JP5299809B2 - Metal recovery from non-ferrous metal smelting residue - Google Patents
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- 238000003723 Smelting Methods 0.000 title claims description 108
- 229910052751 metal Inorganic materials 0.000 title claims description 44
- 239000002184 metal Substances 0.000 title claims description 44
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 11
- 238000011084 recovery Methods 0.000 title description 10
- 238000010828 elution Methods 0.000 claims description 78
- 229910052785 arsenic Inorganic materials 0.000 claims description 73
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 73
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 230000002378 acidificating effect Effects 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 122
- 229910052802 copper Inorganic materials 0.000 description 122
- 239000010949 copper Substances 0.000 description 122
- 239000000779 smoke Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001495 arsenic compounds Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 229940093920 gynecological arsenic compound Drugs 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
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- 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、非鉄金属の製錬工程において生じる残渣から金属を回収する方法に関し、特に、銅製錬工程において硫酸製造時に生じる煙灰から銅及び鉛等の有価金属を回収する方法に関する。 The present invention relates to a method for recovering a metal from a residue generated in a non-ferrous metal smelting process, and more particularly to a method for recovering valuable metals such as copper and lead from smoke ash generated during sulfuric acid production in a copper smelting process.
銅等の非鉄金属の製錬においては、煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣が発生する。このような製錬残渣には、目的とする金属の他に、鉛、ビスマス、亜鉛、砒素及びカドミウム等が含まれており、従来、前工程に戻されて再度原料として炉に投入されたり、成分毎に分離して製錬原料等として利用されたりしている（例えば、特許文献１及び２、並びに非特許文献１参照。）。例えば、特許文献１に記載の処理方法では、銅精錬の煙灰処理又は排ガス浄水処理で発生した重金属を含むスラッジを、例えば付着水分が１０％以下になるまで乾燥させた後、製銅炉に投入して溶解処理している。また、非特許文献１には、複数回溶出処理を行い、銅製錬残渣から硫酸鉛、硫化銅、石膏、銅沈殿物、砒酸鉄、鉄沈殿物、水酸化亜鉛・カドミウムを回収する方法が開示されている。
In the smelting of non-ferrous metals such as copper, smelting residues, which are by-products generated during smelting including smoke ash and slag, are generated. Such smelting residue contains lead, bismuth, zinc, arsenic, cadmium, etc., in addition to the target metal, and has been conventionally returned to the previous process and again put into the furnace as a raw material, They are separated for each component and used as smelting raw materials or the like (for example, see
更に、図２は特許文献２に記載の従来の製錬残渣処理方法を示すフローチャート図である。図２に示すように、特許文献２に記載の処理方法では、銅を多量に含む製錬残渣を経済的に処理するため、銅製錬残渣に硫酸を加えて空気又は酸素を吹き込むことにより、残渣中の銅及び砒素等を溶出させると共に、鉛、ビスマス及びアンチモン等を溶出残渣として分離し、更に、溶出液のｐＨを４．５〜６にすることにより、砒素を銅と共に沈殿させている。この特許文献２に記載の処理方法では、工程を簡略化できると共に、砒素を除去するためにのみ使用する高価な試薬が不要となるため、処理コストを低減することができる。
FIG. 2 is a flowchart showing a conventional smelting residue treatment method described in
しかしながら、前述した特許文献１及び２、並びに非特許文献１に記載の従来の技術は、砒素含有率が低い製錬残渣を対象にした処理方法であり、銅製錬工程において硫酸製造時に生じる煙灰のように、砒素含有率が高い製錬残渣の処理には不向きである。具体的には、製錬残渣に含まれる砒素の多くは、製錬対象物である銅、鉛又は共存物資として存在する鉄、その他の酸化物若しくは硫化物に固定化された状態で存在するため、砒素とこれらを相互に分離することは極めて困難である。このため、前述した従来の処理方法では、残渣中に含まれる砒素を十分に除去することができず、銅及び鉛等の有価物の回収率が低下するという問題がある。また、従来、製錬残渣中の砒素を亜砒酸等の砒素化合物の原料として利用する方法も開発されているが、近年、砒素化合物の需要が減少しており、この方法で大量の煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣を処理することは困難である。更に、このような砒素含有量が高い煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣を産業廃棄物として処理する場合、管理及び処理に多大な費用を要する。このような理由から、砒素含有率が高い煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣を有効活用できる方法が求められている。
However, the conventional techniques described in
本発明は、上述した問題点に鑑みて案出されたものであり、砒素含有量が高い銅製錬残
渣から、砒素を効率的に除去し、銅及び鉛等の有価金属を高収率で回収することができる非鉄金属製錬残渣からの金属回収方法を提供することを目的とする。
The present invention has been devised in view of the above-mentioned problems, and efficiently removes arsenic from a copper smelting residue having a high arsenic content, and recovers valuable metals such as copper and lead in a high yield. It aims at providing the metal recovery method from the nonferrous metal smelting residue which can be done.
