settle and separate. Do. As a result, a copper concentrate with a copper grade of around 30% is obtained. The obtained copper concentrate is sent to the next dry smelting process.
(2)乾式製錬工程
乾式製錬工程では、上記選鉱工程で得られた銅精鉱を自溶炉などの炉を用いて熔解し、転炉及び精製炉を経て銅品位99%程度の粗銅にまで精製する。粗銅はアノードに鋳造された後、次工程の電解工程に送られる。この乾式製錬において、銅精鉱に含まれる砒素は、スラグやダストや粗銅に分配される。スラグは水砕して埋立て材などに利用され、ダストは炉に繰り返される。また、銅精鉱に含まれる硫黄は、亜硫酸ガスとして分離され、硫酸の原料となる。
(2) Dry smelting process In the dry smelting process, the copper concentrate obtained in the above-mentioned beneficiation process is melted using a furnace such as a flash smelting furnace, and then passed through a converter and a refining furnace, and crude copper having a copper grade of about 99% Purify to. After the crude copper is cast on the anode, it is sent to the next electrolysis process. In this dry smelting, arsenic contained in copper concentrate is distributed to slag, dust and crude copper. Slag is granulated and used as landfill, and dust is repeated in the furnace. Further, sulfur contained in the copper concentrate is separated as sulfurous acid gas and becomes a raw material of sulfuric acid.
(3)電解工程
電解工程では、硫酸酸性溶液(電解液)で満たされた電解槽に上記アノードを装入し、カソードとの間に通電して電解精製を行う。この電解精製によって、アノードの銅は溶解された後、カソード上に純度99.99%の電気銅として析出し、製品となる。この時、アノードに分配されていた砒素は電解液中に溶出する。溶出した砒素は、脱銅電解によって脱銅スライムとして回収される。この脱銅スライムは、中間原料とされたり、炉に繰り返されたりする。
(3) Electrolytic process In the electrolytic process, the anode is placed in an electrolytic tank filled with a sulfuric acid acid solution (electrolytic solution), and an electric current is passed between the anode and the cathode for electrolytic purification. By this electrolytic refining, the copper of the anode is dissolved and then deposited on the cathode as electrolytic copper having a purity of 99.99%, resulting in a product. At this time, arsenic distributed to the anode is eluted into the electrolyte. The eluted arsenic is recovered as a copper removal slime by copper removal electrolysis. This copper removal slime is used as an intermediate raw material or is repeated in a furnace.
上述の乾式製錬工程において、スラグに分配された砒素は安定した形態で固定される。しかしダストや脱銅スライムに分配された砒素は不安定な形態であり、そのままの状態で系外に払い出して処分することは望ましくない。そこで、これらのダストや脱銅スライムは、炉に繰り返されたり、別途処理されたりする。こうして銅精鉱中の大部分の砒素分は最終的にスラグに分配され、安定した形態で固定化される。 In the above-mentioned dry smelting process, arsenic distributed in the slag is fixed in a stable form. However, arsenic distributed to dust and decopperized slime is in an unstable form, and it is not desirable to dispose of arsenic out of the system as it is. Therefore, these dust and copper removal slime are repeated in the furnace or processed separately. In this way, most of the arsenic content in the copper concentrate is finally distributed to the slag and fixed in a stable form.
ところで、近年では原料事情が変化し、銅鉱石中の不純物、特に砒素品位は年々増加傾向にあり、得られる銅精鉱中の砒素品位も徐々に高くなってきている。具体的に例示すると、以前の銅精鉱中の砒素品位は0.1〜0.2%程度であったが、近年では砒素品位が1%を超える場合も珍しくない。したがって、銅精鉱の処理量が以前と同じであっても、砒素の含有量が増加しているため、スラグに固定する処理が追いつかない場合も生じてきた。この問題を解決するために、スラグ処理設備を新設したり増強したりすることが考えられるが、多大の投資を必要とし、コストを増加させてしまう。 By the way, in recent years, the raw material situation has changed, and impurities in copper ore, especially arsenic quality, has been increasing year by year, and arsenic quality in the obtained copper concentrate has gradually increased. Specifically, the arsenic grade in the previous copper concentrate was about 0.1 to 0.2%, but it is not uncommon for the arsenic grade to exceed 1% in recent years. Therefore, even if the processing amount of the copper concentrate is the same as before, since the content of arsenic has increased, there has been a case where the processing fixed to the slag cannot catch up. In order to solve this problem, it is conceivable to newly install or reinforce slag treatment equipment, but this requires a great investment and increases the cost.
そこで、銅鉱石から銅精鉱を得る際に砒素を分離除去し、例えば以前と同レベルの砒素品位の銅精鉱にすることが出来れば、このような投資が不要となり、砒素処理の負荷を以前のまま変更することなく操業できると考えられる。 Therefore, if copper concentrate is obtained from copper ore by separating and removing arsenic, for example, if it can be made into copper concentrate with the same level of arsenic as before, such investment is unnecessary and the burden of arsenic treatment is reduced. It can be operated without change as before.
これに関し、特許文献1には、黄鉄鉱に含まれる硫砒鉄鉱を浮遊選鉱を用いて分離する方法が示されている。この方法は、黄鉄鉱に亜硫酸水素ナトリウムなど亜硫酸水素イオンを含む硫酸系の抑制剤を添加し、さらにスラリーのpHを8以下に維持し、かつスラリー温度を30℃以上として浮遊選鉱を行うことで、黄鉄鉱と硫砒鉄鉱とを分離するものである。 In this regard, Patent Document 1 discloses a method of separating arsenite contained in pyrite using flotation. This method includes adding a sulfuric acid-based inhibitor containing bisulfite ions such as sodium bisulfite to pyrite, further maintaining the pH of the slurry at 8 or less, and performing the flotation at a slurry temperature of 30 ° C. or higher. It separates pyrite and arsenite.
