JP2009292660A - Method for manufacturing metal selenium powder - Google Patents
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本発明は、金属セレン粉の製造方法に関し、さらに詳しくは、セレン含有液から還元剤として二酸化イオウを用いて生成させたセレン沈殿を回収して金属セレン粉を製造する方法において、嵩密度及び結晶粒径のバラツキが少なく一定で、荷造りや充填時のハンドリング性に優れた金属セレン粉を、高収率で製造する方法に関する。 The present invention relates to a method for producing a metal selenium powder, and more specifically, in a method for producing a metal selenium powder by recovering selenium precipitates produced from sulfur containing selenium as a reducing agent from a selenium-containing liquid. The present invention relates to a method for producing a metal selenium powder having a small particle size variation and excellent handling properties during packing and filling in a high yield.
従来、セレンは、主として非鉄金属製錬の副産物として、銅等の主金属から分離回収することにより製造されていた。
例えば、銅製錬においては、粗銅から電気銅を製造する電解工程で産出する銅電解スライムから、他の有価金属とともに、セレンの分離回収が行なわれている。この銅電解スライムの製錬方法としては、まず、銅電解スライムから湿式法により脱銅し、次いで、乾式法によりセレン、アンチモン、鉛、スズ、ビスマス、テルルなどを分離し、最後に金、銀、白金族元素の合金を得て、この合金を、電解法を中心とした湿式法により処理することにより、個々の貴金属を分離回収していた。しかしながら、この方法では、貴金属を回収するまでに長期間を要するため製錬系内での滞留期間中の金利負担が大きいこと、かつエネルギーの消費量が大きいことのほか、工程毎に固形物の運搬作業があるために自動化が困難であること、排ガスによる作業環境の汚染があること、銅電解スライムの組成及び化合物形態の変動への対応力が低いことなどの問題点があった。
Conventionally, selenium has been produced by separating and recovering from main metals such as copper as a by-product of non-ferrous metal smelting.
For example, in copper smelting, selenium is separated and recovered together with other valuable metals from a copper electrolytic slime produced in an electrolytic process for producing electrolytic copper from crude copper. As a method for smelting copper electrolytic slime, first, copper is removed from the copper electrolytic slime by a wet method, then selenium, antimony, lead, tin, bismuth, tellurium, etc. are separated by a dry method, and finally gold, silver Then, an alloy of platinum group elements was obtained, and this alloy was treated by a wet method centering on an electrolysis method, whereby individual noble metals were separated and recovered. However, in this method, it takes a long time to recover the precious metal, so that the interest burden during the residence period in the smelting system is large, the energy consumption is large, and the amount of solid matter in each process. There are problems such as difficulty in automation due to transportation work, contamination of working environment by exhaust gas, low ability to cope with variations in composition and compound form of copper electrolytic slime.
そのため、これらの解決策として、近年、湿式法を主とする製錬方法が多数提案され、徐々に採用されている。このような銅電解スライムの製錬方法として、例えば、セレンの分離方法として湿式還元法を採用し、次の（ａ）〜（ｄ）の工程を含む銅電解スライムからの有価金属の回収方法（例えば、特許文献１参照。）が提案されている。
（ａ）銅電解スライムのスラリーを、塩素で処理することにより、金、白金族元素、セレン及びテルルを浸出する。
（ｂ）得られた浸出液に、ビス（２−ブトキシエチル）エーテルを混合して金を有機相に抽出し、この有機相を塩酸で洗浄した後、蓚酸で還元することにより、金を単体として回収する。
（ｃ）金を抽出した後の抽残液に、塩化トリオクチルメチルアンモニウムと燐酸トリブチルとからなる混合物を混合して白金族元素を有機相に抽出し、この有機相を塩酸で洗浄した後、ヒドラジン及び水酸化ナトリウムで還元することにより、白金族元素を単体として集合分離する。
（ｄ）白金族元素を抽出した後の抽残液を、二酸化イオウ（ＳＯ２）により還元し、セレン及びテルルを順次単体として回収する。）
For this reason, in recent years, many smelting methods, mainly wet methods, have been proposed and gradually adopted. As such a copper electrolytic slime smelting method, for example, a wet reduction method is adopted as a method for separating selenium, and a method for recovering valuable metals from copper electrolytic slime including the following steps (a) to (d) ( For example, see Patent Document 1).
(A) The copper electrolytic slime slurry is treated with chlorine to leach gold, platinum group elements, selenium and tellurium.
(B) The obtained leachate is mixed with bis (2-butoxyethyl) ether to extract gold into an organic phase, and this organic phase is washed with hydrochloric acid, and then reduced with oxalic acid, whereby gold is used alone. to recover.
(C) A mixture of trioctylmethylammonium chloride and tributyl phosphate is mixed with the extracted residue after extracting gold to extract a platinum group element into an organic phase, and this organic phase is washed with hydrochloric acid. By reducing with hydrazine and sodium hydroxide, platinum group elements are collected and separated as a simple substance.
(D) The extraction liquid after the platinum group element is extracted is reduced with sulfur dioxide (SO 2 ), and selenium and tellurium are sequentially recovered as simple substances. )
上記方法によれば、銅電解スライムを塩素浸出に付し、得られた浸出液から、簡単な湿式操作のみによって、金、白金族元素、セレン及びテルルをそれぞれ選択的に、かつ高収率で回収することができる。したがって、上記方法は、工業的に極めて有用な方法であり、しかも、銅電解スライムの組成が変動しても金抽出工程以降に支障を来たさないこと、金の回収が完全に行なわれなくとも金属セレンへの混入を防止することができること、さらに、セレンと共沈しやすい白金族元素の金属セレンへの混入を防止することができるとともに、白金、パラジウム及びロジウムに加えて、イリジウム及びルテニウムも回収することができること等の利点があるとしている。 According to the above method, copper electrolytic slime is subjected to chlorine leaching, and gold, platinum group elements, selenium and tellurium are selectively recovered in a high yield from the obtained leachate only by a simple wet operation. can do. Therefore, the above method is an extremely useful method industrially. Moreover, even if the composition of the copper electrolytic slime fluctuates, it does not cause any trouble after the gold extraction step, and the gold is not completely recovered. In addition to being able to prevent contamination with metal selenium, it is possible to prevent contamination of platinum group elements that are likely to coprecipitate with selenium into metal selenium, and in addition to platinum, palladium and rhodium, iridium and ruthenium. There are also advantages such as being able to be recovered.