本発明に係る非鉄金属製錬残渣からの金属回収方法は、砒素を０．１〜３０質量％含有する非鉄金属製錬残渣から金属を回収する方法であって、前記非鉄金属製錬残渣を、不活性ガス雰囲気中で、４００〜１２００℃の温度下で、１〜８時間加熱する工程と、加熱後の非鉄金属製錬残渣を、ｐＨが１．５を超え３．０未満の酸性水溶液に浸漬し、液温を１５〜２５℃に保持しながら、０．５時間以内で溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第１の溶出分離工程と、前記第１の溶出処理工程の溶出残渣を、ｐＨを１未満に調節した酸性水溶液、或いはｐＨを１未満に調節した酸性水溶液と過酸化水素水との混合溶液に浸漬し、液温を２０〜１００℃に保持しながら、０．５〜２時間溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第２の溶出分離工程とを有することを特徴とする。 The metal recovery method from a nonferrous metal smelting residue according to the present invention is a method of recovering a metal from a nonferrous metal smelting residue containing 0.1 to 30% by mass of arsenic, In an inert gas atmosphere, the step of heating at a temperature of 400 to 1200 ° C. for 1 to 8 hours and the non-ferrous metal smelting residue after heating into an acidic aqueous solution having a pH of more than 1.5 and less than 3.0 A first elution separation step in which the elution treatment is performed within 0.5 hour, followed by filtration and separation into an eluate and an elution residue, while dipping and maintaining the liquid temperature at 15 to 25 ° C .; The elution residue of 1 elution treatment step is immersed in an acidic aqueous solution whose pH is adjusted to less than 1 or a mixed solution of an acidic aqueous solution whose pH is adjusted to less than 1 and hydrogen peroxide solution, and the liquid temperature is 20 to 100 ° C. And elution treatment for 0.5-2 hours while maintaining And having a second elution separation step of separating into a dissolution residue.
この非鉄金属製錬残渣からの金属回収方法では、前記加熱工程における加熱温度を６００〜８００℃とすることが好ましい。 In the method for recovering metal from the non-ferrous metal smelting residue, the heating temperature in the heating step is preferably 600 to 800 ° C.
また、鉛を硫酸鉛、カルシウムを硫酸カルシウムとして固定化させて残渣に残留させることができるため、第１の溶出処理工程に用いる酸性水溶液として硫酸水溶液、第２の溶出処理工程に用いる溶液として硫酸水溶液、或いは硫酸水溶液と過酸化水素水との混合溶液を用いることが好ましい。さらに、第２の溶出処理工程では、用いる溶液を硫酸水溶液とした場合より、銅の浸出率が高くなるため、硫酸水溶液と過酸化水素水との混合溶液を用いることが好ましい。 In addition, since lead can be fixed as lead sulfate and calcium as calcium sulfate and can be left in the residue, sulfuric acid aqueous solution is used as the acidic aqueous solution used in the first elution treatment step, and sulfuric acid is used as the solution used in the second elution treatment step. It is preferable to use an aqueous solution or a mixed solution of a sulfuric acid aqueous solution and a hydrogen peroxide solution. Furthermore, in the second elution treatment step, since the copper leaching rate is higher than when the solution used is an aqueous sulfuric acid solution, it is preferable to use a mixed solution of an aqueous sulfuric acid solution and a hydrogen peroxide solution.
本発明によれば、溶出処理前に煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣に高温での加熱処理を行い、製錬残渣に含まれる砒素を揮発分離すると共に、加熱処理後の製錬残渣に残留している砒素を溶出処理により分離しているため、従来の方法に比べて、製錬残渣中の砒素の除去率を大幅に向上させることができ、砒素含有量が高い銅製錬残渣であっても、砒素を効率的に除去し、銅及び鉛等の有価金属を高収率で回収することができる。 According to the present invention, the smelting residue, which is a by-product generated during smelting including smoke ash and slag before elution, is subjected to heat treatment at a high temperature to volatilize and separate arsenic contained in the smelting residue, Since arsenic remaining in the smelting residue after heat treatment is separated by elution treatment, the removal rate of arsenic in the smelting residue can be greatly improved compared to conventional methods, and it contains arsenic. Even if the amount of copper smelting residue is high, arsenic can be efficiently removed and valuable metals such as copper and lead can be recovered in high yield.
以下、本発明の実施形態に係る非鉄金属製錬残渣からの金属回収方法について、添付の図面を参照して詳細に説明する。本実施形態の金属回収方法においては、砒素を０．１〜３０質量％含有する銅製錬残渣から銅及び鉛を回収する。なお、この銅製錬残渣には、前述の砒素、銅及び鉛以外に、例えばアルミニウム、珪素、硫黄、カルシウム及び鉄等が含まれている。 Hereinafter, a method for recovering metal from a nonferrous metal smelting residue according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the metal recovery method of this embodiment, copper and lead are recovered from a copper smelting residue containing 0.1 to 30% by mass of arsenic. The copper smelting residue contains, for example, aluminum, silicon, sulfur, calcium and iron in addition to the arsenic, copper and lead described above.