しかしながら、この方法を銅鉱石や銅精鉱からの砒素の分離にそのまま適用することは困難である。なぜなら、例えば黄銅鉱や斑銅鉱などを主成分とする銅精鉱では、砒素は四面砒銅鉱((CuFe)12As4S13)や硫砒銅鉱(Cu3AsS4)などの砒素鉱物として存在する場合が多く、これらの砒素鉱物は、黄銅鉱や斑銅鉱などと似た浮遊特性を持つため、浮遊選鉱によって銅と砒素とを分離することは困難なためである。 However, it is difficult to apply this method as it is to the separation of arsenic from copper ore and copper concentrate. This is because, for example, in copper concentrates mainly composed of chalcopyrite and porphyry, arsenic exists as arsenic minerals such as tetrahedral arsenite ((CuFe) 12 As 4 S 13 ) and arsenous pyrite (Cu 3 AsS 4 ). In many cases, these arsenic minerals have floating characteristics similar to those of chalcopyrite and porphyry, so it is difficult to separate copper and arsenic by flotation.
また、特許文献2には、砒素を含む銅精鉱を対象として、銅精鉱を90〜120℃で加熱処理した後、銅の抑制剤としてヘキサシアノ鉄(II)酸カリウム(黄血塩:K4[Fe(CN)6])を銅精鉱1トン(t)あたり10〜15kg添加することで、砒素鉱物を浮遊させ、沈降する黄銅鉱や斑銅鉱などと分離する方法が示されている。 Further, in Patent Document 2, copper concentrate containing arsenic is subjected to heat treatment at 90 to 120 ° C., and then potassium hexacyanoferrate (II) (yellow blood salt: K) is used as a copper inhibitor. 4 [Fe (CN) 6 ]) is added to 10 to 15 kg per ton (t) of copper concentrate to suspend arsenic minerals and separate them from precipitated chalcopyrite and porphyry. .
この方法は加熱により銅精鉱中の銅鉱物表面を酸化し、表面に不活性の酸化皮膜を形成することで銅鉱物と砒素鉱物の表面での表面化学的あるいは結晶化学的な状態に違いを生じさせ、後の浮遊選鉱における浮遊性の差を生じさせるものと考えられている。しかし、この方法を実操業で用いるには、大量の銅精鉱を加熱する設備とエネルギーを必要とし、その分コストが増加するという問題があった。 This method oxidizes the surface of the copper mineral in the copper concentrate by heating, and forms an inactive oxide film on the surface, thereby making a difference in the surface chemical or crystal chemical state on the surface of the copper mineral and the arsenic mineral. This is thought to cause a difference in floatability in subsequent flotation. However, in order to use this method in actual operation, there is a problem that equipment and energy for heating a large amount of copper concentrate are required, and the cost increases accordingly.
さらに、特許文献3には、砒素を含む非鉄金属硫化鉱物を対象として、空気、過酸化水素、その他の酸化剤を添加し、ザンセートを捕収剤、ポリアミン及び硫黄化合物の混合物を抑制剤としてpH9〜10で浮選することによって砒素鉱物を抑制する方法が示されている。この方法では、主として硫化ニッケル鉱と砒素鉱物との分離方法が述べられているが、銅鉱物と砒素鉱物との分離性は明らかにされていない。 Further, in Patent Document 3, for non-ferrous metal sulfide minerals containing arsenic, air, hydrogen peroxide, and other oxidizing agents are added, and xanthate is used as a collecting agent, and a mixture of polyamine and sulfur compound is used as a suppressing agent. A method of suppressing arsenic minerals by flotation at -10 is shown. This method mainly describes a method for separating nickel sulfide ore and arsenic mineral, but the separation between copper mineral and arsenic mineral has not been clarified.
また、非特許文献1には、銅鉱物を含有するスラリーを過酸化水素で処理した後に、硝酸ナトリウムを加えてpH5に調整し、浮遊選鉱を行う方法が示されている。また同じ文献には、銅鉱物に過酸化水素とEDTAを添加し、その後に水酸化カリウムでpH11に調整して浮遊選鉱を行う方法も提案されている。しかし、これら二つの方法は、劇物を使用するなど取扱い時の安全性やコストの点で問題があった。 Non-Patent Document 1 discloses a method in which a slurry containing copper mineral is treated with hydrogen peroxide and then sodium nitrate is added to adjust the pH to 5 to perform flotation. The same document also proposes a method of performing flotation by adding hydrogen peroxide and EDTA to a copper mineral and then adjusting the pH to 11 with potassium hydroxide. However, these two methods have problems in terms of safety and cost during handling such as using deleterious substances.
以上述べたように、いずれの方法も、浮遊選鉱法を用いて含銅物から高効率に砒素鉱物を分離するのは困難であった。 As described above, in any of the methods, it was difficult to separate arsenic minerals from copper-containing materials with high efficiency using the flotation method.
本発明の目的は、上記の従来技術の問題点に鑑み、砒素鉱物を含有する含銅物から効率よく砒素鉱物を分離する選鉱方法を提供することにある。 An object of the present invention is to provide a beneficiation method for efficiently separating an arsenic mineral from a copper-containing material containing the arsenic mineral in view of the above-described problems of the prior art.