ここで、上記方法の（ｄ）の工程としては、具体的には、白金族元素を抽出した後の抽残液を二酸化イオウで還元する際に、反応容器内の液の酸化還元電位を４００〜５００ｍＶに維持し、かつ液温度を５０〜８０℃に維持するとともに、還元開始前に、反応容器内に供給した抽残液に予め金属セレン粉を懸濁させ、その後抽残液を連続的に給液しながら、二酸化イオウで連続還元する方法が提案されている。このとき、還元開始時の液中のセレン濃度と連続還元時の液中のセレン濃度との差を極力小さく、例えば５ｇ／Ｌ以下に保持するものである。 Here, as the step (d) of the above method, specifically, when the extraction residual liquid after extracting the platinum group element is reduced with sulfur dioxide, the oxidation-reduction potential of the liquid in the reaction vessel is set to 400. -500 mV, and the liquid temperature is maintained at 50-80 ° C, and before starting the reduction, the metal selenium powder is suspended in advance in the extraction residual liquid supplied in the reaction vessel, and then the extraction residual liquid is continuously added. A method of continuous reduction with sulfur dioxide while supplying liquid to the water has been proposed. At this time, the difference between the selenium concentration in the liquid at the start of reduction and the selenium concentration in the liquid at the time of continuous reduction is kept as small as possible, for example, 5 g / L or less.
ここで、反応槽への給液を連続的に行なうことと、反応槽内の初期セレン濃度と連続還元反応時のセレン濃度の差を極力小さく保つこととにより、単位時間当たり新規発生するゴム状セレンの割合を低く抑えることができる。同時に、還元初期に少量の（実施例では、１０ｇ／Ｌ相当である。）金属セレン粉を懸濁することにより、新規発生するセレンが金属セレン粉の表面に析出し、ゴム状セレンが析出しても相互の融着を防止することが可能であるとしている。また、上記セレンの濃度変化が大きいほど、ゴム状セレンが多く析出するが、変動幅が５ｇ／Ｌ以下であればゴム状セレンの析出が抑えられるとしている。 Here, by continuously supplying the liquid to the reaction tank and keeping the difference between the initial selenium concentration in the reaction tank and the selenium concentration at the time of the continuous reduction reaction as small as possible, a rubber-like newly generated per unit time is obtained. The ratio of selenium can be kept low. At the same time, by suspending a small amount of metal selenium powder (corresponding to 10 g / L in the examples) at the initial stage of reduction, newly generated selenium is deposited on the surface of the metal selenium powder, and rubbery selenium is deposited. However, it is possible to prevent mutual fusion. Further, the larger the selenium concentration change, the more rubbery selenium precipitates. However, if the fluctuation range is 5 g / L or less, the precipitation of rubbery selenium is suppressed.
しかしながら、このような工程では、セレンの還元反応を完全には進めるのは難しく、セレン沈澱として得られる金属セレン粉の収率は９５％程度と不十分であった。しかも、セレンの収率の問題だけでなく、排水処理工程では、セレン酸（Ｈ２ＳｅＯ４）の形態で残留する高濃度のセレンを処理することがさらに困難であるため、処理コストの増大を招くことが問題となっていた。さらに、金属セレン粉としては、反応槽への付着防止のため結晶状のものが取り扱い易いが、得られた金属セレン粉は、結晶粒子径が小さく、嵩密度が安定しない、などの問題点があった。 However, in such a process, it is difficult to completely proceed the reduction reaction of selenium, and the yield of metal selenium powder obtained as selenium precipitation is about 95%, which is insufficient. In addition to the problem of selenium yield, in the wastewater treatment process, it is more difficult to treat the high concentration of selenium remaining in the form of selenic acid (H 2 SeO 4 ). Inviting was a problem. Furthermore, as the metal selenium powder, a crystalline one is easy to handle to prevent adhesion to the reaction vessel, but the obtained metal selenium powder has problems such as small crystal particle diameter and unstable bulk density. there were.
本発明の目的は、上記の従来技術の問題点に鑑み、セレン含有液から還元剤として二酸化イオウを用いて生成させたセレン沈殿を回収して金属セレン粉を製造する方法において、嵩密度及び結晶粒径のバラツキが少なく一定で、荷造りや充填時のハンドリング性に優れた金属セレン粉を、高収率で製造する方法を提供することにある。 In view of the above-mentioned problems of the prior art, an object of the present invention is to recover a selenium precipitate produced from sulfur containing selenium as a reducing agent from a selenium-containing liquid to produce a metal selenium powder. An object of the present invention is to provide a method for producing a metal selenium powder having a small particle size variation and a constant and excellent handling property during packing and filling in a high yield.
本発明者らは、上記目的を達成するために、セレン含有液から還元剤として二酸化イオウを用いて生成させたセレン沈殿を回収する方法について、鋭意研究を重ねた結果、反応槽内で、セレン含有液に亜硫酸（ＳＯ２）ガスを吹込んで還元反応に付し、生成されたセレン沈殿を回収して金属セレン粉を得る際、該セレン含有液の塩酸濃度を特定値に調整し、該反応槽内へ特定量のセレン沈殿を繰り返したうえ、該還元反応の液温度と酸化還元電位とを特定値に制御したところ、嵩密度及び結晶粒径のバラツキが少なく一定で、ハンドリング性に優れた金属セレン粉を、高収率で製造することができることを見出し、本発明を完成した。 In order to achieve the above object, the present inventors have conducted extensive research on a method for recovering selenium precipitates produced using sulfur dioxide as a reducing agent from a selenium-containing liquid. When a sulfurous acid (SO 2 ) gas is blown into the liquid containing the solution and subjected to a reduction reaction, and the resulting selenium precipitate is recovered to obtain metal selenium powder, the hydrochloric acid concentration of the liquid containing selenium is adjusted to a specific value, After repeating a specific amount of selenium precipitation in the tank, and controlling the liquid temperature and oxidation-reduction potential of the reduction reaction to specific values, the bulk density and crystal grain size variation were small and constant, and the handling property was excellent. The present inventors have found that metal selenium powder can be produced in a high yield and completed the present invention.
