JP6480357B2 - Method for treating Sb-containing residue - Google Patents
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- JP6480357B2 JP6480357B2 JP2016021199A JP2016021199A JP6480357B2 JP 6480357 B2 JP6480357 B2 JP 6480357B2 JP 2016021199 A JP2016021199 A JP 2016021199A JP 2016021199 A JP2016021199 A JP 2016021199A JP 6480357 B2 JP6480357 B2 JP 6480357B2
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- 238000000034 method Methods 0.000 title claims description 31
- 238000002386 leaching Methods 0.000 claims description 43
- 238000002844 melting Methods 0.000 claims description 37
- 230000008018 melting Effects 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000000571 coke Substances 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 29
- 238000006722 reduction reaction Methods 0.000 description 17
- 229910052787 antimony Inorganic materials 0.000 description 10
- 239000011669 selenium Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 229910052711 selenium Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 229910052745 lead Inorganic materials 0.000 description 6
- 229910052714 tellurium Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- -1 etc. Inorganic materials 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 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
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- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、Ｓｂ含有残渣の処理方法に関する。 The present invention relates to a method for treating Sb-containing residues.
銅電解澱物からの精金銀工程では、Ｓｂ含有残渣として塩化鉛出浸出残渣が発生する。例えば、塩化鉛出浸出残渣は、銅電解澱物を湿式処理して得られる塩化銀を除去した浸出残渣（特許文献１参照）である。 In the fine silver process from copper electrolytic starch, lead chloride leaching residue is generated as an Sb-containing residue. For example, the lead chloride leaching residue is a leaching residue obtained by removing silver chloride obtained by wet treatment of a copper electrolytic starch (see Patent Document 1).
この塩化鉛出浸出残渣からのＳｂ（アンチモン）の回収が望まれている。 Recovery of Sb (antimony) from this lead chloride leaching residue is desired.
本発明は上記の課題に鑑み、Ｓｂ含有残渣からのＳｂの回収を効率よく行うことができるＳｂ含有残渣の処理方法を提供すること目的とする。 An object of this invention is to provide the processing method of the Sb containing residue which can perform recovery | restoration of Sb from an Sb containing residue efficiently in view of said subject.
本発明に係るＳｂ含有残渣の処理方法は、Ｓｂ含有残渣を溶解炉にて溶解させる処理方法において、前記溶解炉内に、前記Ｓｂ含有残渣を投入し、前記Ｓｂ含有残渣に対して重量比で０％以上１０％以下のコークスを投入する投入工程と、前記溶解炉内において、前記Ｓｂ含有残渣と前記コークスとを溶解する工程と、前記溶解したＳｂ含有残渣に追加のコークスを添加して、総量で前記Ｓｂ含有残渣に対して重量比で５％以上３０％以下とし、前記Ｓｂ含有残渣を溶解還元させる溶解還元工程と、を含む。 The processing method of the Sb-containing residue according to the present invention is a processing method in which the Sb-containing residue is melted in a melting furnace. The Sb-containing residue is introduced into the melting furnace and is in a weight ratio with respect to the Sb-containing residue. and adding step of introducing at least 0% to 10% of the coke in the melting furnace, comprising the steps of dissolving the said coke and the Sb-containing residue was added an additional coke Sb-containing residue obtained by the melting, A dissolution reduction step for dissolving and reducing the Sb-containing residue in a total amount of 5% to 30% by weight with respect to the Sb-containing residue.
前記溶解炉内の温度を１０００℃±１００℃としてもよい。前記溶解炉から発生するダストを、前記Ｓｂ含有残渣とともに前記溶解炉に投入してもよい。前記Ｓｂ含有残渣は、銅電解澱物から脱銅して塩化浸出し、塩化浸出後液を冷却することで析出した沈殿にアルカリ浸出を行った際の浸出残渣としてもよい。前記溶解還元工程によって得られた溶融メタルに対してソーダ処理することで、不純物を前記溶融メタルから分離するソーダ処理工程と、前記ソーダ処理工程後の前記溶融メタルからＳｂを酸化揮発させる揮発工程と、を含んでいてもよい。前記揮発工程における前記溶融メタルのＳｂ濃度が５０ｍａｓｓ％以下であってもよい。 The temperature in the melting furnace may be 1000 ° C. ± 100 ° C. Dust generated from the melting furnace may be charged into the melting furnace together with the Sb-containing residue. The Sb-containing residue may be a leaching residue when alkali leaching is performed on a precipitate deposited by removing copper from a copper electrolytic starch, leaching with chloride, and cooling the solution after leaching. A soda treatment process for separating impurities from the molten metal by subjecting the molten metal obtained by the dissolution and reduction process to a soda process, and a volatilization process for oxidizing and volatilizing Sb from the molten metal after the soda treatment process. , May be included. The Sb concentration of the molten metal in the volatilization step may be 50 mass% or less.