上記の課題を解決するため、本発明が提供する含銅物からの砒素鉱物の分離方法は、砒素鉱物を含む含銅物に水を添加してスラリーにした後、該スラリーのpHを8〜12に調整して浮遊選鉱することによって含銅物から砒素鉱物を分離する方法であって、銅イオンとのキレートを生成するキレート剤を用いて含銅物を処理する工程、及び酸化剤を用いて砒素鉱物を酸化処理する工程の内の少なくとも一方を行うことを特徴としている。 In order to solve the above problems, the method for separating arsenic mineral from a copper-containing material provided by the present invention adds water to a copper-containing material containing arsenic mineral to form a slurry, and then adjusts the pH of the slurry to 8 to 8. 12 is a method of separating arsenic minerals from copper-containing materials by flotation after adjusting to 12, using a chelating agent that generates a chelate with copper ions, and using an oxidizing agent Then, at least one of the steps of oxidizing the arsenic mineral is performed.
上記本発明の砒素鉱物の分離方法においては、キレート剤にトリエチレンテトラミン及び/又はエチレンジアミン四酢酸を用いることが好ましい。また、酸化剤には空気及び/又は酸素を使用することが好ましい。 In the arsenic mineral separation method of the present invention, it is preferable to use triethylenetetramine and / or ethylenediaminetetraacetic acid as the chelating agent. Moreover, it is preferable to use air and / or oxygen as the oxidizing agent.
本発明によれば、特別な設備や危険な薬品を使用することなく、砒素や黄鉄鉱を多く含む含銅物から高品位の銅精鉱を得ることができる。このようにして得られた高品位の銅精鉱を用いて銅を製錬することにより、製錬工程中の砒素による環境への影響を抑制できる。また、砒素副産物の処理負荷の増加に伴う投資と操業費を抑制できる。 According to the present invention, high-grade copper concentrate can be obtained from a copper-containing material containing a large amount of arsenic and pyrite without using special equipment or dangerous chemicals. By smelting copper using the high-grade copper concentrate obtained in this way, the influence of arsenic on the environment during the smelting process can be suppressed. In addition, investment and operating costs associated with increased processing load of arsenic by-products can be suppressed.
以下、本発明による含銅物からの砒素鉱物の分離方法の一具体例を、含銅物が銅鉱石の場合を例にとって説明する。なお、本発明で処理する砒素鉱物や黄鉄鉱を多く含む含銅物中の金属品位や鉱物の種類は、特に限定するものではない。浮遊選鉱を行うには、砒素鉱物や黄鉄鉱が単体粒子で存在していなければ効果的でないため、粉砕等の前処理を行って、砒素鉱物の多くが単体分離されていることが望ましい。 Hereinafter, a specific example of the method for separating an arsenic mineral from a copper-containing material according to the present invention will be described by taking a case where the copper-containing material is copper ore as an example. In addition, the metal grade and the kind of mineral in the copper-containing material containing a large amount of arsenic mineral and pyrite to be treated in the present invention are not particularly limited. In order to perform flotation, it is not effective if arsenic minerals and pyrite are not present as single particles. Therefore, it is desirable that most of the arsenic minerals are separated by pretreatment such as grinding.
また、本発明が対象とする含銅物は銅鉱石に限定されるものでなく、銅精鉱であってもよい。この場合は、従来から行われている一般的な浮遊選鉱法を用いて先ず不純物を多く含む低品位の銅精鉱を回収し、次に本発明の分離方法に従って砒素鉱物や黄鉄鉱を分離して高品位の銅精鉱を回収することになる。すなわち、低品位の銅精鉱から高品位の銅精鉱を回収する場合にも本発明を適用することができる。この場合、中間原料となる不純物を高濃度に含む銅精鉱の銅品位には特に限定がない。 Further, the copper-containing material targeted by the present invention is not limited to copper ore, but may be copper concentrate. In this case, low-grade copper concentrate containing a large amount of impurities is first recovered using a conventional flotation method that has been conventionally used, and then arsenic minerals and pyrite are separated according to the separation method of the present invention. High quality copper concentrate will be recovered. That is, the present invention can also be applied to recovering high-grade copper concentrate from low-grade copper concentrate. In this case, there is no particular limitation on the copper quality of the copper concentrate containing the impurity as an intermediate raw material at a high concentration.
本発明の一具体例の砒素鉱物の分離方法では、先ず高品位に砒素を含有する銅鉱石に対して必要に応じて水を添加した上で粉砕し、粉砕された銅鉱石に所定量の水を加えてスラリー化する。次に得られたスラリーに水酸化カルシウムなどのアルカリを添加し、スラリーのpHを8〜12、より好ましくは8.5〜11.5の範囲に調整する。そして、このpH調整されたスラリーを浮遊選鉱に供し、浮上した鉱石(浮鉱)として高品位の銅精鉱を得る。 In the method for separating arsenic mineral according to one specific example of the present invention, high-quality copper ore containing arsenic is first pulverized after adding water as necessary, and a predetermined amount of water is added to the pulverized copper ore. To make a slurry. Next, an alkali such as calcium hydroxide is added to the obtained slurry, and the pH of the slurry is adjusted to a range of 8 to 12, more preferably 8.5 to 11.5. Then, this pH-adjusted slurry is subjected to flotation, and high-grade copper concentrate is obtained as a floated ore (floating ore).
