JP7213659B2 - Recovery method of PGM - Google Patents
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Description
本発明は、白金族元素（本発明において「ＰＧＭ」と記載する場合がある。）を含有する各種の部材、例えば、使用済みの自動車排ガス浄化用触媒、使用済みの電子基板やリードフレーム、使用済みの石油化学系触媒等を被処理物とし、当該ＰＧＭを含有する被処理物からのＰＧＭの回収方法に関する。 The present invention provides various members containing a platinum group element (sometimes referred to as "PGM" in the present invention), such as used automobile exhaust gas purification catalysts, used electronic substrates and lead frames, and used The present invention relates to a method for recovering PGM from an object to be treated containing the PGM, wherein a used petrochemical catalyst or the like is an object to be treated.
従来から、使用済みの自動車排ガス浄化用触媒のように、ＰＧＭを含有する各種の部材を被処理物とし、当該ＰＧＭを含有する被処理物からＰＧＭを回収する方法が提案されている。例えば、本発明出願人は、ＰＧＭを含有する被処理物を銅源材料と共に加熱溶融し、生成した溶融メタル中にＰＧＭを吸収させる、効率の良いＰＧＭの乾式回収法を開示している（特許文献１参照）。 Conventionally, various PGM-containing members, such as used catalysts for purifying automobile exhaust gas, have been proposed as objects to be treated, and methods for recovering PGM from the PGM-containing objects to be treated have been proposed. For example, the applicant of the present invention has disclosed an efficient dry recovery method for PGM, in which an object to be processed containing PGM is heated and melted together with a copper source material, and the PGM is absorbed in the resulting molten metal (Patent Reference 1).
特許文献１に係るＰＧＭの乾式回収法においては、ＰＧＭを含有する被処理物と、酸化銅を含有する銅源材料とを、フラックス成分および還元剤と共に密閉型の電気炉に装填して溶融する。そして、生成した酸化物主体の溶融スラグ層の下方に沈降した溶融メタル中に、ＰＧＭを濃縮させてこれを回収する（本発明において「還元溶錬」と記載する場合がある）。一方、銅含有量が低下した前記溶融スラグを前記電気炉から排出し、また前記銅源材料として一定粒径を有する粒状銅源材料を用いる、という構成を有している。
In the PGM dry recovery method according to
本発明者らは、上述の成果に満足することなく、ＰＧＭを含有する被処理物からのさらに高効率なＰＧＭ回収方法について研究を行なった。
即ち、本発明が解決しようとする課題は、ＰＧＭを含有する被処理物からの高効率なＰＧＭ回収方法を提供することである。
The inventors of the present invention have not been satisfied with the results described above, and have conducted research on a more efficient method for recovering PGM from a PGM-containing material to be treated.
That is, the problem to be solved by the present invention is to provide a highly efficient PGM recovery method from a PGM-containing material to be treated.
上述の課題を解決する為、本発明者らは、ＰＧＭを含有する被処理物からのＰＧＭ回収方法について、還元溶錬工程を初めとする各工程を詳細に検討した。そして、当該検討の結果、従来の技術に係る還元溶錬工程においては、電気炉内に溶けきらない被処理物が残留する場合があることを知見した。そして、炉内に溶けきらない被処理物が残留する場合、ＰＧＭが溶融スラグ側へ移動してしまい、ＰＧＭの回収率が低下することを知見した。 In order to solve the above-mentioned problems, the present inventors have studied in detail each step including the reduction smelting step for a method for recovering PGM from a PGM-containing material to be treated. As a result of the study, the inventors have found that in the reduction smelting process according to the conventional technology, there are cases where unmelted materials remain in the electric furnace. Further, the inventors have found that when unmelted materials to be processed remain in the furnace, the PGM moves to the molten slag side, and the recovery rate of the PGM decreases.
本発明者らは、従来技術において炉内に溶けきらない被処理物が残留する原因を研究した結果、電気炉内の温度設定において課題があることに想到した。
従来、還元溶錬工程における電気炉内の温度設定は、エネルギーコストの上昇や電気炉壁の劣化を抑制する観点から、電気炉内が過剰に高温になることを避けるように設定されていた。また、従来技術における電気炉内の温度測定は、熱電対や赤外線高温計を電気炉壁外部に設置し、間接的に炉内温度を測定することがあった。
本発明者らの検討によれば、当該電気炉壁外部からの間接的温度測定では、上述した電気炉内の温度を参照・制御しながらの還元溶錬工程を実施するには、測定精度に不足があると考えられた。
The inventors of the present invention investigated the cause of the incompletely melted material remaining in the furnace in the prior art, and found that there was a problem in setting the temperature in the electric furnace.