本発明に係るＳｂ含有残渣の処理方法によれば、Ｓｂ含有残渣からＳｂを効率よく回収することができる。 According to the method for treating a Sb-containing residue according to the present invention, Sb can be efficiently recovered from the Sb-containing residue.
本発明の対象である「不純物を含むＳｂ」とは、不純物を含むメタル状のＳｂのことである。Ｓｂは、銅電解澱物中の各種の有価物の一つである。銅電解澱物中の各種の有価物を分離回収していく中で、Ｓｂも濃縮される。本明細書では、「不純物を含むＳｂ」として、濃縮されたが、まだ、多くの不純物を含む状態のＳｂであり、濃縮回収工程における中間状態を対象とする。以下、「不純物を含むＳｂ」の一例として、銅電解澱物には各種有価物が濃縮する工程の中の発生するＳｂを多く含む塩化鉛出浸出残渣からの処理方法を例にして説明するが、これに限定されるものではない。 “Sb containing impurities”, which is the subject of the present invention, is a metallic Sb containing impurities. Sb is one of various valuable materials in the copper electrolytic starch. Sb is also concentrated while various valuables in the copper electrolytic starch are separated and recovered. In this specification, although it concentrated as "Sb containing an impurity", it is Sb of a state which still contains many impurities, and it is aimed at the intermediate state in a concentration collection process. Hereinafter, as an example of “Sb containing impurities”, a copper electrolytic starch will be described with an example of a treatment method from a lead chloride leaching residue containing a large amount of Sb generated in the process of concentrating various valuable materials. However, the present invention is not limited to this.
銅電解澱物には各種有価物が濃縮されている。この銅電解澱物を硫酸浴にリパルプし、空気を吹き付け酸化浸出することで、銅電解澱物が脱銅される。銅電解澱物中のＳｂ（アンチモン）は酸化物となり、脱銅した澱物中に留まる。脱銅した澱物に対しては、塩化浸出を行う。得られる塩化銀を分離した塩化浸出後液を冷却することによって、鉛とアンチモンを沈殿析出させることができる。析出した鉛とアンチモンの析出物にアルカリ浸出を行って不純物を除去することで、浸出残渣中にアンチモンを濃縮することができる。この浸出残渣が、塩化鉛出浸出残渣である。塩化鉛出浸出残渣は、Ｓｂ含有残渣の一例である。 Various valuable materials are concentrated in the copper electrolytic starch. The copper electrolytic starch is depulped by repulping the copper electrolytic starch into a sulfuric acid bath, blowing air and oxidizing and leaching. Sb (antimony) in the copper electrolytic starch becomes an oxide and remains in the decoppered starch. Chlorinated leaching is performed on the decoppered starch. Lead and antimony can be precipitated by cooling the solution after leaching of chloride from which the resulting silver chloride has been separated. Antimony can be concentrated in the leaching residue by performing alkaline leaching on the deposited lead and antimony precipitate to remove impurities. This leaching residue is a lead chloride leaching residue. The lead chloride leaching residue is an example of an Sb-containing residue.