浮遊選鉱(浮選)時はスラリーのpHが8未満であると、砒素鉱物の浮上を十分に抑制することができなくなり、砒素と銅との分離の割合を示す下記式1で定義される分離度が低下する。一方、スラリーのpHが12を超えると、水酸化カルシウムなどのアルカリの消費量が急激に増大する上、銅鉱物の浮上が抑制されて下記式1の分離度が低下する。 At the time of flotation (flotation), if the pH of the slurry is less than 8, the arsenic mineral flotation cannot be sufficiently suppressed, and the separation defined by the following formula 1 showing the separation ratio of arsenic and copper The degree decreases. On the other hand, when the pH of the slurry exceeds 12, the consumption of alkali such as calcium hydroxide increases rapidly, and the floating of the copper mineral is suppressed and the degree of separation of the following formula 1 decreases.
[式1]
[Formula 1]
この式1に示す分離度は、浮鉱側に含有される銅の分配率が高くて砒素の分配率が低くなるほど高い値となる。すなわち、この分離度の値が高ければ本発明の目的に合った好ましい結果が得られており、分離度の値が低ければ好ましくない結果が生じていることになる。 The degree of separation shown in Equation 1 becomes higher as the distribution ratio of copper contained in the floatation side is higher and the distribution ratio of arsenic is lower. That is, if the value of the degree of separation is high, a preferable result suitable for the purpose of the present invention is obtained, and if the value of the degree of separation is low, an undesirable result is obtained.
ところで、発明者らは上記浮選の際、本来浮上しないはずの砒素鉱物までもが浮遊することがあり、その原因としてスラリーの水相及びけん濁している砒素鉱物の表面に存在する可溶性の銅(以降、可溶性銅とも称する)が砒素鉱物と捕収剤との結合を促し、これによって砒素鉱物が浮遊することを見出した。この可溶性銅は、含銅物が酸化して生じたと考えられる。 By the way, the inventors may float even the arsenic mineral that should not float during the flotation, and the cause is soluble copper present on the surface of the slurry aqueous phase and suspended arsenic mineral. (Hereinafter, also referred to as soluble copper) promoted the binding between the arsenic mineral and the scavenger, thereby finding that the arsenic mineral floats. This soluble copper is considered to be produced by oxidation of the copper-containing material.
そこで本発明者らは、上記浮選に供されるスラリーにキレート剤を添加して可溶性銅を錯化し、砒素鉱物の表面から可溶性銅を除去することによって砒素鉱物の浮遊性を低下させ、よって砒素鉱物と銅精鉱との浮選分離を確実に行うことを可能にした。 Therefore, the present inventors add a chelating agent to the slurry subjected to the flotation to complex soluble copper and reduce the arsenic mineral's floatability by removing soluble copper from the surface of the arsenic mineral, thus The flotation separation of arsenic mineral and copper concentrate was made possible.
添加するキレート剤には、銅との錯生成定数が高いものが好ましい。具体的には、TETA(トリエチレンテトラミン)やEDTA(エチレンジアミン四酢酸)等を挙げることができる。これらキレート剤の種類や添加量は、予備試験などを行って、対象物に含まれる可溶性銅に対して必要十分な量を予め求めておき、その基準に従って適宜決定すれば良い。 The chelating agent to be added preferably has a high complex formation constant with copper. Specific examples include TETA (triethylenetetramine) and EDTA (ethylenediaminetetraacetic acid). The type and amount of these chelating agents may be determined appropriately according to the criteria by conducting a preliminary test and obtaining in advance a necessary and sufficient amount for the soluble copper contained in the object.
キレート剤を添加するタイミングは、浮選の際に添加する捕収剤の添加と同時かそれ以前であれば特に限定はないが、粉砕工程よりも前の段階か又は粉砕工程中に添加するのが好ましい。なぜなら、粉砕に伴って空気が巻き込まれるので、その酸化作用により発生した可溶性銅を迅速かつ効果的に除去できるからである。なお、この粉砕工程において、後述する酸化工程に先立って砒素鉱物に対してある程度の酸化処理を施すことが可能である。 The timing of adding the chelating agent is not particularly limited as long as it is the same as or earlier than the addition of the collection agent added at the time of flotation, but it is added before the pulverization process or during the pulverization process. Is preferred. This is because air is entrained with the pulverization, so that soluble copper generated by the oxidation action can be removed quickly and effectively. In this pulverization step, it is possible to subject the arsenic mineral to some degree of oxidation prior to the oxidation step described later.
キレート剤及び水の存在下で含銅物を粉砕する場合は、粉砕後に生じるスラリーの水相部分にキレート剤によって錯体となった可溶性銅が溶存している。このため、粉砕後は当該スラリーをろ過又は沈降濃縮等によって固液分離するのが好ましい。これにより、可溶性銅を含む水相部分を固形分から分離することができる。得られた固形分は、再度水を添加してリパルプ(スラリー化)した後、次の酸化工程に送る。 When the copper-containing material is pulverized in the presence of a chelating agent and water, soluble copper that is complexed by the chelating agent is dissolved in the aqueous phase portion of the slurry that is produced after pulverization. For this reason, after the pulverization, the slurry is preferably subjected to solid-liquid separation by filtration or sedimentation concentration. Thereby, the aqueous phase part containing soluble copper can be isolate | separated from solid content. The obtained solid content is repulped by adding water again (slurry) and then sent to the next oxidation step.
なお、上記固液分離によって除去された水相にはキレート剤が含まれるため、適宜処理を施してキレート剤の回収を行うのが好ましい。例えば、水相に水硫化ナトリウム等の硫化剤を添加することにより、当該水相内に蓄積している銅やその他の金属成分を硫化物の形態で沈殿させて分離することができる。これにより、キレート剤の錯化能力を回復し、再び粉砕工程に繰り返して使用できる。 Since the aqueous phase removed by the solid-liquid separation contains a chelating agent, it is preferable to recover the chelating agent by appropriately performing a treatment. For example, by adding a sulfurizing agent such as sodium hydrosulfide to the aqueous phase, copper and other metal components accumulated in the aqueous phase can be precipitated and separated in the form of sulfide. Thereby, the complexing ability of the chelating agent can be recovered and used again in the pulverization step.