すなわち、本発明の第１の発明によれば、反応槽内で、セレン含有液に亜硫酸ガスを吹込んで還元反応に付し、生成されるセレン沈殿を回収して金属セレン粉を得る際、下記の（１）〜（４）の要件を満足することを特徴とする金属セレン粉の製造方法が提供される。
（１）前記セレン含有液の塩酸濃度を、２〜２．５ｍｏｌ／Ｌに調整する。
（２）前記反応槽内へ、該反応槽内に供給するセレン含有液から生成するセレン質量の３〜５倍に当たるセレン沈殿を繰り返す。
（３）前記還元反応の液温度を、６０〜８０℃に制御する。
（４）前記還元反応の酸化還元電位（銀／塩化銀電極基準）を、４６０〜５２０ｍＶに制御する。
That is, according to the first invention of the present invention, when a selenium-containing liquid is blown into a selenium-containing liquid and subjected to a reductive reaction in the reaction tank, the produced selenium precipitate is recovered to obtain metal selenium powder. A method for producing metal selenium powder is provided, which satisfies the requirements (1) to (4).
(1) The hydrochloric acid concentration of the selenium-containing liquid is adjusted to 2 to 2.5 mol / L.
(2) The selenium precipitation equivalent to 3-5 times the mass of selenium produced | generated from the selenium containing liquid supplied in this reaction tank is repeated in the said reaction tank.
(3) The liquid temperature of the reduction reaction is controlled to 60 to 80 ° C.
(4) The oxidation-reduction potential (silver / silver chloride electrode reference) of the reduction reaction is controlled to 460 to 520 mV.
また、本発明の第２の発明によれば、第１の発明において、さらに、下記の（５）の要件を満足することを特徴とする金属セレン粉の製造方法が提供される。
（５）前記反応槽内での滞留時間を、少なくとも１６時間に設定する。
According to the second invention of the present invention, in the first invention, there is further provided a method for producing metal selenium powder characterized by satisfying the following requirement (5).
(5) The residence time in the reaction vessel is set to at least 16 hours.
また、本発明の第３の発明によれば、第１又は２の発明において、さらに、下記の（６）の要件を満足することを特徴とする金属セレン粉の製造方法が提供される。
（６）前記反応槽内に備えた攪拌機の撹拌動力を、該反応槽内の単位液量当たり１．５〜２．０ｋｗ／ｍ３に調整する。
In addition, according to the third invention of the present invention, there is provided a method for producing metal selenium powder characterized in that, in the first or second invention, the following requirement (6) is satisfied.
(6) The stirring power of the stirrer provided in the reaction tank is adjusted to 1.5 to 2.0 kw / m 3 per unit liquid amount in the reaction tank.
また、本発明の第４の発明によれば、第１〜３いずれかの発明において、前記セレン含有液は、非鉄金属製錬の湿式工程から産出する亜セレン酸及びセレン酸を含む酸性水溶液であることを特徴とする金属セレン粉の製造方法が提供される。 According to a fourth invention of the present invention, in any one of the first to third inventions, the selenium-containing liquid is an acidic aqueous solution containing selenious acid and selenic acid produced from a non-ferrous metal smelting wet process. A method for producing metal selenium powder is provided.
本発明の金属セレン粉の製造方法は、還元剤として二酸化イオウを用いて生成させたセレン沈殿を回収するセレン含有液から金属セレン粉を製造する方法において、嵩密度及び結晶粒径のバラツキが少なく一定で、荷造りや充填時のハンドリング性に優れた金属セレン粉を、９８％以上の高収率で製造することができるので、その工業的価値は極めて大きい。しかも、収率の向上により、金属セレン粉を回収後の液中のセレン濃度としては、０．５ｍｇ／Ｌ以下が安定して得られるようになり、排水の高次水処理設備へのセレン負荷量の大幅な低減につながる。 The method for producing metal selenium powder of the present invention is a method for producing metal selenium powder from a selenium-containing liquid that recovers selenium precipitates produced using sulfur dioxide as a reducing agent, and there is little variation in bulk density and crystal grain size. Since the metal selenium powder that is constant and excellent in handling property during packing and filling can be produced with a high yield of 98% or more, its industrial value is extremely large. Moreover, due to the improved yield, the selenium concentration in the liquid after recovering the metal selenium powder can be stably obtained at 0.5 mg / L or less, and the selenium load on the high-order water treatment facility for wastewater This leads to a significant reduction in quantity.
以下、本発明の金属セレン粉の製造方法を詳細に説明する。
本発明の金属セレン粉の製造方法は、反応槽内で、セレン含有液に亜硫酸ガスを吹込んで還元反応に付し、生成されるセレン沈殿を回収して金属セレン粉を得る際、下記の（１）〜（４）の要件を満足することを特徴とする。
（１）前記セレン含有液の塩酸濃度を、２〜２．５ｍｏｌ／Ｌに調整する。
（２）前記反応槽内へ、該反応槽内に供給するセレン含有液から生成するセレン質量の３〜５倍に当たるセレン沈殿を繰り返す。
（３）前記還元反応の液温度を、６０〜８０℃に制御する。
（４）前記還元反応の酸化還元電位（銀／塩化銀電極基準）を、４６０〜５２０ｍＶに制御する。
Hereinafter, the manufacturing method of the metal selenium powder of this invention is demonstrated in detail.
In the method for producing metal selenium powder of the present invention, when a selenium-containing liquid is blown into a selenium-containing liquid and subjected to a reduction reaction, the produced selenium precipitate is recovered to obtain metal selenium powder. It satisfies the requirements 1) to (4).
(1) The hydrochloric acid concentration of the selenium-containing liquid is adjusted to 2 to 2.5 mol / L.
(2) The selenium precipitation equivalent to 3-5 times the mass of selenium produced | generated from the selenium containing liquid supplied in this reaction tank is repeated in the said reaction tank.
(3) The liquid temperature of the reduction reaction is controlled to 60 to 80 ° C.
(4) The redox potential (silver / silver chloride electrode reference) of the reduction reaction is controlled to 460 to 520 mV.