図１は、塩化鉛出浸出残渣の処理方法を表す工程図である。図１で例示するように、出発原料は、塩化鉛出浸出残渣である。この塩化鉛出浸出残渣には、塩化鉛とともにＳｂ（アンチモン）などの不純物が濃縮されている。塩化鉛出浸出残渣の成分は、例えば、Ｓｂ、Ｐｂ（鉛）、Ｓｅ（セレン）、Ｔｅ（テルル）、Ｃｕ（銅）、Ｆｅ（鉄）、Ｓｎ（錫）、Ａｇ（銀）などである。例えば、塩化鉛出浸出残渣の各品位は、Ｓｂ：５０ｍａｓｓ％以下、Ｐｂ：３０ｍａｓｓ％以下、Ｓｅ：１ｍａｓｓ％以下、Ｔｅ：５ｍａｓｓ％以下、Ｃｕ：７ｍａｓｓ％以下である。 FIG. 1 is a process diagram showing a method for treating a lead chloride leaching residue. As illustrated in FIG. 1, the starting material is lead chloride leaching residue. In this lead chloride leaching residue, impurities such as Sb (antimony) are concentrated together with lead chloride. The components of the lead chloride leaching residue are, for example, Sb, Pb (lead), Se (selenium), Te (tellurium), Cu (copper), Fe (iron), Sn (tin), Ag (silver), and the like. . For example, each grade of the lead chloride leaching residue is Sb: 50 mass% or less, Pb: 30 mass% or less, Se: 1 mass% or less, Te: 5 mass% or less, and Cu: 7 mass% or less.
（乾燥工程）
塩化鉛出浸出残渣には水分が含まれていることから、乾燥によって水分量を低減する。例えば、塩化鉛出浸出残渣をコルゲート缶などに入れ、蒸気熱を用いた乾燥設備等で乾燥を行う。
(Drying process)
Since the lead chloride leaching residue contains moisture, the moisture content is reduced by drying. For example, the lead chloride leaching residue is put in a corrugated can and dried with a drying facility using steam heat.
（投入工程）
次に、乾燥後の塩化鉛出浸出残渣をソーダ灰（無水炭酸ソーダ）などとともに溶解炉に投入し、塩化鉛出浸出残渣に対して重量比で０〜１０％のコークスを溶解炉に投入する。溶解炉の温度は、１０００℃±１００℃とすることが好ましい。この場合、溶解炉内が弱還元雰囲気となる。弱還元雰囲気では、塩化鉛出浸出残渣に含まれるアンチモン酸ソーダ（ＮａＳｂＯ３）が酸化ナトリウムと酸化アンチモン（Ｓｂ２Ｏ３、Ｓｂ２Ｏ５）とに分解すると推定される。アンチモン酸ソーダ（ＮａＳｂＯ３）の融点が１４２７℃であるのに対して、Ｓｂ２Ｏ３の融点：６５６℃およびＳｂ２Ｏ５の融点：３８０℃が低くなっている。また、Ｓｂ２Ｏ３およびＳｂ２Ｏ５の融点は、上記溶解炉の温度よりも低くなっている。したがって、塩化鉛出浸出残渣の溶解を促進することができる。
(Input process)
Next, the lead chloride leaching residue after drying is put into a melting furnace together with soda ash (anhydrous sodium carbonate) and the like, and 0 to 10% by weight of coke with respect to the lead chloride leaching residue is put into the melting furnace. . The temperature of the melting furnace is preferably 1000 ° C. ± 100 ° C. In this case, the inside of the melting furnace is a weak reducing atmosphere. In a weak reducing atmosphere, it is estimated that sodium antimonate (NaSbO 3 ) contained in the lead chloride leaching residue is decomposed into sodium oxide and antimony oxide (Sb 2 O 3 , Sb 2 O 5 ). The melting point of sodium antimonate (NaSbO 3 ) is 1427 ° C., whereas the melting point of Sb 2 O 3 is 656 ° C. and the melting point of Sb 2 O 5 is 380 ° C. The melting points of Sb 2 O 3 and Sb 2 O 5 are lower than the temperature of the melting furnace. Therefore, dissolution of the lead chloride leaching residue can be promoted.
（溶解還元工程）
また、上記コークスの添加によって、塩化鉛出浸出残渣を還元することができる。還元によって、塩化鉛出浸出残渣中の塩化成分から塩素が除去され、溶融メタルと、溶融スラグとに分離する。溶融メタルには、Ｓｂ，Ｐｂ，Ａｇなどが含まれる。溶融スラグには、ソーダ灰に含まれるＮａ，Ｏなどとともに、Ｓｅ，Ｔｅなどが含まれる。なお、溶解炉から発生するダストにはＳｂ，Ｐｂなどが含まれるため、溶解炉に塩化鉛出浸出残渣とともに再度投入される。
(Dissolution reduction process)
Moreover, the lead chloride leaching residue can be reduced by the addition of the coke. By the reduction, chlorine is removed from the chloride component in the lead chloride leaching residue and separated into molten metal and molten slag. The molten metal includes Sb, Pb, Ag, and the like. The molten slag contains Se, Te, etc., as well as Na, O, etc., contained in soda ash. Since dust generated from the melting furnace contains Sb, Pb, etc., the dust is again fed into the melting furnace together with the lead chloride leaching residue.