酸化工程では、可溶性銅の除去された含銅物を含むスラリーに酸化剤を加えて適度な酸化条件下にする。これにより、砒素鉱物だけを選択的に酸化処理することが可能となり、砒素鉱物の疎水性を低下させて砒素鉱物と含銅物との分離性を改善することができる。使用する酸化剤には、空気、酸素、次亜塩素酸ナトリウム、オゾン等一般的な酸化剤から適宜選定することができる。この中では、純酸素をボンベからスラリー中に吹き込む方法が最も容易かつ効果的である。 In the oxidation step, an oxidizing agent is added to the slurry containing the copper-containing material from which the soluble copper has been removed to obtain appropriate oxidation conditions. As a result, only the arsenic mineral can be selectively oxidized, and the hydrophobicity of the arsenic mineral can be reduced to improve the separability between the arsenic mineral and the copper-containing material. The oxidizing agent to be used can be appropriately selected from general oxidizing agents such as air, oxygen, sodium hypochlorite and ozone. Of these, the method of blowing pure oxygen from a cylinder into the slurry is the easiest and most effective.
酸化剤の添加量は、対象となる鉱石や鉱物によって変化するため、予備試験を行なって定めれば良い。あるいはスラリーの酸化還元電位を測定し、得られた電位値と予備試験で得た結果を比較するなどして管理する方法も効果がある。例えば酸化剤に純酸素を用いる場合は、スラリーに5〜60分程度吹込むのが好ましい。この時間が60分を超えて長時間になると、含銅物が再び酸化して浮上し難くなる。一方、5分未満では酸化の効果がほとんど得られない。 Since the amount of oxidant added varies depending on the target ore or mineral, it may be determined by conducting a preliminary test. Alternatively, a method of managing by measuring the oxidation-reduction potential of the slurry and comparing the obtained potential value with the result obtained in the preliminary test is also effective. For example, when pure oxygen is used as the oxidizing agent, it is preferable to blow it into the slurry for about 5 to 60 minutes. When this time exceeds 60 minutes and becomes a long time, the copper-containing material is oxidized again and is difficult to float. On the other hand, if it is less than 5 minutes, the oxidation effect is hardly obtained.
上記したキレート剤の添加による可溶性銅の除去処理や酸化剤の添加による酸化処理における処理条件は、処理される含銅物の酸化状態によって適宜調整するのが好ましい。具体的には、原料としての含銅物がほとんど酸化されていない場合には、キレート剤の添加量を減らすか若しくは全く添加しないのが好ましい。一方、原料としての含銅物が既に適度な酸化を受けている場合は、酸化剤の添加量を減らすか若しくは全く添加しないのが好ましい。 It is preferable to appropriately adjust the treatment conditions in the removal treatment of soluble copper by addition of the chelating agent and the oxidation treatment by addition of an oxidizing agent according to the oxidation state of the copper-containing material to be treated. Specifically, when the copper-containing material as a raw material is hardly oxidized, it is preferable to reduce the addition amount of the chelating agent or not add it at all. On the other hand, when the copper-containing material as a raw material has already undergone appropriate oxidation, it is preferable to reduce the addition amount of the oxidizing agent or not add it at all.
このように、処理される含銅物の酸化状態に応じて、銅イオンとのキレートを生成するキレート剤を用いて含銅物を処理する工程を行うか、若しくは酸化剤を用いて砒素鉱物を酸化処理する工程を行うか、又はこれらの工程を両方とも行うか適宜選択するのが好ましい。なお、含銅物の酸化状態は、前述したように、スラリー化したときの酸化還元電位を測定する等の予備試験を行うことにより判断することができる。 Thus, depending on the oxidation state of the copper-containing material to be treated, a step of treating the copper-containing material using a chelating agent that forms a chelate with copper ions is performed, or an arsenic mineral is added using an oxidizing agent. It is preferable to appropriately select whether to perform the oxidation treatment or to perform both of these steps. In addition, as described above, the oxidation state of the copper-containing material can be determined by performing a preliminary test such as measuring the oxidation-reduction potential when it is slurried.
キレート剤を用いて含銅物を処理する工程及び/又は酸化剤を用いて砒素鉱物を酸化処理する工程で処理されたスラリーは、次に浮遊選鉱工程に送られる。ここでスラリーに起泡剤及び捕収剤を添加すると共に空気を吹き込むことにより、水に対する親和性の違いを利用して含銅物を浮鉱と沈鉱とに分離することができる。すなわち、含銅物中に含まれる脈石及び砒素鉱物を沈鉱とし、含銅物中に含まれる低砒素品位の銅精鉱を浮鉱として分離することができる。 The slurry treated in the step of treating the copper-containing material using the chelating agent and / or the step of oxidizing the arsenic mineral using the oxidizing agent is then sent to the flotation process. Here, by adding a foaming agent and a collection agent to the slurry and blowing air, the copper-containing material can be separated into floatation and sedimentation using the difference in affinity for water. That is, the gangue and arsenic minerals contained in the copper-containing material can be separated into precipitates, and the low arsenic grade copper concentrate contained in the copper-containing material can be separated as floatation.