図１は本実施形態の非鉄金属製錬残渣からの金属回収方法を示すフローチャート図である。図１に示すように、本実施形態の金属回収方法においては、先ず、銅製錬残渣を、窒素等の不活性ガス雰囲気中で、４００〜１２００℃の温度下で、１〜８時間加熱し、銅製錬残渣から砒素を揮発分離する（ステップＳ１）。これにより、銅製錬残渣に含まれる砒素の５０〜８０質量％程度が分離され、加熱後の銅精錬残渣中の砒素含有量を７質量％以下に低減することができる。この工程において砒素は、純度が高い砒酸又は亜砒酸として回収されるため、例えば半導体材料、半導体レーザ及び発光ダイオード等への利用が期待される。一方、ステップＳ１の加熱により、銅製錬残渣中の銅及び鉛も揮発するが、その量は僅かであり、処理前の銅製錬残渣に含まれていた量に対して、銅９９質量％以上、鉛９９質量％以上が加熱後の銅精錬残渣に残留する。 FIG. 1 is a flowchart showing a method for recovering metal from nonferrous metal smelting residue according to this embodiment. As shown in FIG. 1, in the metal recovery method of the present embodiment, first, a copper smelting residue is heated in an inert gas atmosphere such as nitrogen at a temperature of 400 to 1200 ° C. for 1 to 8 hours, Arsenic is volatilely separated from the copper smelting residue (step S1). Thereby, about 50-80 mass% of arsenic contained in the copper smelting residue is separated, and the arsenic content in the copper smelting residue after heating can be reduced to 7 mass% or less. In this step, arsenic is recovered as arsenic acid or arsenous acid having a high purity, so that it is expected to be used for semiconductor materials, semiconductor lasers, light emitting diodes, and the like. On the other hand, although the copper and lead in the copper smelting residue are volatilized by heating in step S1, the amount thereof is slight, and 99% by mass or more of copper with respect to the amount contained in the copper smelting residue before treatment, 99 mass% or more of lead remains in the copper refining residue after heating.
このとき、加熱温度が４００℃未満の場合、砒酸鉄が分解されないため、後述するステップＳ３の工程において溶出残渣Ｂ１中に砒素が残留する。一方、加熱温度が１２００℃を超えると、銅及び鉛の揮発が著しくなると共に残渣が溶融するため、処理が困難となる。また、加熱時間が１時間未満の場合、砒酸鉄等の砒素化合物の分解が不十分となる。一方、８時間を超えて加熱しても、砒素の揮発量に変化はなく、加熱のためのエネルギー費のみが増加するため、経済性が悪くなる。よって、ステップＳ１では、４００〜１２００℃の温度下で、１〜８時間加熱する。なお、加熱温度は６００〜８００℃にすることが好ましく、これにより、砒素化合物を効率よく分解し、後述するステップＳ２での処理量の減量及び処理工程の簡略化ができ、更に、高温で加熱することによる銅及び鉛の揮発を最小限に抑えることができると共に、設備費及びエネルギー費の増加も防止することができる。また、加熱時の雰囲気を不活性ガス雰囲気としている理由は、砒素の酸化を抑制し、分解した砒素を揮発しやすい三酸化二砒素にすることで、砒素の揮発量を増加させ、後述するステップＳ２での処理量を減少させるためである。 At this time, when the heating temperature is less than 400 ° C., iron arsenate is not decomposed, so that arsenic remains in the elution residue B1 in the step S3 described later. On the other hand, if the heating temperature exceeds 1200 ° C., the volatilization of copper and lead becomes remarkable and the residue melts, so that the treatment becomes difficult. In addition, when the heating time is less than 1 hour, the decomposition of an arsenic compound such as iron arsenate is insufficient. On the other hand, even if the heating is performed for more than 8 hours, the volatilization amount of arsenic does not change, and only the energy cost for heating increases, resulting in poor economic efficiency. Therefore, in step S1, heating is performed at a temperature of 400 to 1200 ° C. for 1 to 8 hours. The heating temperature is preferably 600 to 800 ° C., whereby the arsenic compound can be efficiently decomposed, the amount of treatment can be reduced in step S2 to be described later, and the treatment process can be simplified. In addition to minimizing the volatilization of copper and lead, it is possible to prevent an increase in equipment costs and energy costs. Further, the reason why the atmosphere during the heating is an inert gas atmosphere is that the arsenic volatilization amount is increased by suppressing the arsenic oxidation and making the decomposed arsenic volatile arsenic trioxide, thereby increasing the amount of volatilization of arsenic. This is to reduce the processing amount in S2.