本発明において、反応槽内へ、該反応槽内に供給するセレン含有液から生成するセレン質量の３〜５倍に当たるセレン沈殿を繰り返すこと（（２）の要件）が重要な技術的意義を持つ。すなわち、このように多量のセレン沈殿の存在下に、所定の塩酸濃度に調整したセレン含有液に、所定の液温度と酸化還元電位の条件下に、亜硫酸ガスを吹込んで還元反応を行なうことにより、嵩密度及び結晶粒径のバラツキが少なく一定でハンドリング性に優れた金属セレン粉を９８％以上の高収率で製造することができる。
これに対して、従来の方法、例えば、前述した銅電解スライムからの有価金属の回収方法において、具体策として採用された、反応槽内の初期セレン濃度と連続還元反応時のセレン濃度の差を極力小さく保つこと、還元初期に少量の金属セレン粉を懸濁すること等を特徴とする方法では、セレン収率が９５％程度であった。
In the present invention, it is important to repeat selenium precipitation corresponding to 3 to 5 times the selenium mass generated from the selenium-containing liquid supplied into the reaction tank (requirement of (2)). . That is, in the presence of such a large amount of selenium precipitate, by performing a reduction reaction by blowing sulfurous acid gas into a selenium-containing liquid adjusted to a predetermined hydrochloric acid concentration under the conditions of a predetermined liquid temperature and oxidation-reduction potential. Further, it is possible to produce a metal selenium powder that is constant and excellent in handling properties with little variation in bulk density and crystal grain size, with a high yield of 98% or more.
On the other hand, the difference between the initial selenium concentration in the reaction tank and the selenium concentration during the continuous reduction reaction, which was adopted as a specific measure in the conventional method, for example, the method for recovering valuable metals from the copper electrolytic slime described above. In a method characterized by keeping it as small as possible and suspending a small amount of metal selenium powder in the initial stage of reduction, the selenium yield was about 95%.
ここで、上記製造方法では、（２）の要件は、還元反応後に得られるセレン沈殿を含むスラリーの一部を該反応槽に繰り返すことにより達成される。ここで、繰り返しスラリー中のセレン沈殿は、セレンの還元析出の種晶として作用し、液中のセレンをより多く析出させるとともに、生成される金属セレン粉の粒径を大きくし、かつバラツキの少ない一定の大きさに均一化する効果を発揮する。これは、嵩密度をバラツキの少ない一定の値に均一化するための一助としての効果をも有する。 Here, in the said manufacturing method, the requirements of (2) are achieved by repeating a part of slurry containing the selenium precipitation obtained after a reductive reaction to this reaction tank. Here, the selenium precipitation in the slurry repeatedly acts as a seed crystal for the reduction precipitation of selenium, precipitates more selenium in the liquid, increases the particle size of the generated metal selenium powder, and has less variation. Demonstrates the effect of uniformizing to a certain size. This also has the effect of helping to equalize the bulk density to a constant value with little variation.
上記製造方法でセレン沈殿の繰り返し量としては、反応槽内に供給するセレン含有液から生成するセレン質量の３〜５倍に当たる量である。すなわち、セレン沈殿の繰り返し量が前記セレン質量の３倍未満では、種晶としての効果不足からセレン沈殿の収率が低下する。一方、セレン沈殿の繰り返し量が前記セレン質量の５倍を超えると、それ以上、セレン沈殿の収率向上の効果は見られない。また、繰り返しスラリーは、通常の場合冷却されるので、繰り返し量が多くなりすぎると、反応槽の温度を維持するため反応槽に設けた加温設備の負荷が大きくなる。このとき、撹拌機の運転動力の損失も大きくなる。
なお、ここで、必要に応じて、スラリーを濃縮し、循環する液量を減少させることができる。
因みに、反応槽へ供給するセレン含有液中のセレン濃度が１８．５ｇ／Ｌ程度の場合であれば、還元反応後、単位液量当たりのセレン沈殿の含有割合を表すスラリー濃度（単位：ｇ／Ｌ）は、これとほぼ同じとなる。このとき、例えば、給液流量が３０Ｌ／ｍｉｎの場合では、１００〜１５０Ｌ／ｍｉｎの流量（３．３〜５．０倍に相当する。）で繰り返しスラリーを反応槽に循環すればよいことになる。
The amount of selenium precipitation repeated in the above production method is an amount corresponding to 3 to 5 times the mass of selenium produced from the selenium-containing liquid supplied into the reaction vessel. That is, when the repetition amount of selenium precipitation is less than 3 times the selenium mass, the yield of selenium precipitation decreases due to insufficient effect as a seed crystal. On the other hand, when the repetition amount of selenium precipitation exceeds 5 times the selenium mass, no further effect of improving the yield of selenium precipitation is observed. In addition, since the repeated slurry is usually cooled, if the amount of repetition is too large, the load on the heating equipment provided in the reaction tank increases to maintain the temperature of the reaction tank. At this time, the loss of the driving power of the agitator also increases.
Here, if necessary, the slurry can be concentrated to reduce the amount of circulating liquid.
Incidentally, if the selenium concentration in the selenium-containing liquid supplied to the reaction tank is about 18.5 g / L, the slurry concentration (unit: g / g) representing the content ratio of selenium precipitation per unit liquid volume after the reduction reaction. L) is almost the same as this. At this time, for example, when the liquid supply flow rate is 30 L / min, the slurry may be repeatedly circulated to the reaction tank at a flow rate of 100 to 150 L / min (corresponding to 3.3 to 5.0 times). Become.
上記製造方法に用いるセレン含有液としては、特に限定されるものではなく、セレンを含有する鉱石、中間物、スクラップ等の原料の処理過程において、湿式工程から産出するセレン、或いはセレンと他の金属元素を含有する水溶液が挙げられるが、この中で、特に非鉄金属製錬の湿式工程から産出する亜セレン酸（Ｈ２ＳｅＯ３）及びセレン酸（Ｈ２ＳｅＯ４）を含む酸性水溶液が好ましく用いられる。
前記酸性水溶液としては、前述した銅電解スライムからの有価金属の回収方法において、銅電解スライムを塩素浸出して得られる浸出液から、金及び白金族元素を溶媒抽出法で分離した際の抽残液が挙げられる。すなわち、本発明の方法は、前述した銅電解スライムからの有価金属の回収方法のセレンを回収する工程（（ｄ）の工程）として効果的に利用することができる。
The selenium-containing liquid used in the above production method is not particularly limited, and selenium produced from a wet process or selenium and other metals in the process of raw materials such as ores, intermediates and scraps containing selenium. An aqueous solution containing an element can be mentioned, and among these, an acidic aqueous solution containing selenious acid (H 2 SeO 3 ) and selenic acid (H 2 SeO 4 ) produced from a non-ferrous metal smelting wet process is particularly preferably used. It is done.