Conventionally, the temperature setting in the electric furnace in the reduction smelting process has been set so as to avoid excessively high temperature in the electric furnace from the viewpoint of suppressing the increase in energy cost and deterioration of the electric furnace wall. Further, in the conventional technology, the temperature inside the electric furnace is sometimes measured indirectly by installing a thermocouple or an infrared pyrometer outside the wall of the electric furnace.
According to the studies of the present inventors, in the indirect temperature measurement from the outside of the electric furnace wall, the measurement accuracy is not sufficient to perform the reduction smelting process while referring to and controlling the temperature inside the electric furnace. thought to be deficient.
即ち、ＰＧＭの回収率を向上させるには、還元溶錬工程における電気炉内温度を上昇させて、被処理物の十分な溶融を実現すればよいと考えられた。しかし、炉内温度を、単純に上昇させることは、エネルギーコストの上昇や、電気炉内部の炉壁の劣化促進につながるものである。 That is, in order to improve the recovery rate of PGM, it was considered that the temperature in the electric furnace in the reduction smelting process should be raised to achieve sufficient melting of the material to be treated. However, simply raising the temperature inside the furnace leads to an increase in energy costs and accelerated deterioration of the furnace wall inside the electric furnace.
ここで本発明者らはさらに研究を行い、電気炉の炉頂温度を測定し、当該測定された電気炉の炉頂温度によって、電気炉の温度制御を行いながら還元溶錬工程を行う構成に想到した。そして、当該構成を用いながら、電気炉の炉頂温度と、炉内の溶融物の溶け残り解消や炉壁の劣化抑制との関係を研究した。その結果、本発明者らは、エネルギーコストの上昇や炉壁の劣化を抑制しながら、炉内の溶融物の溶け残りが解消できることに想到した。 Here, the present inventors conducted further research, measured the top temperature of the electric furnace, and performed the reduction smelting process while controlling the temperature of the electric furnace according to the measured top temperature of the electric furnace. I thought of it. Using this configuration, the inventors studied the relationship between the top temperature of the electric furnace and the elimination of unmelted material in the furnace and the suppression of deterioration of the furnace wall. As a result, the present inventors have conceived that it is possible to eliminate unmelted molten material in the furnace while suppressing an increase in energy cost and deterioration of the furnace wall.
具体的には、電気炉の炉頂温度を、温度低下により被処理物の溶け残りが増加し始める温度より２０℃以上高めに制御しながら還元溶錬工程を行うことにより、炉内の溶融物の溶け残りが解消できることを知見した。さらに具体的には、ＰＧＭを含有する被処理物と、Ｃｕおよび／またはＣｕ２Ｏと、フラックスと、Ｃ（炭素）含有材料とを電気炉に入れて還元溶錬し、これら全てを溶融して溶融スラグ層と電気炉メタル層とを形成した後の溶融スラグ層抽出時に、前記電気炉の炉頂温度を９００℃以上１２００℃以下に制御することで、炉内の溶融物の溶け残り解消と、炉壁の劣化抑制とを実現できることを知見し、本発明を完成した。 Specifically, the reduction smelting process is performed while controlling the furnace top temperature of the electric furnace to be 20 ° C. or more higher than the temperature at which the unmelted material starts to increase due to the temperature decrease, thereby reducing the molten material in the furnace. It was found that the undissolved residue of can be eliminated. More specifically, an object to be treated containing PGM, Cu and/or Cu 2 O, flux, and a C (carbon)-containing material are placed in an electric furnace for reduction smelting, and all of these are melted. At the time of extracting the molten slag layer after forming the molten slag layer and the electric furnace metal layer, the top temperature of the electric furnace is controlled to 900 ° C. or higher and 1200 ° C. or lower, thereby eliminating the unmelted material in the furnace. and suppression of deterioration of the furnace wall, and completed the present invention.