次に、加熱後の銅製錬残渣を、ｐＨが１．５を超え３．０未満の酸性水溶液に浸漬し、溶出温度を１５〜２０℃、溶出時間を０．５時間以下として溶出処理を行い、加熱後の銅製錬残渣に残留している砒素を酸性水溶液中に溶出させる（ステップＳ２）。その後、ろ過して溶出液Ａ１と溶出残渣Ｂ１とに分離する（ステップＳ３）。これにより、溶出残渣Ｂ１中の砒素濃度を１質量％以下に低減することができる。なお、この溶出処理により、加熱後の銅製錬残渣中の銅及び鉛も酸性水溶液中に溶出するが、その量は僅かであり、処理前の銅製錬残渣に含まれていた量に対して、銅９０質量％以上、鉛９９質量％以上が溶出残渣に残留する。なお、酸性水溶液としては、低コストの硫酸水溶液を用いることが好ましい。 Next, the copper smelting residue after heating is immersed in an acidic aqueous solution having a pH of more than 1.5 and less than 3.0, and an elution treatment is performed with an elution temperature of 15 to 20 ° C. and an elution time of 0.5 hours or less. The arsenic remaining in the copper smelting residue after heating is eluted in the acidic aqueous solution (step S2). Then, it filters and isolate | separates into the eluate A1 and the elution residue B1 (step S3). Thereby, the arsenic density | concentration in the elution residue B1 can be reduced to 1 mass% or less. In addition, by this elution treatment, copper and lead in the copper smelting residue after heating are also eluted in the acidic aqueous solution, but the amount is slight, with respect to the amount contained in the copper smelting residue before treatment, 90 mass% or more of copper and 99 mass% or more of lead remain in the elution residue. As the acidic aqueous solution, it is preferable to use a low-cost sulfuric acid aqueous solution.
上述した溶出処理において、酸性水溶液のｐＨが１．５以下の場合は銅の溶出量が増大し、一方、酸性水溶液のｐＨが３．０以上の場合は砒素の溶出量が減少する。また、溶出温度が１５℃未満の場合、冷却するためのエネルギーが必要となり、一方、溶出温度が２５℃を超えると、浸出促進効果が働き、銅が溶出されやすくなる。更に、溶出時間が０．５時間未満の場合は、銅がほとんど溶出しないため、浸出時間は０．５時間以上必要である。 In the elution treatment described above, the elution amount of copper increases when the pH of the acidic aqueous solution is 1.5 or less, while the elution amount of arsenic decreases when the pH of the acidic aqueous solution is 3.0 or more. Moreover, when the elution temperature is less than 15 ° C., energy for cooling is required. On the other hand, when the elution temperature exceeds 25 ° C., the leaching promoting effect works and copper is easily eluted. Furthermore, when the elution time is less than 0.5 hours, copper is hardly eluted, so that the leaching time is 0.5 hours or more.
次に、ステップＳ３で分離した溶出残渣Ｂ１を、ｐＨを１未満に調節した酸性水溶液、或いはｐＨを１未満に調節した酸性水溶液と過酸化水素水との混合溶液に浸漬し、溶出温度を２０〜１００℃、溶出時間を０．５〜２時間として溶出処理を行い、銅を溶出させる（ステップＳ４）。その後、ろ過して銅を含有する溶出液Ａ２と鉛を含有する溶出残渣Ｂ２とに分離する（ステップＳ５）。これにより、溶出液Ａ２には、処理前の銅製錬残渣に含まれていた量に対して８０質量％以上の銅が溶出し、溶出残渣Ｂ２には処理前の銅製錬残渣に含まれていた量に対して７０質量％以上の鉛が含有される。また、このとき、過酸化水素との混合溶液を用いると、銅の溶出率をより向上させることができる。溶出液Ａ２中の銅は、例えばセメンテーション、溶媒抽出、イオン浮選及びキレート吸着等を利用することにより回収することができ、回収された銅は銅製錬の原料等に利用することができる。また、溶出残渣Ｂ２中の鉛は、例えば浮遊選鉱法により鉛成分とカルシウム成分を分離することができ、鉛成分は鉛精錬の原料等に利用することができる。 Next, the elution residue B1 separated in step S3 is immersed in an acidic aqueous solution whose pH is adjusted to less than 1, or a mixed solution of an acidic aqueous solution whose pH is adjusted to less than 1 and hydrogen peroxide, and an elution temperature of 20 is set. Elution is performed at -100 ° C. and an elution time of 0.5-2 hours to elute copper (step S4). Then, it filters and isolate | separates into the eluate A2 containing copper, and the elution residue B2 containing lead (step S5). Thereby, 80 mass% or more of copper eluted in the eluate A2 with respect to the amount contained in the copper smelting residue before treatment, and the elution residue B2 was contained in the copper smelting residue before treatment. 70 mass% or more of lead is contained with respect to the amount. At this time, if a mixed solution with hydrogen peroxide is used, the elution rate of copper can be further improved. Copper in the eluate A2 can be recovered by using, for example, cementation, solvent extraction, ion flotation, chelate adsorption, and the like, and the recovered copper can be used as a raw material for copper smelting. The lead in the elution residue B2 can be separated into a lead component and a calcium component by, for example, a flotation process, and the lead component can be used as a raw material for lead refining.
上述の如く、本実施形態の非鉄金属製錬残渣からの金属回収方法においては、溶出処理前に煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣に高温での加熱処理を行い、製錬残渣に含まれる砒素を揮発分離すると共に、加熱処理後の製錬残渣に残留している砒素を溶出処理により分離しているため、従来の方法に比べて、製錬残渣中の砒素の除去率を大幅に向上させることができる。その結果、砒素含有量が高い銅製錬残渣であっても、砒素を効率的に除去し、銅及び鉛等の有価金属を高収率で回収することができる。 As described above, in the metal recovery method from the non-ferrous metal smelting residue of this embodiment, the smelting residue, which is a by-product generated during smelting including smoke ash and slag, is subjected to heat treatment at a high temperature before the elution process. And volatile separation of arsenic contained in the smelting residue, and separation of arsenic remaining in the smelting residue after heat treatment by elution treatment, so compared to the conventional method, The arsenic removal rate can be greatly improved. As a result, even a copper smelting residue having a high arsenic content can efficiently remove arsenic and recover valuable metals such as copper and lead in a high yield.