このように、本発明では選鉱工程において砒素濃縮物と低砒素品位の銅精鉱とを得ることができるので、含銅物の砒素含有量が増加しても、乾式製錬工程において、スラグ処理や脱銅電解など砒素を除去し回収する設備を増強するといった多大な投資を必要とせずに、以前と同様に処理して製品電気銅を得ることができる。また、砒素濃縮物は、別途処理することで、砒素を回収して金属砒素や砒素化合物などの原料として用いることができる上、砒素濃縮物に分配した銅を回収することもできる。 As described above, in the present invention, since the arsenic concentrate and the low arsenic grade copper concentrate can be obtained in the beneficiation process, the slag treatment is performed in the dry smelting process even if the arsenic content of the copper-containing material is increased. It is possible to obtain product electrolytic copper by performing the same treatment as before without requiring a great investment such as enhancing the equipment for removing and collecting arsenic such as copper removal and electrolysis. In addition, the arsenic concentrate can be separately treated to collect arsenic and use it as a raw material for metal arsenic, arsenic compounds, and the like, and it is also possible to recover copper distributed to the arsenic concentrate.
なお、上記した砒素鉱物の分離方法では最初に含銅物の粉砕を行ったが、含銅物が細かな銅精鉱で構成される場合は、かかる粉砕処理をバイパスしてもよい。また、キレート剤は含銅物の粉砕後に添加してもよいが、前述したように粉砕前に水と共にキレート剤を添加したほうが、粉砕に伴う含銅物の酸化を抑制できるので好ましい。含銅物にキレート剤を添加するときは、含銅物に水を加えてスラリーにした後に添加してもよいし、含銅物にキレート剤を添加した後に水を加えてスラリーにしてもよい。 In the above arsenic mineral separation method, the copper-containing material is first pulverized. However, when the copper-containing material is composed of fine copper concentrate, the pulverization process may be bypassed. The chelating agent may be added after pulverization of the copper-containing material, but as described above, it is preferable to add the chelating agent together with water before pulverization because oxidation of the copper-containing material accompanying pulverization can be suppressed. When adding a chelating agent to a copper-containing material, water may be added to the copper-containing material to make a slurry, or after adding a chelating agent to the copper-containing material, water may be added to make a slurry. .
以下に示す実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。なお、以下の実施例では、化学分析値はICP発光分析法を用いて求め、鉱物割合は顕微鏡観察によって求めた。また、含銅物には下記の表1に示す化学分析値及び鉱物割合を有する各銅精鉱を使用した。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, the chemical analysis value was determined using an ICP emission analysis method, and the mineral ratio was determined by microscopic observation. Moreover, each copper concentrate which has the chemical analysis value and mineral ratio which are shown in following Table 1 was used for the copper containing material.
[実施例1]
含銅物として上記表1の内のオーストラリア産銅精鉱Aを用い、これを図1に示すフローに沿って処理して低砒素品位銅精鉱と砒素濃縮物とを得た。具体的には、上記表1のオーストラリア産銅精鉱A100gに水100mlを混合し、さらにTETA(トリエチレンテトラミン)を銅精鉱1tに対して100kg添加し、ボールミルで80%通過粒径が25μmになるように粉砕した(粉砕工程1及び可溶性銅除去工程2)。
[Example 1]
Australian copper concentrate A in Table 1 above was used as the copper-containing material, and this was processed along the flow shown in FIG. 1 to obtain low arsenic grade copper concentrate and arsenic concentrate. Specifically, 100 ml of water is mixed with 100 g of Australian copper concentrate A in Table 1 above, 100 kg of TETA (triethylenetetramine) is added to 1 t of copper concentrate, and 80% passing particle size is 25 μm with a ball mill. (Crushing step 1 and soluble copper removal step 2).
粉砕物を取り出してろ紙及びヌッチェを用いて固液分離し、溶出した銅(可溶性銅)及びTETAを含む水溶液を固形分から分離した(キレート剤回収工程3)。得られた固形分に水を加えてリパルプし、全体の体積が400mlのスラリーとした(スラリー化工程4)。このスラリーを、セル容量0.5Lのアジテア型浮遊選鉱試験機に装入し、攪拌を開始した。 The pulverized product was taken out and subjected to solid-liquid separation using filter paper and Nutsche, and an aqueous solution containing eluted copper (soluble copper) and TETA was separated from the solid content (chelating agent recovery step 3). Water was added to the obtained solid content and repulped to obtain a slurry having a total volume of 400 ml (slurry step 4). This slurry was charged into an agitaire type flotation tester having a cell capacity of 0.5 L, and stirring was started.
撹拌しながら、純酸素を2リットル/min吹き込み、これを10min続けた(酸化工程5)。次に、スラリーに水酸化カルシウムを添加してpHを11.0に調整した後、捕収剤として、米国Cytec Industries Inc.社製の商品名AP208を銅精鉱1tあたり75gの添加量に相当する0.0075g添加した。 While stirring, pure oxygen was blown at 2 liter / min, and this was continued for 10 min (oxidation step 5). Next, after adjusting the pH to 11.0 by adding calcium hydroxide to the slurry, US Cytec Industries Inc. The product name AP208 manufactured by the company was added in the amount of 0.0075 g corresponding to the added amount of 75 g per ton of copper concentrate.