As the acidic aqueous solution, in the above-described method for recovering valuable metals from copper electrolytic slime, a residual solution obtained by separating gold and platinum group elements by a solvent extraction method from a leachate obtained by leaching copper electrolytic slime with chlorine Is mentioned. That is, the method of the present invention can be effectively used as the step (step (d)) of recovering selenium in the method for recovering valuable metals from the copper electrolytic slime described above.
上記製造方法において、セレン含有液の塩酸濃度を、２〜２．５ｍｏｌ／Ｌに調整する。
すなわち、前記塩酸濃度が２ｍｏｌ／Ｌ未満では、得られる金属セレン粉中に、液中に共存する不純物元素の共沈量が上昇する。一方、塩酸濃度が２．５ｍｏｌ／Ｌを超えると、セレン沈殿の収率のさらなる向上もなく、後工程の中和処理で使用する中和剤を増加させる。
ここで、塩酸濃度の調整方法としては、特に限定されるものではなく、反応槽内のセレン含有液の塩酸濃度に応じて直接塩酸を添加するか、或いは、セレン含有液の塩酸濃度の調整槽を設置して、セレン含有液を反応槽に供給する前に塩酸を添加する方法が用いられる。
In the said manufacturing method, the hydrochloric acid density | concentration of a selenium containing liquid is adjusted to 2-2.5 mol / L.
That is, when the hydrochloric acid concentration is less than 2 mol / L, the coprecipitation amount of the impurity element coexisting in the liquid increases in the obtained metal selenium powder. On the other hand, when the hydrochloric acid concentration exceeds 2.5 mol / L, there is no further improvement in the yield of selenium precipitation, and the neutralizing agent used in the neutralization treatment in the subsequent step is increased.
Here, the method for adjusting the hydrochloric acid concentration is not particularly limited, and hydrochloric acid is directly added according to the hydrochloric acid concentration in the selenium-containing liquid in the reaction tank, or the hydrochloric acid concentration adjusting tank in the selenium-containing liquid. And a method of adding hydrochloric acid before supplying the selenium-containing liquid to the reaction vessel is used.
上記製造方法において、還元反応の液温度を、６０〜８０℃に制御する。
すなわち、一般的に、亜セレン酸水溶液の亜硫酸ガスによる還元においては、高温度ほど結晶性が向上し、例えば、８０〜１００℃の温度が六方晶形の金属セレン粉を得るため最適である。ところが、一般的にゴム状セレンが析出しやすい６０〜８０℃の温度範囲においても、上記製造方法において、反応槽を連続運転しながら、還元反応の液温度をこの範囲の温度に制御することにより、粒子径が大きく、ろ過性が良好である金属セレン粉が得られる。なお、前記液温度が６０℃未満では、生成するセレン沈殿は、無定形のアモルファス状セレン（赤色セレン）となり、反応槽内への付着が増加するので好ましくない。
ここで、液温度の制御としては、特に限定されるものではなく、蒸気、電熱ヒーターなどによる加温装置を液中に浸漬して行なうことができる。この加温装置の材質としては、塩酸に対し耐食性のあるものとすることが望ましい。
In the said manufacturing method, the liquid temperature of a reductive reaction is controlled to 60-80 degreeC.
That is, in general, in the reduction of a selenite aqueous solution with sulfurous acid gas, the crystallinity is improved as the temperature is higher. For example, a temperature of 80 to 100 ° C. is optimal for obtaining a hexagonal metal selenium powder. However, even in a temperature range of 60 to 80 ° C., where rubbery selenium is likely to precipitate, in the above production method, the liquid temperature of the reduction reaction is controlled to a temperature within this range while continuously operating the reaction vessel. A metal selenium powder having a large particle size and good filterability is obtained. In addition, when the said liquid temperature is less than 60 degreeC, the produced | generated selenium precipitation turns into amorphous amorphous selenium (red selenium), and since adhesion to a reaction tank increases, it is unpreferable.
Here, the control of the liquid temperature is not particularly limited, and can be performed by immersing a heating device such as steam or an electric heater in the liquid. As a material of the heating device, it is desirable to have corrosion resistance against hydrochloric acid.
上記製造方法において、還元反応の酸化還元電位（銀／塩化銀電極基準）を、４６０〜５２０ｍＶに制御する。これにより、セレン含有液中にテルル、白金属元素などが共存する場合にも、これらの共沈を防止しながら、セレン沈殿を生成することができる。ここで、前記酸化還元電位（銀／塩化銀電極基準）が４６０ｍＶ未満では、セレン沈殿の収率は向上するが、テルル等が不純物元素として混入する。一方、前記酸化還元電位（銀／塩化銀電極基準）が５２０ｍＶを超えると、亜硫酸ガスによる還元反応が進みにくくなるので、液中に残留するセレンの濃度が上昇する。
ここで、前記酸化還元電位の制御としては、特に限定されるものではなく、所定の酸化還元電位の範囲内になるように自動制御で亜硫酸ガスの吹き込み量を調整することが好ましい。また、上記製造方法で用いる亜硫酸ガスとしては、ＳＯ２濃度が１０体積％以上を含有する精製した製錬排ガスが用いられるが、通常の工業用亜硫酸ガスがより好ましい。
In the said manufacturing method, the oxidation-reduction potential (silver / silver chloride electrode reference | standard) of a reduction reaction is controlled to 460-520 mV. Thereby, even when tellurium, a white metal element, and the like coexist in the selenium-containing liquid, selenium precipitates can be generated while preventing these coprecipitations. Here, when the oxidation-reduction potential (silver / silver chloride electrode standard) is less than 460 mV, the yield of selenium precipitation is improved, but tellurium or the like is mixed as an impurity element. On the other hand, when the oxidation-reduction potential (silver / silver chloride electrode reference) exceeds 520 mV, the reduction reaction by the sulfurous acid gas becomes difficult to proceed, so that the concentration of selenium remaining in the liquid increases.
Here, the control of the oxidation-reduction potential is not particularly limited, and it is preferable to adjust the blowing amount of sulfurous acid gas by automatic control so as to be within the range of a predetermined oxidation-reduction potential. As the sulfur dioxide used in the above production method, smelting exhaust gas purification SO 2 concentration contains more than 10 vol% is used, conventional industrial sulfur dioxide is more preferable.