なお、本実施形態においては、銅製錬残渣から銅及び鉛を回収する方法について述べたが、本発明はこれに限定されるものではなく、銅以外の非鉄金属の煙灰、スラグ類を含む製錬時に発生する副産物類である製錬残渣にも適用することができ、同様の効果が得られる。また、銅及び鉛以外の有価成分についても、砒素を分離した後の溶出残渣から公知の方法を適用して適宜分離回収することができる。 In the present embodiment, the method for recovering copper and lead from the copper smelting residue has been described, but the present invention is not limited to this, and smelting includes smoke ash and slag of non-ferrous metals other than copper. It can also be applied to smelting residue, which is a by-product sometimes generated, and the same effect can be obtained. Further, valuable components other than copper and lead can be appropriately separated and recovered from the elution residue after separating arsenic by applying a known method.
以下、本発明の効果について、実施例及び比較例を挙げて具体的に説明する。先ず、本発明の実施例として、砒素含有量が１４．４質量％、銅含有量が２．２質量％、鉛含有量が４．４質量％の銅製錬残渣から、図１に示す方法で銅及び鉛を回収した。具体的には、
先ず、銅製錬残渣を、窒素雰囲気中、７００℃の温度下で、２時間加熱処理し、砒素を揮発分離した。これにより、処理前の銅製錬残渣に含まれる砒素の８０質量％を分離することができた。また、加熱後の銅製錬残渣の質量は、処理前の銅製錬残渣の６２％に減少しており、砒素含有量が５．７質量％、銅含有量が３．７質量％、鉛含有量が５．６％であった。そして、加熱後の銅製錬残渣中への残留率（加熱後の銅製錬残渣中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が２４％、銅が１０４％、鉛が７９％であった。
Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples. First, as an example of the present invention, from a copper smelting residue having an arsenic content of 14.4% by mass, a copper content of 2.2% by mass, and a lead content of 4.4% by mass, the method shown in FIG. Copper and lead were recovered. In particular,
First, the copper smelting residue was heat-treated in a nitrogen atmosphere at a temperature of 700 ° C. for 2 hours to volatilize and separate arsenic. Thereby, 80% by mass of arsenic contained in the copper smelting residue before treatment could be separated. Moreover, the mass of the copper smelting residue after heating is reduced to 62% of the copper smelting residue before treatment, the arsenic content is 5.7% by mass, the copper content is 3.7% by mass, and the lead content Was 5.6%. And the residual rate in the copper smelting residue after heating (amount in the copper smelting residue after heating / amount contained in the copper smelting residue before treatment) is 24% for arsenic, 104% for copper, lead Was 79%.
次に、加熱後の残渣を、０．２ｍｏｌ／リットルの硫酸水溶液にパルプ濃度１００ｇ／リットルで浸漬し、液の温度を２０℃に保持して、攪拌しながら０．２５時間溶出処理を行った。その後、０．２μｍのメンブランフィルターで濾過し、溶出液Ａ１と溶出残渣Ｂ１とに分離した。そして、溶出液Ａ１をＩＣＰにより分析したところ、砒素含有量が５１９６ｍｇ／リットル、銅が１５０ｍｇ／リットル、鉛が３４ｍｇ／リットルであり、溶出液Ａ１への溶出率（溶出液Ａ１中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が２３％、銅が４％、鉛が０．５％であった。一方、１２０℃で５時間以上乾燥させた後の溶出残渣Ｂ１の質量は、処理前の銅製錬残渣の６０％であり、砒素含有量が０．８質量％、銅含有量が３．３質量％、鉛含有量が７．５％であった。また、残留率（溶出残渣Ｂ１中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が３．１％、銅が９０％、鉛が１０１％であった。 Next, the residue after heating was immersed in a 0.2 mol / liter sulfuric acid aqueous solution at a pulp concentration of 100 g / liter, the temperature of the liquid was kept at 20 ° C., and the elution treatment was performed for 0.25 hours with stirring. . Then, it filtered with the 0.2 micrometer membrane filter, and isolate | separated into the eluate A1 and the elution residue B1. When the eluate A1 was analyzed by ICP, the arsenic content was 5196 mg / liter, copper was 150 mg / liter, and lead was 34 mg / liter. The amount contained in the previous copper smelting residue was 23% for arsenic, 4% for copper, and 0.5% for lead. On the other hand, the mass of the elution residue B1 after drying at 120 ° C. for 5 hours or more is 60% of the copper smelting residue before treatment, the arsenic content is 0.8 mass%, and the copper content is 3.3 mass. % And lead content was 7.5%. The residual ratio (amount in the elution residue B1 / amount contained in the copper smelting residue before treatment) was 3.1% for arsenic, 90% for copper, and 101% for lead.