即ち、上述の課題を解決する為の第１の発明は、
ＰＧＭを含有する被処理物と、Ｃｕおよび／またはＣｕ2Ｏと、フラックスと、Ｃ（炭素）含有材料とを電気炉に入れて加熱し、これらを溶融して溶融スラグ層と電気炉メタル層とを形成した後に前記溶融スラグを抽出し、ＰＧＭを含有する電気炉メタルを抽出して得る還元溶錬工程と、
前記電気炉メタルを酸化炉に移して酸化溶融し、Ｃｕ2Ｏスラグ層とＰＧＭ合金層とを形成した後に、Ｃｕ2Ｏスラグを抽出し、ＰＧＭが濃縮されたＰＧＭ合金を得る酸化溶錬工程と、を行うＰＧＭの回収方法であって、
前記還元溶錬工程における溶融スラグ抽出時に、前記電気炉の炉頂温度を９００℃以上１２００℃以下に制御することを特徴とするＰＧＭの回収方法である。
That is, the first invention for solving the above-mentioned problems is
An object to be treated containing PGM, Cu and/or Cu 2 O, flux, and a C (carbon)-containing material are placed in an electric furnace and heated to melt them to form a molten slag layer and an electric furnace metal layer. a reduction smelting step of extracting the molten slag after forming and extracting an electric furnace metal containing PGM;
An oxidizing smelting process for transferring the electric furnace metal to an oxidation furnace and oxidizing and melting it to form a Cu 2 O slag layer and a PGM alloy layer, and then extracting the Cu 2 O slag to obtain a PGM-enriched PGM alloy. and a PGM recovery method comprising:
The PGM recovery method is characterized in that the furnace top temperature of the electric furnace is controlled to 900° C. or more and 1200° C. or less when extracting molten slag in the reduction smelting step.
本発明によれば、電気炉の炉頂温度を制御することにより、ＰＧＭを含有する被処理物から高効率にＰＧＭ合金を回収することができる。 According to the present invention, a PGM alloy can be efficiently recovered from a PGM-containing object to be processed by controlling the furnace top temperature of the electric furnace.
本発明に係るＰＧＭの回収方法について図面を参照しながら、［１］還元溶錬、［２］酸化溶錬、［３］従来の技術に係る還元溶錬の課題、［４］本発明に係る還元溶錬、［５］本発明に係る酸化溶錬、および［６］本発明に係るＰＧＭ回収方法例、の順に説明する。
図１は、本発明に係るＰＧＭの回収方法例の工程フロー図である。
While referring to the drawings for the PGM recovery method according to the present invention, [1] reduction smelting, [2] oxidation smelting, [3] problems of reduction smelting according to the conventional technology, [4] according to the present invention Reduction smelting, [5] oxidation smelting according to the present invention, and [6] example of PGM recovery method according to the present invention will be described in this order.
FIG. 1 is a process flow diagram of an example of a PGM recovery method according to the present invention.
［１］還元溶錬
図１に示すように、ＰＧＭを含有する被処理物（２）である、例えばセラミックス製自動車触媒の粉砕物と、抽出剤（３）であるＣｕおよび／またはＣｕ２Ｏと、フラックス（１）であるＣａＯおよび／またはＳｉＯ２と、そして還元剤（４）であるＣ（炭素）含有材料とを、電気炉（５）内に装填する。そして電気炉（５）内の電極に通電し、前記装填物を加熱し溶融させる。
[1] Reduction smelting As shown in FIG. 1, the object to be treated (2) containing PGM, such as pulverized ceramic automobile catalyst, and the extractant (3) Cu and/or Cu 2 O , a flux (1) of CaO and/or SiO 2 and a reducing agent (4) of a C (carbon)-containing material are loaded into an electric furnace (5). Then, the electrodes in the electric furnace (5) are energized to heat and melt the charge.
すると、電気炉（５）内において、酸化物（ＣａＯ－ＳｉＯ２－Ａｌ２Ｏ３）を主体とする溶融スラグ（７）層の下方に、Ｃｕ合金である電気炉メタル（６）が沈降する。このとき、当該下方に沈降した電気炉メタル（６）中にはＰＧＭが濃縮している。この後、Ｃｕ含有量が３．０質量％以下にまで低下した溶融スラグ（７）を、当該電気炉（５）から抽出し排出する。 Then, in the electric furnace (5), the electric furnace metal (6), which is a Cu alloy, settles below the molten slag ( 7 ) layer mainly composed of oxides ( CaO-- SiO.sub.2 --Al.sub.2O.sub.3). . At this time, PGM is concentrated in the electric furnace metal (6) that has settled down. Thereafter, the molten slag (7) in which the Cu content has decreased to 3.0% by mass or less is extracted from the electric furnace (5) and discharged.