上記製造方法において、反応槽内での滞留時間としては、特に限定されるものではないが、液中のセレンの還元反応を完結させるためには、還元反応を上記した（１）〜（４）の要件を満足する条件下に行なう際、少なくとも１６時間に設定することが好ましい。これにより、９８％以上のセレン収率を得ることができる。 In the above production method, the residence time in the reaction vessel is not particularly limited, but in order to complete the reduction reaction of selenium in the liquid, the reduction reaction described above (1) to (4) It is preferable to set at least 16 hours when the conditions are satisfied. Thereby, a selenium yield of 98% or more can be obtained.
上記製造方法において、反応槽内に備えた攪拌機の撹拌動力としては、特に限定されるものではないが、該反応槽内の単位液量当たり１．５〜２．０ｋｗ／ｍ３に調整することが好ましい。すなわち、反応槽内のスラリーを攪拌する攪拌機の動力は、得られる金属セレン粉の嵩密度のバラツキに関係するものである。ここで、前記攪拌動力が１．５ｋｗ／ｍ３未満では、得られる金属セレン粉の嵩密度のバラツキにより均一化の効果がやや低い。一方、前記攪拌動力が２．０ｋｗ／ｃｍ３を超えると、嵩密度の均一化のさらなる向上効果は得られず、電力消費量が大きくなり、しかも操業の安全面からの問題が生じる。 In the above production method, the stirring power of the stirrer provided in the reaction tank is not particularly limited, but is adjusted to 1.5 to 2.0 kw / m 3 per unit liquid amount in the reaction tank. Is preferred. That is, the power of the stirrer that stirs the slurry in the reaction tank is related to the variation in the bulk density of the obtained metal selenium powder. Here, when the stirring power is less than 1.5 kw / m 3 , the effect of homogenization is slightly low due to variations in the bulk density of the obtained metal selenium powder. On the other hand, when the agitation power exceeds 2.0 kw / cm 3 , the further improvement effect of uniforming the bulk density cannot be obtained, the power consumption becomes large, and the problem from the safety aspect of operation arises.
上記製造方法に用いるセレン還元設備としては、特に限定されるものではなく、連続式のほかバッチ式のものが採用されるが、例えば、還元反応の制御のため、撹拌機と加熱装置を備えた反応槽が用いられる。ここで、前記反応槽としては、例えば２槽を連結し、第１反応槽に、所定の塩酸濃度に調整したセレン含有液を、所定の流量で供給する。なお、第１反応槽から第２反応槽へのスラリーの移動手段としては、オーバーフローによるものが簡便であり、かつ各反応槽に邪魔板を設けてスラリーのショートパスを防止する。 The selenium reduction facility used in the above production method is not particularly limited, and a continuous type as well as a batch type are adopted. For example, a stirrer and a heating device are provided for controlling the reduction reaction. A reaction vessel is used. Here, as the reaction tank, for example, two tanks are connected, and a selenium-containing liquid adjusted to a predetermined hydrochloric acid concentration is supplied to the first reaction tank at a predetermined flow rate. In addition, as a means for moving the slurry from the first reaction tank to the second reaction tank, an overflow means is simple, and a baffle plate is provided in each reaction tank to prevent a short path of the slurry.
前記セレン還元設備の操業において、各反応槽の攪拌機を所定の撹拌動力で運転し、所定の液温度に制御しながら、酸化還元電位を亜硫酸ガスの吹き込み量で自動制御する。また、第２反応槽から排出されたスラリーの取り扱いのため、必要に応じて、冷却槽を備えることができる。ここで、第２反応槽から排出されたスラリーは、その後の排水処理工程などでの取り扱いを容易とするため、室温程度まで冷却する。次いで冷却されたセレン沈殿を含むスラリーを所定割合で、第１反応槽に繰り返す。その後、冷却槽に一定以上の液量が貯まったときに、固液分離装置にて分離して金属セレン粉を回収する。 In the operation of the selenium reduction facility, the oxidation-reduction potential is automatically controlled by the amount of sulfurous acid gas blown while the stirrer of each reaction vessel is operated with a predetermined stirring power and controlled to a predetermined liquid temperature. Moreover, a cooling tank can be provided as needed for handling the slurry discharged from the second reaction tank. Here, the slurry discharged from the second reaction tank is cooled to about room temperature in order to facilitate handling in a subsequent wastewater treatment process or the like. The cooled slurry containing selenium precipitate is then repeated in the first reaction tank at a predetermined rate. Thereafter, when a certain amount or more of liquid is stored in the cooling tank, the metal selenium powder is recovered by separation with a solid-liquid separator.
以下に、本発明の実施例及び比較例によって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、実施例及び比較例で用いた金属の分析、嵩密度及び平均粒径の評価方法は、次の通りである。
（１）金属の分析：ＩＣＰ発光分析法で行った。
（２）嵩密度の測定：容積既知の容器を用いて、金属セレン粉の重量を測定する方法で求めた。
（３）平均粒径の測定：ＭＩＣＲＯＴＲＡＣＫ ＨＲＡ（ＭＯＤＥＬ：９３２０−Ｘ１００）を使用して測定した。
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, the analysis method of the metal used by the Example and the comparative example, and the evaluation method of a bulk density and an average particle diameter are as follows.
(1) Metal analysis: ICP emission analysis was performed.
(2) Measurement of bulk density: It was determined by a method of measuring the weight of metal selenium powder using a container with a known volume.
(3) Measurement of average particle diameter: It was measured using MICROTRACK HRA (MODEL: 9320-X100).