さらに、起泡剤として、MIBC(メチルイソブチルカービノール)を銅精鉱1tあたり90gの添加量に相当する0.0090g添加した。これらの添加量は、予備実験によって最良の結果が得られる量から求めた。これらの捕収剤と起泡剤とを添加した後、2分間攪拌しながらpHを測定し、pHが低下している場合には消石灰を添加してpHを11.0に調整した。 Further, as a foaming agent, MIBC (methyl isobutyl carbinol) was added in an amount of 0.0090 g corresponding to an addition amount of 90 g per 1 ton of copper concentrate. These addition amounts were determined from the amounts that gave the best results by preliminary experiments. After adding these collector and foaming agent, the pH was measured while stirring for 2 minutes, and when the pH was lowered, slaked lime was added to adjust the pH to 11.0.
その後、攪拌を継続し、空気をおおよそ2リットル/minの流量で吹き込みながら4分間浮選し、浮鉱(低砒素銅精鉱)と沈鉱(砒素濃縮物)とに分離した(浮遊選鉱工程6)。この実施例においては、簡略化のため精選工程を省略し、1回の浮選で工程を終了した。このようにして、試料1の砒素濃縮物と低砒素銅精鉱とを作製した。 After that, stirring was continued, and the air was blown for 4 minutes while blowing air at a flow rate of approximately 2 liters / min. 6). In this example, the simplification process was omitted for simplification, and the process was completed by one flotation. Thus, the arsenic concentrate of sample 1 and the low arsenic copper concentrate were produced.
次に、酸化工程5における純酸素の吹き込み時間を、それぞれ20、30、及び45min続けた以外は上記試料1の場合と同様にして試料2〜4の砒素濃縮物と低砒素銅精鉱とを作製した。 Next, the arsenic concentrates and low arsenic copper concentrates of Samples 2 to 4 were obtained in the same manner as in Sample 1 except that the pure oxygen blowing time in the oxidation step 5 was continued for 20, 30 and 45 minutes, respectively. Produced.
更に、酸化工程5を実施しない以外は上記試料1の場合と同様にして試料5の砒素濃縮物と低砒素銅精鉱とを作製した。また、キレート剤を添加しないこと、すなわち可溶性銅除去工程2を実施しない以外は上記試料2の場合と同様にして試料6の砒素濃縮物と低砒素銅精鉱とを作製した。そして比較のため、酸化工程5及び可溶性銅除去工程2を共に実施しないことに加えて浮選時のpHを11.0に代えて7.0にした以外は上記試料1の場合と同様にして試料7の砒素濃縮物と低砒素銅精鉱とを作製した。 Further, the arsenic concentrate and low arsenic copper concentrate of Sample 5 were produced in the same manner as in Sample 1 except that the oxidation step 5 was not performed. Further, the arsenic concentrate and low arsenic copper concentrate of Sample 6 were prepared in the same manner as in Sample 2 except that the chelating agent was not added, that is, the soluble copper removal step 2 was not performed. For comparison, in addition to not performing both the oxidation step 5 and the soluble copper removal step 2, the same as in the case of the sample 1 except that the pH at the time of flotation was changed to 7.0 instead of 11.0. Sample 7 arsenic concentrate and low arsenic copper concentrate were prepared.
このようにして得た試料1〜7について、低砒素銅精鉱の歩留及び品位、低砒素銅精鉱及び砒素濃縮物の実収率、並びに分離度を主な処理条件と共に表2に示す。なお、実収率は、砒素濃縮物及び低砒素銅精鉱にそれぞれ含まれる銅及び砒素の量を、処理前の含銅物に含まれるそれぞれの量で除して得た値であり、歩留は低砒素銅精鉱の重量を処理前の銅精鉱の重量で除すことによって得た値である。また、分離度は前述した式1から得た値である。 Table 2 shows the yield and quality of the low arsenic copper concentrate, the actual yield of the low arsenic copper concentrate and the arsenic concentrate, and the degree of separation, along with the main processing conditions, for the samples 1 to 7 thus obtained. The actual yield is a value obtained by dividing the amount of copper and arsenic contained in the arsenic concentrate and low arsenic copper concentrate by the amount contained in the copper-containing material before treatment, respectively. Is a value obtained by dividing the weight of the low arsenic copper concentrate by the weight of the copper concentrate before treatment. The degree of separation is a value obtained from Equation 1 described above.
上記表2から分かるように、比較例の試料7は銅の実収率と分離度がそれぞれ63.0%と0.7であった。これに対して、試料1は銅の実収率が71.5%、分離度が6.1と共に高い値となった。また、純酸素吹き込み時間をそれぞれ20、30、及び45minに延長した試料2〜4は、銅の実収率が徐々に低下した。これは、本来浮遊性を有する銅鉱物の一部が酸化されて親水化したことに因るものと考えられる。 As can be seen from Table 2 above, the sample 7 of the comparative example had a copper actual yield and a degree of separation of 63.0% and 0.7, respectively. On the other hand, Sample 1 had a high copper yield of 71.5% and a degree of separation of 6.1. In addition, in Samples 2 to 4 in which the pure oxygen blowing time was extended to 20, 30 and 45 min, respectively, the actual yield of copper gradually decreased. This is thought to be due to the fact that part of the copper mineral that originally has free-floating property has been oxidized to become hydrophilic.
また、酸化工程5を省略した試料5は、砒素鉱物の浮遊性がやや高くなり、分離度は4.0となった。一方、キレート剤の添加による可溶性銅の除去を行わなかった試料6は、砒素鉱物の浮遊性が増して分離度が2.4となった。これらはいずれも試料7の0.7を大きく上回っているものの、オーストラリア産銅精鉱Aの場合は、可溶性銅除去工程2と酸化工程5の両方を適用することにより効果的に砒素鉱物の浮遊を抑制できることが分かる。 Further, in Sample 5 in which the oxidation step 5 was omitted, the arsenic mineral floatability was slightly high, and the degree of separation was 4.0. On the other hand, Sample 6 in which the soluble copper was not removed by the addition of the chelating agent increased the arsenic mineral's floatability and the degree of separation became 2.4. Although these are much higher than the 0.7 of sample 7, in the case of Australian copper concentrate A, the floating of arsenic mineral is effectively achieved by applying both soluble copper removal process 2 and oxidation process 5. It can be seen that it can be suppressed.