次に、溶出残渣Ｂ１を、１ｍｏｌ／リットルの硫酸水溶液９．３３ｍｌと３０体積％の過酸化水素水０．６７ｍｌとの混合溶液に浸漬し、パルプ濃度１００ｇ／リットルで浸漬し、液の温度を６０〜６５℃に保持して、攪拌しながら０．５〜２時間溶出処理を行った。その後、０．２μｍのメンブランフィルターで濾過し、溶出液Ａ２と溶出残渣Ｂ２とに分離した。そして、溶出液Ａ２をＩＣＰにより分析したところ、砒素含有量が４４７ｍｇ／リットル、銅が４０００ｍｇ／リットル、鉛が１８ｍｇ／リットルであり、溶出液Ａ２への溶出率（溶出液Ａ２中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が２％、銅が１０８％、鉛が０．２％であった。一方、溶出残渣Ｂ１の質量は処理前の銅製錬残渣の３８％であり、砒素含有量が０．３質量％、銅含有量が０．３質量％、鉛含有量が８．５％であった。また、残留率（溶出残渣Ｂ２中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が０．３％、銅が５％、鉛が７４％であった。
Next, the elution residue B1 is immersed in a mixed solution of 9.33 ml of 1 mol / liter sulfuric acid aqueous solution and 0.67 ml of 30% by volume hydrogen peroxide solution, and is immersed at a pulp concentration of 100 g / liter. The elution treatment was performed for 0.5 to 2 hours while stirring at a temperature of 60 to 65 ° C. Then, it filtered with the 0.2 micrometer membrane filter, and isolate | separated into the eluate A2 and the elution residue B2. When the eluate A2 was analyzed by ICP, the arsenic content was 447 mg / liter, copper was 4000 mg / liter, and lead was 18 mg / liter, and the elution rate into the eluent A2 (amount / treatment in the eluent A2) The amount contained in the previous copper smelting residue was 2% for arsenic, 108% for copper, and 0.2% for lead. On the other hand, the mass of the elution residue B1 was 38% of the copper smelting residue before treatment, the arsenic content was 0.3% by mass, the copper content was 0.3% by mass, and the lead content was 8.5%. It was. The residual ratio (amount in elution residue B2 / amount contained in the copper smelting residue before treatment) was 0.3% for arsenic, 5% for copper, and 74% for lead.
また、本発明の比較例として、加熱処理を行わずに、砒素含有量が１４．４質量％、銅含有量が２．２質量％、鉛含有量が４．４質量％の銅製錬残渣から、従来の処理方法で銅及び鉛を回収した。具体的には、銅製錬残渣３０ｇを１ｍｏｌ／リットルの硫酸水溶液３００ｍｌ中で１時間溶出した後、濾過し、１００ｍｌの純水で洗浄した。その結果、濾液及び洗浄液を合わせた溶液（４００ｍｌ）は、銅が３０８ｍｇ／リットル、鉛が２ｍｇ／リットルであったが、溶出液中での回収率は銅が１９％、鉛が０．１％にすぎなかった。また、溶出残渣２０．９ｇ中には４．６質量％の砒素が残留しており、その残留率は２２％であった。 Moreover, as a comparative example of the present invention, from a copper smelting residue having an arsenic content of 14.4% by mass, a copper content of 2.2% by mass, and a lead content of 4.4% by mass without performing heat treatment. Copper and lead were recovered by conventional processing methods. Specifically, 30 g of copper smelting residue was eluted in 300 ml of 1 mol / liter sulfuric acid aqueous solution for 1 hour, filtered, and washed with 100 ml of pure water. As a result, the combined solution (400 ml) of the filtrate and the washing solution was 308 mg / liter for copper and 2 mg / liter for lead, but the recovery rate in the eluate was 19% for copper and 0.1% for lead. It was only. In addition, 4.6% by mass of arsenic remained in 20.9 g of the elution residue, and the residual rate was 22%.
以下、本発明の効果について、実施例及び比較例を挙げて具体的に説明する。先ず、本発明の実施例として、砒素含有量が１９．８質量％、銅含有量が２．９質量％、鉛含有量が４．７質量％の銅製錬残渣から、図１に示す方法で銅及び鉛を回収した。具体的には、先ず、銅製錬残渣を、窒素雰囲気中、７００℃の温度下で、２時間加熱処理し、砒素を揮発分離した。これにより、処理前の銅製錬残渣に含まれる砒素の８５質量％を分離することができた。また、加熱後の銅製錬残渣の質量は、処理前の銅製錬残渣の６０％に減少しており、砒素含有量が５．１質量％、銅含有量が３．８質量％、鉛含有量が７．１％であった。そして、加熱後の銅製錬残渣中への残留率（加熱後の銅製錬残渣中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が１６％、銅が７９％、鉛が９１％であった。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples. First, as an example of the present invention, from a copper smelting residue having an arsenic content of 19.8% by mass, a copper content of 2.9% by mass, and a lead content of 4.7% by mass, the method shown in FIG. Copper and lead were recovered. Specifically, first, a copper smelting residue was heat-treated in a nitrogen atmosphere at a temperature of 700 ° C. for 2 hours to volatilize and separate arsenic. As a result, 85% by mass of arsenic contained in the copper smelting residue before treatment could be separated. Moreover, the mass of the copper smelting residue after heating is reduced to 60% of the copper smelting residue before treatment, the arsenic content is 5.1% by mass, the copper content is 3.8% by mass, and the lead content Was 7.1%. The residual ratio in the copper smelting residue after heating (the amount in the copper smelting residue after heating / the amount contained in the copper smelting residue before treatment) is 16% for arsenic, 79% for copper, lead Was 91%.