（実施例１）
セレン還元設備として、攪拌機と蒸気加熱装置付きの容量１５ｍ３の反応槽２槽（第１反応槽、第２反応槽）を連結し、さらに第２反応槽を出たスラリーの冷却槽を備えたものを使用した。なお、第１反応槽から第２反応槽へのスラリーの移動は、オーバーフロー方式であり、各反応槽に邪魔板を設け、ショートパスを防止した。
ここで、第１反応槽に、塩酸濃度を２．３ｍｏｌ／Ｌに調整した塩酸水溶液（セレン濃度：１８．５ｇ／Ｌ）を、約３０Ｌ／ｍｉｎの流量で供給した。このときの液温度は６０℃に制御した。また、還元反応の酸化還元電位（銀／塩化銀電極基準）は、５００ｍＶを維持するように、液中にＳＯ２濃度１０体積％の精製した製錬排ガスを吹き込むことにより自動制御された。なお、各槽の攪拌機は、単位液量当たり１．５ｋｗ／ｍ３の撹拌動力で運転された。
また、第２反応槽から排出されたセレン沈殿を含むスラリーは、冷却槽にて室温程度まで冷却された。冷却されたスラリーを、１００Ｌ／ｍｉｎの流量で第１反応槽に繰り返した。なお、このときのセレン沈殿の繰り返し量は、反応槽内に供給するセレン含有液から生成するセレン質量に対し、繰返し沈殿比（返送／生成）は、３．３倍であった。さらに、冷却槽に一定以上の液量が貯まったとき、固液分離装置にて分離して金属セレン粉を回収した。
(Example 1)
As a selenium reduction facility, two reactors with a capacity of 15 m 3 with a stirrer and a steam heating device (first reaction tank, second reaction tank) were connected, and a cooling tank for slurry that was discharged from the second reaction tank was further provided. I used something. In addition, the movement of the slurry from the 1st reaction tank to the 2nd reaction tank was an overflow system, and the baffle plate was provided in each reaction tank, and the short pass was prevented.
Here, a hydrochloric acid aqueous solution (selenium concentration: 18.5 g / L) adjusted to a hydrochloric acid concentration of 2.3 mol / L was supplied to the first reaction vessel at a flow rate of about 30 L / min. The liquid temperature at this time was controlled at 60 ° C. In addition, the oxidation-reduction potential (silver / silver chloride electrode standard) of the reduction reaction was automatically controlled by blowing purified smelting exhaust gas having a SO 2 concentration of 10% by volume into the liquid so as to maintain 500 mV. The stirrer in each tank was operated with a stirring power of 1.5 kW / m 3 per unit liquid volume.
Moreover, the slurry containing the selenium precipitate discharged from the second reaction tank was cooled to about room temperature in the cooling tank. The cooled slurry was repeated in the first reaction vessel at a flow rate of 100 L / min. In addition, the repetition amount of selenium precipitation at this time was 3.3 times the repetition precipitation ratio (return / generation) with respect to the selenium mass produced | generated from the selenium containing liquid supplied in a reaction tank. Furthermore, when a certain amount or more of liquid was stored in the cooling tank, the metal selenium powder was recovered by separation with a solid-liquid separator.
上記条件下に３ヶ月間の操業を行なった。この間、金属セレン粉回収後の液中のセレン濃度及びセレン収率を求めた。結果を、それぞれ図１、２に示す。また、得られた金属セレン粉の嵩密度と平均粒径を求めた。結果を表１に示す。
なお、図１より、金属セレン粉回収後の液中のセレン濃度は、０．１８〜０．２３ｍｇ／Ｌであった。また、図２より、セレン収率は９８．８〜９９．３％であった。
The operation was performed for 3 months under the above conditions. During this time, the selenium concentration and selenium yield in the liquid after metal selenium powder recovery was determined. The results are shown in FIGS. Moreover, the bulk density and average particle diameter of the obtained metal selenium powder were determined. The results are shown in Table 1.
In addition, the selenium density | concentration in the liquid after metal selenium powder collection | recovery was 0.18-0.23 mg / L from FIG. Moreover, from FIG. 2, the selenium yield was 98.8 to 99.3%.
（実施例２）
各槽の攪拌機を、単位液量当たり１．０ｋｗ／ｍ３の撹拌動力で運転したこと以外は実施例１と同様にして８ヶ月間の操業を行った。この間、金属セレン粉回収後の液中のセレン濃度及びセレン収率を求めた。結果を、それぞれ図１、２に示す。また、得られた金属セレン粉の嵩密度と平均粒径を求めた。結果を表１に示す。
なお、図１より、金属セレン粉回収後の液中のセレン濃度は、０．１６〜０．３８ｍｇ／Ｌであり、実施例１と比べると、液中のセレン濃度のバラツキが大きくなっており、この違いは、撹拌動力に起因するものである。また、図２より、セレン収率は９８．０〜９８．８％であった。
(Example 2)
The operation was carried out for 8 months in the same manner as in Example 1 except that the agitator in each tank was operated with a stirring power of 1.0 kw / m 3 per unit liquid volume. During this time, the selenium concentration and selenium yield in the liquid after metal selenium powder recovery was determined. The results are shown in FIGS. Moreover, the bulk density and average particle diameter of the obtained metal selenium powder were determined. The results are shown in Table 1.
In addition, from FIG. 1, the selenium concentration in the liquid after metal selenium powder recovery is 0.16-0.38 mg / L, and the variation in the selenium concentration in the liquid is larger than that in Example 1. This difference is due to the stirring power. Moreover, the selenium yield was 98.0-98.8% from FIG.
（比較例１）
各槽の攪拌機を、単位液量当たり１．０ｋｗ／ｍ３の撹拌動力で運転したこと、及びセレン沈殿を含むスラリーの繰り返しを行なわなかったこと以外は実施例１と同様にして３ヶ月間の操業を行った。この間、金属セレン粉回収後の液中のセレン濃度及びセレン収率を求めた。結果を、それぞれ図１、２に示す。また、得られた金属セレン粉の嵩密度と平均粒径を求めた。結果を表１に示す。
なお、図１より、金属セレン粉回収後の液中のセレン濃度は、０．６４〜０．７６ｍｇ／Ｌであった。また、図２より、セレン収率は９５．３〜９７．２％であった。
(Comparative Example 1)
The stirrer in each tank was operated at a stirring power of 1.0 kW / m 3 per unit liquid volume, and the slurry containing selenium precipitation was not repeated for 3 months as in Example 1. The operation was performed. During this time, the selenium concentration and selenium yield in the liquid after metal selenium powder recovery was determined. The results are shown in FIGS. Moreover, the bulk density and average particle diameter of the obtained metal selenium powder were determined. The results are shown in Table 1.
In addition, the selenium density | concentration in the liquid after metal selenium powder collection | recovery was 0.64-0.76 mg / L from FIG. Moreover, the selenium yield was 95.3-97.2% from FIG.