[実施例2]
含銅物として上記表1のオーストラリア産銅精鉱Aに代えてペルー産銅精鉱Bを使用した以外は上記実施例1の試料1及び2の場合と同様にして、それぞれ試料8及び9の砒素濃縮物と低砒素銅精鉱とを作製した。また、酸化工程5における純酸素の吹き込み時間を60min続けた以外は上記試料8の場合と同様にして試料10の砒素濃縮物と低砒素銅精鉱とを作製した。
[Example 2]
As in the case of Samples 1 and 2 in Example 1 above, except for using the Peruvian copper concentrate B instead of the Australian copper concentrate A in Table 1 above as the copper-containing material, Arsenic concentrate and low arsenic copper concentrate were prepared. Further, the arsenic concentrate and low arsenic copper concentrate of Sample 10 were produced in the same manner as in Sample 8 except that the pure oxygen blowing time in the oxidation step 5 was continued for 60 minutes.
更に、酸化工程5を実施しない以外は上記試料8の場合と同様にして試料11の砒素濃縮物と低砒素銅精鉱とを作製した。そして比較のため、酸化工程5及び可溶性銅除去工程2を共に実施しないことに加えて浮選時のpHを11.0に代えて7.0にした以外は上記試料8の場合と同様にして試料12の砒素濃縮物と低砒素銅精鉱とを作製した。 Further, the arsenic concentrate and low arsenic copper concentrate of Sample 11 were prepared in the same manner as in Sample 8 except that the oxidation step 5 was not performed. For comparison, in addition to not performing both the oxidation step 5 and the soluble copper removal step 2, the same as in the case of the sample 8 except that the pH at the time of flotation was changed to 7.0 instead of 11.0. Sample 12 arsenic concentrate and low arsenic copper concentrate were prepared.
このようにして得た試料8〜12について、低砒素銅精鉱の歩留及び品位、低砒素銅精鉱及び砒素濃縮物の実収率、並びに分離度を主な処理条件と共に表3に示す。なお、実収率、歩留及び分離度は実施例1と同様にして得た値である。 Table 3 shows the yield and quality of the low arsenic copper concentrate, the actual yield of the low arsenic copper concentrate and the arsenic concentrate, and the degree of separation, along with the main processing conditions, for the samples 8 to 12 thus obtained. The actual yield, yield, and degree of separation are values obtained in the same manner as in Example 1.
上記表3から分かるように、比較例の試料12は銅の実収率と分離度がそれぞれ84.5%と2.1であったのに対して、試料8は銅の実収率が81.9%と僅かに低下し、分離度は4.3に上昇した。酸素吹き込み時間をそれぞれ20minと60minに延長した試料9及び10は、分離度がそれぞれ4.7及び6.7に上昇したが、銅の実収率はそれぞれ72.8%と72.1%に低下した。この結果から、ペルー産銅精鉱Bの場合は、目的に応じて可溶性銅除去工程2及び酸化工程5の内のいずれかを適用したり、これら両方の工程を適用したりすることによって効果的に砒素鉱物の浮遊を抑制できることが分かる。 As can be seen from Table 3 above, Sample 12 of the comparative example had an actual copper yield and resolution of 84.5% and 2.1, respectively, whereas Sample 8 had an actual copper yield of 81.9. %, The degree of separation increased to 4.3. Samples 9 and 10 with the oxygen blowing time extended to 20 min and 60 min, respectively, increased the separation to 4.7 and 6.7, respectively, but the actual copper yield decreased to 72.8% and 72.1%, respectively. did. From this result, in the case of Peruvian copper concentrate B, it is effective to apply either soluble copper removal step 2 or oxidation step 5 depending on the purpose, or to apply both of these steps. It can be seen that floating of arsenic mineral can be suppressed.
1 粉砕工程
2 可溶性銅除去工程
3 キレート剤回収工程
4 スラリー化工程
5 酸化工程
6 浮遊選鉱工程
1 Crushing process 2 Soluble copper removal process 3 Chelating agent recovery process 4 Slurry process 5 Oxidation process 6 Flotation process
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JP2021074640A (en) * | 2019-11-05 | 2021-05-20 | 国立大学法人九州大学 | Mineral processing method |
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CN103191833A (en) * | 2013-04-23 | 2013-07-10 | 昆明理工大学 | Cuprite vulcanizing strengthening method in mixed copper ore floatation |
JP2021074640A (en) * | 2019-11-05 | 2021-05-20 | 国立大学法人九州大学 | Mineral processing method |
JP7299592B2 (en) | 2019-11-05 | 2023-06-28 | 国立大学法人九州大学 | beneficiation method |
WO2022044599A1 (en) * | 2020-08-27 | 2022-03-03 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for selectively recovering arsenic-containing copper mineral, and flotation agent used in same |
JP7390632B2 (en) | 2020-08-27 | 2023-12-04 | 独立行政法人エネルギー・金属鉱物資源機構 | Method for selectively recovering arsenic-containing copper minerals and flotation agent used therein |
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JP7385872B2 (en) | 2021-12-17 | 2023-11-24 | 国立大学法人九州大学 | Ore beneficiation method |
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