次に、加熱後の残渣を、０．２ｍｏｌ／リットルの硫酸水溶液にパルプ濃度１００ｇ／リットルで浸漬し、液の温度を２０℃に保持して、攪拌しながら０．２５時間溶出処理を行った。その後、０．２μｍのメンブランフィルターで濾過し、溶出液Ａ１と溶出残渣Ｂ１とに分離した。そして、溶出液Ａ１をＩＣＰにより分析したところ、砒素含有量が４９００ｍｇ／リットル、銅が７０ｍｇ／リットル、鉛が４０ｍｇ／リットルであり、溶出液Ａ１への溶出率（溶出液Ａ１中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が１４％、銅が１％、鉛が０．５％であった。一方、１２０℃で５時間以上乾燥させた後の溶出残渣Ｂ１の質量は、処理前の銅製錬残渣の５８％であり、砒素含有量が０．５質量％、銅含有量が３．７質量％、鉛含有量が７．３％であった。また、残留率（溶出残渣Ｂ１中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が１．５％、銅が７４％、鉛が９１％であった。 Next, the residue after heating was immersed in a 0.2 mol / liter sulfuric acid aqueous solution at a pulp concentration of 100 g / liter, the temperature of the liquid was kept at 20 ° C., and the elution treatment was performed for 0.25 hours with stirring. . Then, it filtered with the 0.2 micrometer membrane filter, and isolate | separated into the eluate A1 and the elution residue B1. When the eluate A1 was analyzed by ICP, the arsenic content was 4900 mg / liter, copper was 70 mg / liter, and lead was 40 mg / liter, and the elution rate into the eluent A1 (amount / treatment in eluent A1 The amount contained in the previous copper smelting residue was 14% for arsenic, 1% for copper, and 0.5% for lead. On the other hand, the mass of the elution residue B1 after drying at 120 ° C. for 5 hours or more is 58% of the copper smelting residue before treatment, the arsenic content is 0.5 mass%, and the copper content is 3.7 mass. % And lead content was 7.3%. The residual ratio (amount in elution residue B1 / amount contained in the copper smelting residue before treatment) was 1.5% for arsenic, 74% for copper, and 91% for lead.
次に、溶出残渣Ｂ１を、１ｍｏｌ／リットルの硫酸水溶液９．３３ｍｌと３０体積％の過酸化水素水０．６７ｍｌとの混合溶液に浸漬し、パルプ濃度１００ｇ／リットルで浸漬し、液の温度を６０〜６５℃に保持して、攪拌しながら０．５〜２時間溶出処理を行った。その後、０．２μｍのメンブランフィルターで濾過し、溶出液Ａ２と溶出残渣Ｂ２とに分離した。そして、溶出液Ａ２をＩＣＰにより分析したところ、砒素含有量が３２０ｍｇ／リットル、銅が３７００ｍｇ／リットル、鉛が８０ｍｇ／リットルであり、溶出液Ａ２への溶出率（溶出液Ａ２中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が１％、銅が７２％、鉛が１％であった。一方、溶出残渣Ｂ１の質量は処理前の銅製錬残渣の２９％であり、砒素含有量が０．３質量％、銅含有量が０．６質量％、鉛含有量が１４．１％であった。また、残留率（溶出残渣Ｂ２中の量／処理前の銅製錬残渣に含まれていた量）は、砒素が０．４％、銅が６％、鉛が８８％であった。
Next, the elution residue B1 is immersed in a mixed solution of 9.33 ml of 1 mol / liter sulfuric acid aqueous solution and 0.67 ml of 30% by volume hydrogen peroxide solution, and is immersed at a pulp concentration of 100 g / liter. The elution treatment was performed for 0.5 to 2 hours while stirring at a temperature of 60 to 65 ° C. Then, it filtered with the 0.2 micrometer membrane filter, and isolate | separated into the eluate A2 and the elution residue B2. When the eluate A2 was analyzed by ICP, the arsenic content was 320 mg / liter, copper was 3700 mg / liter, and lead was 80 mg / liter, and the elution rate into the eluent A2 (amount / treatment in the eluent A2) The amount contained in the previous copper smelting residue was 1% for arsenic, 72% for copper, and 1% for lead. On the other hand, the mass of the elution residue B1 was 29% of the copper smelting residue before treatment, the arsenic content was 0.3% by mass, the copper content was 0.6% by mass, and the lead content was 14.1%. It was. The residual ratio (amount in elution residue B2 / amount contained in the copper smelting residue before treatment) was 0.4% for arsenic, 6% for copper, and 88% for lead.