なお、上記溶解炉の温度範囲においては、コークスは固体状態で存在する。塩化鉛出浸出残渣が溶解しなければ、上記の還元は、固固反応によって進むことになる。この場合、良好な反応性が得られないため、還元率が低下する。これに対して、塩化鉛出浸出残渣が溶解すれば、上記の還元は、固液反応によって進むことになる。この場合、良好な反応性が得られるため、還元率が向上する。 Note that coke exists in a solid state in the temperature range of the melting furnace. If the lead chloride leaching residue does not dissolve, the above reduction proceeds by a solid-solid reaction. In this case, since a good reactivity cannot be obtained, the reduction rate decreases. On the other hand, if the lead chloride leaching residue is dissolved, the above reduction proceeds by a solid-liquid reaction. In this case, good reactivity can be obtained, so that the reduction rate is improved.
コークスの投入量が少な過ぎると、Ｓｂの還元反応が不十分になるため、Ｓｂがスラグへ残留するおそれがある。一方で、コークスの投入量が多すぎると、Ｓｂの還元率が低下するおそれがある。したがって、コークスの投入量には最適な範囲が存在する。本発明者の鋭意研究によって、溶解炉に対する塩化鉛出浸出残渣の投入量に対するコークスの投入量は、重量比で、５％以上３０％以下とすることが好ましいことがわかった。この範囲では、溶融メタルへのＳｂの分配率が特に高くなる。 If the amount of coke input is too small, the reduction reaction of Sb becomes insufficient, so that Sb may remain in the slag. On the other hand, if the input amount of coke is too large, the reduction rate of Sb may be reduced. Therefore, there is an optimum range for the amount of coke input. As a result of diligent research by the present inventors, it has been found that the amount of coke to be added to the amount of lead chloride leaching residue in the melting furnace is preferably 5% to 30% by weight. In this range, the distribution ratio of Sb to the molten metal is particularly high.
そこで、還元率を向上させるために、必要に応じて追加でコークスを溶解炉に投入することが好ましい。この場合において、溶解炉に投入する塩化鉛出浸出残渣に対するコークスの総量（重量比）が５％〜３０％になるように、コークスを投入する。溶解炉に投入する塩化鉛出浸出残渣に対するコークスの総量（重量比）は、１０％以上１５％以下とすることがより好ましい。また、投入工程で投入するコークスの投入量は、溶解還元工程で投入するコークスの投入量以下であることが好ましい。この工程で得られるメタル状のＳｂは、本実施形態が対象とする「不純物を含むＳｂ」となりうる。さらに、溶融メタルの状態で揮発工程に持ち込むことも可能である。 Therefore, in order to improve the reduction rate, it is preferable to add coke to the melting furnace as needed. In this case, the coke is introduced so that the total amount (weight ratio) of coke with respect to the lead chloride leaching residue introduced into the melting furnace is 5% to 30%. More preferably, the total amount (weight ratio) of coke relative to the lead chloride leaching residue introduced into the melting furnace is 10% or more and 15% or less. Moreover, it is preferable that the amount of coke input in the input step is equal to or less than the amount of coke input in the dissolution reduction step. The metal-like Sb obtained in this step can be “Sb containing impurities” targeted by the present embodiment. Furthermore, it is possible to bring it into the volatilization process in the form of molten metal.