（比較例２、３）
反応温度を、それぞれ５９℃（比較例２）、５７℃（比較例３）としたこと以外は実施例１と同様にして操業を行った。得られた金属セレン粉の平均粒径を求めた。結果を表１に示す。なお、比較例２で得られた金属セレン粉は、結晶セレンとアモルファスセレンの中間の性状を持つものであり、また、比較例３で得られた金属セレン粉は、結晶同士が２次凝集を起こし粗大化したものであった。
(Comparative Examples 2 and 3)
The operation was performed in the same manner as in Example 1 except that the reaction temperatures were 59 ° C. (Comparative Example 2) and 57 ° C. (Comparative Example 3), respectively. The average particle size of the obtained metal selenium powder was determined. The results are shown in Table 1. The metal selenium powder obtained in Comparative Example 2 has intermediate properties between crystalline selenium and amorphous selenium, and the metal selenium powder obtained in Comparative Example 3 has secondary aggregation between crystals. It was raised and coarsened.
表１より、実施例１、２では、セレン含有液の塩酸濃度を所定値に調整し、反応槽内へ、該反応槽内に供給するセレン含有液から生成するセレン質量の所定の倍数に当たるセレン沈殿を繰り返し、還元反応の液温度及び還元反応の酸化還元電位を所定値に制御し、本発明の方法に従って行われたので、結晶粒径のバラツキが小さく、同時に嵩密度が高く均一化された金属セレン粉が９８％以上の高収率で得られることが分かる。なお、実施例１と比べて実施例２の嵩密度のバラツキがやや大きいが、この違いは、撹拌動力の差による。
これに対して、比較例１〜３では、セレン沈殿の繰り返し、或いは液温度がこれらの条件に合わないので、セレン収率又は金属セレン粉の析出状態において満足すべき結果が得られないことが分かる。
なお、図３は、得られた金属セレン粉の嵩密度の変化を示すが、図３より、撹拌動力の適正化により、実施例１では、嵩密度のバラツキが大きく改善されることが分かる。
From Table 1, in Examples 1 and 2, the hydrochloric acid concentration of the selenium-containing liquid was adjusted to a predetermined value, and selenium corresponding to a predetermined multiple of the selenium mass generated from the selenium-containing liquid supplied into the reaction tank into the reaction tank. Precipitation was repeated, and the liquid temperature of the reduction reaction and the oxidation-reduction potential of the reduction reaction were controlled to predetermined values, and this was carried out according to the method of the present invention, so that the variation in crystal grain size was small and at the same time the bulk density was high and uniform. It can be seen that metal selenium powder is obtained in a high yield of 98% or more. In addition, although the variation of the bulk density of Example 2 is a little large compared with Example 1, this difference is based on the difference in stirring power.
In contrast, in Comparative Examples 1 to 3, since the repetition of selenium precipitation or the liquid temperature does not meet these conditions, satisfactory results may not be obtained in the selenium yield or the deposited state of the metal selenium powder. I understand.
In addition, although FIG. 3 shows the change of the bulk density of the obtained metal selenium powder, it can be seen from FIG. 3 that the variation in the bulk density is greatly improved in Example 1 by the optimization of the stirring power.
以上より明らかなように、本発明の金属セレン粉の製造方法は、セレンを含有する液から、セレンを効率的に、かつ高収率で回収し、しかも排水のセレン負荷を低減することができるので、特に銅製錬を始め、非鉄金属製錬分野で産出するセレンを含有する酸性水溶液からのセレンの回収方法として好適である。 As is clear from the above, the method for producing metal selenium powder of the present invention can recover selenium efficiently and in high yield from a liquid containing selenium, and can reduce the selenium load of waste water. Therefore, it is particularly suitable as a method for recovering selenium from an acidic aqueous solution containing selenium produced in the field of non-ferrous metal smelting including copper smelting.
Claims (4)
（１）前記セレン含有液の塩酸濃度を、２〜２．５ｍｏｌ／Ｌに調整する。
（２）前記反応槽内へ、該反応槽内に供給するセレン含有液から生成するセレン質量の３〜５倍に当たるセレン沈殿を繰り返す。
（３）前記還元反応の液温度を、６０〜８０℃に制御する。
（４）前記還元反応の酸化還元電位（銀／塩化銀電極基準）を、４６０〜５２０ｍＶに制御する。 In the reaction vessel, sulfur dioxide gas is blown into the selenium-containing liquid to be subjected to a reduction reaction, and when the produced selenium precipitate is recovered to obtain metal selenium powder, the following requirements (1) to (4) are satisfied. The manufacturing method of the metal selenium powder characterized by the above-mentioned.
(1) The hydrochloric acid concentration of the selenium-containing liquid is adjusted to 2 to 2.5 mol / L.
(2) The selenium precipitation equivalent to 3-5 times the mass of selenium produced | generated from the selenium containing liquid supplied in this reaction tank is repeated in the said reaction tank.
(3) The liquid temperature of the reduction reaction is controlled to 60 to 80 ° C.
(4) The redox potential (silver / silver chloride electrode reference) of the reduction reaction is controlled to 460 to 520 mV.
（５）前記反応槽内での滞留時間を、少なくとも１６時間に設定する。 Furthermore, the requirements for following (5) are satisfied, The manufacturing method of the metal selenium powder of Claim 1 characterized by the above-mentioned.
(5) The residence time in the reaction vessel is set to at least 16 hours.
（６）前記反応槽内に備えた攪拌機の撹拌動力を、該反応槽内の単位液量当たり１．５〜２．０ｋｗ／ｍ３に調整する。 Furthermore, the requirements for following (6) are satisfied, The manufacturing method of the metal selenium powder of Claim 1 or 2 characterized by the above-mentioned.
(6) The stirring power of the stirrer provided in the reaction tank is adjusted to 1.5 to 2.0 kw / m 3 per unit liquid amount in the reaction tank.
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| CN102120122A (en) * | 2010-12-14 | 2011-07-13 | 东营方圆有色金属有限公司 | Selenium absorption column dilute acid concentrating process |
| CN102284236A (en) * | 2011-06-16 | 2011-12-21 | 中国恩菲工程技术有限公司 | Equipment for treating gas fume |
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| CN112850659A (en) * | 2021-01-08 | 2021-05-28 | 北京高能时代环境技术股份有限公司 | Selenium extraction method of selenium-containing smelting slag |
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