また、本発明の比較例として、加熱処理を行わずに、砒素含有量が１９．８質量％、銅含有量が２．９質量％、鉛含有量が４．７質量％の銅製錬残渣から、従来の処理方法で銅及び鉛を回収した。具体的には、銅製錬残渣３０ｇを１ｍｏｌ／リットルの硫酸水溶液３００ｍｌ中で１時間溶出した後、濾過し、１００ｍｌの純水で洗浄した。その結果、濾液及び洗浄液を合わせた溶液（４００ｍｌ）は、銅が６６９ｍｇ／リットル、鉛が２６３ｍｇ／リットルであったが、溶出液中での回収率は銅が２９％、鉛が７％にすぎなかった。また、溶出残渣１９．４ｇ中には５．７質量％の砒素が残留しており、その残留率は１９％であった。 Further, as a comparative example of the present invention, without performing heat treatment, from a copper smelting residue having an arsenic content of 19.8 mass%, a copper content of 2.9 mass%, and a lead content of 4.7 mass% Copper and lead were recovered by conventional processing methods. Specifically, 30 g of copper smelting residue was eluted in 300 ml of 1 mol / liter sulfuric acid aqueous solution for 1 hour, filtered, and washed with 100 ml of pure water. As a result, the combined solution (400 ml) of the filtrate and the washing solution had 669 mg / liter of copper and 263 mg / liter of lead, but the recoveries in the eluate were 29% for copper and 7% for lead. There wasn't. Further, 5.7% by mass of arsenic remained in 19.4 g of the elution residue, and the residual rate was 19%.
Claims (3)
前記非鉄金属製錬残渣を、不活性ガス雰囲気中で、４００〜１２００℃の温度下で、１〜８時間加熱する工程と、
加熱後の非鉄金属製錬残渣を、ｐＨが１．５を超え３．０未満の酸性水溶液に浸漬し、液温を１５〜２５℃に保持しながら、０．５時間以内で溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第１の溶出分離工程と、
前記第１の溶出処理工程の溶出残渣を、ｐＨを１未満に調節した酸性水溶液、或いはｐＨを１未満に調節した酸性水溶液と過酸化水素水との混合溶液に浸漬し、液温を２０〜１００℃に保持しながら、０．５〜２時間溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第２の溶出分離工程と、
を有することを特徴とする非鉄金属製錬残渣からの金属回収方法。 A method of recovering a metal from a nonferrous metal smelting residue containing 0.1 to 30% by mass of arsenic,
Heating the non-ferrous metal smelting residue in an inert gas atmosphere at a temperature of 400 to 1200 ° C. for 1 to 8 hours;
The non-ferrous metal smelting residue after heating is immersed in an acidic aqueous solution having a pH of more than 1.5 and less than 3.0, and elution treatment is performed within 0.5 hours while maintaining the liquid temperature at 15 to 25 ° C. And a first elution separation step of separating the eluate and the elution residue by filtration,
The elution residue of the first elution treatment step is immersed in an acidic aqueous solution having a pH adjusted to less than 1, or a mixed solution of an acidic aqueous solution having a pH adjusted to less than 1 and hydrogen peroxide, and the liquid temperature is set to 20 to A second elution separation step of performing elution treatment for 0.5 to 2 hours while maintaining at 100 ° C., followed by filtration and separation into an eluate and an elution residue;
A method for recovering a metal from a non-ferrous metal smelting residue, comprising:
前記非鉄金属製錬残渣を、不活性ガス雰囲気中で、４００〜１２００℃の温度下で、１〜８時間加熱する工程と、
加熱後の非鉄金属製錬残渣を、ｐＨが１．５を超え３．０未満の硫酸水溶液に浸漬し、液温を１５〜２５℃に保持しながら、０．５時間以内で溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第１の溶出分離工程と、
前記第１の溶出処理工程の溶出残渣を、ｐＨを１未満に調節した硫酸水溶液と過酸化水素水との混合溶液に浸漬し、液温を２０〜１００℃に保持しながら、０．５〜２時間溶出処理を行った後濾過して、溶出液と溶出残渣とに分離する第２の溶出分離工程と、
を有することを特徴とする非鉄金属製錬残渣からの金属回収方法。 A method of recovering a metal from a nonferrous metal smelting residue containing 0.1 to 30% by mass of arsenic,
Heating the non-ferrous metal smelting residue in an inert gas atmosphere at a temperature of 400 to 1200 ° C. for 1 to 8 hours;
The non-ferrous metal smelting residue after heating is immersed in a sulfuric acid aqueous solution having a pH of more than 1.5 and less than 3.0, and elution treatment is performed within 0.5 hours while maintaining the liquid temperature at 15 to 25 ° C. And a first elution separation step of separating the eluate and the elution residue by filtration,
The elution residue of the first elution treatment step is immersed in a mixed solution of a sulfuric acid aqueous solution and a hydrogen peroxide solution whose pH is adjusted to less than 1, while maintaining the liquid temperature at 20 to 100 ° C., 0.5 to A second elution separation step of performing elution treatment for 2 hours and then filtering to separate into an eluate and an elution residue;
A method for recovering a metal from a non-ferrous metal smelting residue, comprising:
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