（ソーダ処理工程）
しかしながら、不純物および不純物の量によっては、溶融メタルを揮発工程に直接持ち込むことが好ましくない場合がある。たとえば、Ｓｅ，Ｔｅ，Ａｓなどを多く含む場合である。この場合には、溶融メタルを苛性ソーダ溶液でソーダ処理する必要がある。ソーダ処理によって、Ｓｅ，Ｔｅ，Ａｓなどを、スカムとして溶融メタルから分離することができる。溶融メタルには、Ｐｂ，Ａｇ，Ｂｉの１種以上が不純物として含まれるので、本実施形態が対象とする「不純物を含むＳｂ」として、ソーダ処理工程後のメタルは、揮発工程に持ち込まれる。溶融メタルの状態で揮発工程に持ち込むことも可能である。
(Soda treatment process)
However, depending on the impurities and the amount of impurities, it may not be preferable to bring the molten metal directly into the volatilization process. For example, it includes a large amount of Se, Te, As and the like. In this case, it is necessary to soda the molten metal with a caustic soda solution. By soda treatment, Se, Te, As, etc. can be separated from the molten metal as scum. Since one or more of Pb, Ag, and Bi are contained as impurities in the molten metal, the metal after the soda treatment process is brought into the volatilization process as “Sb containing impurities” targeted by the present embodiment. It is also possible to bring it into the volatilization process in the form of molten metal.
（揮発工程）
溶融還元によって得られたメタルおよびソーダ処理によって得られたメタルを「不純物を含むＳｂ」として、揮発炉に投入し、熱によって溶解する。さらに、溶湯を酸化することによって、Ｓｂを酸化させて揮発性のＳｂ２Ｏ３を生成する。例えば、溶湯に対して酸素を吹き付ける、吹き込む、酸化剤を添加する、などによってＳｂを酸化させることができる。Ｓｂ２Ｏ３は揮発性が高いため、溶湯から揮発する。それにより、Ｓｂを回収することができる。例えば、溶湯温度を６６０℃〜７００℃とし、溶湯への吹きつけ空気量を溶湯表面１ｍ２あたり５１〜５６Ｎｍ３／ｈとすることが好ましい。溶湯温度を６８０℃〜７００℃とすることがより好ましい。また、溶湯中のＳｂ濃度を５０ｍａｓｓ％以下、好ましくは４０ｍａｓｓ％以下とすることで、不揮発性のＳｂ２Ｏ４，Ｓｂ６Ｏ１３などの生成を抑制して、Ｓｂ２Ｏ３を生成することができる。なお、溶湯中のＳｂ濃度を希釈するに際して、Ｓｂ品位の低い（４０ｍａｓｓ％以下）原料を用いることができる。例えば、ＰｂやＢｉなどの低融点金属を主成分とする原料を用いることが好ましい。ただし、Ｐｂは揮発性を有していることから、Ｂｉを用いることがより好ましい。なお、揮発によって得られた揮発滓は、上記の溶解炉に戻して還元に供することが好ましい。
(Volatile process)
The metal obtained by the smelting reduction and the metal obtained by the soda treatment are put into a volatilization furnace as “Sb containing impurities” and melted by heat. Further, by oxidizing the molten metal, Sb is oxidized to generate volatile Sb 2 O 3 . For example, Sb can be oxidized by blowing oxygen to the molten metal, blowing it, or adding an oxidizing agent. Since Sb 2 O 3 has high volatility, it volatilizes from the molten metal. Thereby, Sb can be recovered. For example, the molten metal temperature is preferably 660 ° C. to 700 ° C., and the amount of air blown onto the molten metal is preferably 51 to 56 Nm 3 / h per 1 m 2 of the molten metal surface. More preferably, the molten metal temperature is 680 ° C to 700 ° C. Moreover, the production of nonvolatile Sb 2 O 4 , Sb 6 O 13, etc. is suppressed and Sb 2 O 3 is produced by setting the Sb concentration in the molten metal to 50 mass% or less, preferably 40 mass% or less. Can do. In addition, when diluting Sb density | concentration in a molten metal, a raw material with low Sb quality (40 mass% or less) can be used. For example, it is preferable to use a raw material whose main component is a low melting point metal such as Pb or Bi. However, it is more preferable to use Bi because Pb has volatility. The volatile soot obtained by volatilization is preferably returned to the melting furnace and used for reduction.
本実施形態によれば、Ｓｂ含有残渣を溶解炉にて溶解させる処理方法において、溶解炉内に、Ｓｂ含有残渣を投入し、Ｓｂ含有残渣に対して重量比で０％以上１０％以下のコークスを投入する投入工程が行われる。それにより、溶解炉内が弱還元性雰囲気となり、Ｓｂ含有残渣の溶解が促進される。投入工程後、追加のコークスを添加しもしくは添加しないで、総量でＳｂ含有残渣に対して重量比で５％以上３０％以下とすることで、還元率を向上させることができる。また、ソーダ処理によって、Ｓｅ，Ｔｅなどを溶液中に浸出させ、スカムとして溶融メタルから分離することができる。また、ソーダ処理後のメタル中のＳｂを酸化させることで、Ｓｂを揮発分離することができる。 According to the present embodiment, in the treatment method of dissolving the Sb-containing residue in the melting furnace, the Sb-containing residue is introduced into the melting furnace, and the coke having a weight ratio of 0% to 10% with respect to the Sb-containing residue. A charging process for charging is performed. Thereby, the inside of the melting furnace becomes a weak reducing atmosphere, and dissolution of the Sb-containing residue is promoted. After the charging step, the reduction rate can be improved by adding 5 to 30% by weight with respect to the Sb-containing residue in total with or without adding additional coke. Further, by soda treatment, Se, Te and the like can be leached into the solution and separated from the molten metal as scum. Moreover, Sb can be volatilized and separated by oxidizing Sb in the metal after the soda treatment.
溶解炉中で塩化鉛出浸出残渣を酸化させた後に、コークスを添加して還元を行った。還元においては、溶解炉を１０００℃に維持し、還元時間を８時間とした。また、塩化鉛出浸出残渣に対するコークスの添加率を、重量比で、５％（サンプル１）、１０％（サンプル２）、１５％（サンプル３）、２５％（サンプル４）とした。この場合の、Ｓｂ，Ａｇ，Ｓｅの分配率を測定した。図２（ａ）は、Ｓｂの分配率を示す。図２（ｂ）は、Ｓｅの分配率を示す。表１は、各分配率の数値を示す
図２（ａ）および表１に示すように、サンプル２〜４において、溶融メタルへのＳｂの分配率が高くなった。これは、コークスの添加量を重量比で１０％以上３０％以下とすることで、還元率が向上したからであると考えられる。また、サンプル２およびサンプル３では、サンプル１およびサンプル４よりも、溶融メタルへのＳｂの分配率が高くなった。 As shown in FIG. 2A and Table 1, in Samples 2 to 4, the distribution ratio of Sb to the molten metal was high. This is presumably because the reduction rate was improved by setting the amount of coke added to 10% to 30% by weight. In addition, in Sample 2 and Sample 3, the distribution ratio of Sb to the molten metal was higher than in Sample 1 and Sample 4.
以上、本発明の実施例について詳述したが、本発明は係る特定の実施例に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.
Claims (6)
前記溶解炉内に、前記Ｓｂ含有残渣を投入し、前記Ｓｂ含有残渣に対して重量比で０％以上１０％以下のコークスを投入する投入工程と、
前記溶解炉内において、前記Ｓｂ含有残渣と前記コークスとを溶解する工程と、
前記溶解したＳｂ含有残渣に追加のコークスを添加して、総量で前記Ｓｂ含有残渣に対して重量比で５％以上３０％以下とし、前記Ｓｂ含有残渣を溶解還元させる溶解還元工程と、を含むことを特徴とするＳｂ含有残渣の処理方法。 In the processing method of dissolving the Sb-containing residue in a melting furnace,
A charging step of charging the Sb-containing residue into the melting furnace and charging coke at a weight ratio of 0% to 10% with respect to the Sb-containing residue;
Melting the Sb-containing residue and the coke in the melting furnace;
A step of dissolving and reducing the Sb-containing residue by adding additional coke to the dissolved Sb-containing residue so that the total amount is 5% to 30% by weight with respect to the Sb-containing residue. A method for treating an Sb-containing residue.
前記ソーダ処理工程後の前記溶融メタルからＳｂを酸化揮発させる揮発工程と、を含むことを特徴とする請求項１〜４のいずれか一項に記載のＳｂ含有残渣の処理方法。 A soda treatment process for separating impurities from the molten metal by performing a soda process on the molten metal obtained by the dissolution and reduction process;
A method for treating a Sb-containing residue according to any one of claims 1 to 4, further comprising a volatilization step of oxidizing and volatilizing Sb from the molten metal after the soda treatment step.
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