即ち、本発明において「電気炉メタル（６）」とは、被処理物（２）の粉砕物と還元剤（４）とフラックス（１）と抽出剤（３）とを、電気炉（５）で溶融した後に、生成した溶融スラグ（７）を抽出し排出して得られる、ＰＧＭを含有する銅合金主体の溶湯を示す。 That is, in the present invention, the "electric furnace metal (6)" means the pulverized material of the object (2), the reducing agent (4), the flux (1), and the extracting agent (3) in the electric furnace (5). shows a PGM-containing copper alloy-based molten metal obtained by extracting and discharging the generated molten slag (7) after melting at .
以上説明した、被処理物（２）の粉砕物他の電気炉（５）装填物を溶融した後、溶融スラグ（７）を抽出分離して排出し、電気炉メタル（６）を得るまでの工程が「還元溶錬」であり、鉄鋼製錬において高炉で酸化鉄の鉱石を還元して銑鉄を得るのと類似の手法である。 After melting the pulverized material of the material to be processed (2) and other materials charged in the electric furnace (5), the molten slag (7) is extracted, separated and discharged to obtain the electric furnace metal (6). The process is "reduction smelting", which is similar to the method used in iron and steel smelting to reduce iron oxide ore in a blast furnace to obtain pig iron.
［２］酸化溶錬
還元溶錬にて得られたＰＧＭが濃縮した電気炉メタル（６）を電気炉（５）から抽出し、溶融状態のまま酸化炉（９）に移し替え、さらに、空気および／または酸素を吹き込んで酸化する。すると電気炉メタル（６）は、酸化物主体のＣｕ２Ｏスラグ（１１）層と、ＰＧＭがさらに濃縮したＰＧＭ合金（１０）層とに層分離する。
[2] Oxidation smelting The electric furnace metal (6) enriched with PGM obtained by reduction smelting is extracted from the electric furnace (5), transferred in a molten state to the oxidation furnace (9), and further treated with air. and/or oxidized by blowing oxygen. Then, the electric furnace metal (6) separates into a Cu 2 O slag (11) layer mainly composed of oxides and a PGM alloy (10) layer in which PGM is further concentrated.
即ち、本発明において「ＰＧＭ合金（１０）」とは、酸化炉にて、電気炉メタル（６）へ空気および／または酸素を吹き込んで酸化した後に、生成したＣｕ２Ｏスラグを抜き出して得られる、銅とＰＧＭとを主成分として含む合金物質を示す。 That is, the "PGM alloy (10)" in the present invention is obtained by blowing air and/or oxygen into the electric furnace metal (6) for oxidation in an oxidation furnace, and then extracting the generated Cu 2 O slag. , shows an alloy material containing copper and PGM as main components.
このＰＧＭ合金（１０）層の湯面上に生成したＣｕ２Ｏスラグ（１１）層を酸化炉（９）外に排出した後、再び、空気および／または酸素を吹き込んで、酸化物主体のＣｕ２Ｏスラグ（１１）層と、ＰＧＭがさらに濃縮したＰＧＭ合金（１０）層とに層分離させる。そして、ＰＧＭ合金（１０）層の湯面上に生成したＣｕ２Ｏスラグ（１１）層を、再び酸化炉（９）外に排出する。 After discharging the Cu 2 O slag (11) layer formed on the surface of the PGM alloy (10) layer to the outside of the oxidation furnace (9), air and/or oxygen is blown again to form Cu mainly composed of oxides. Layer separation into a 2 O slag (11) layer and a PGM alloy (10) layer in which the PGM is further enriched. Then, the Cu 2 O slag (11) layer formed on the surface of the PGM alloy (10) layer is discharged out of the oxidation furnace (9) again.
そして、以上説明した酸化炉（９）における酸化処理と、Ｃｕ２Ｏスラグ（１１）層の排出処理とを繰り返すことにより、ＰＧＭ合金（１０）層中におけるＰＧＭ含有量をさらに濃縮させる。 By repeating the oxidation treatment in the oxidation furnace (9) and the discharge treatment of the Cu2O slag ( 11 ) layer described above, the PGM content in the PGM alloy (10) layer is further concentrated.
以上説明した、酸化炉（９）内において、濃縮されたＰＧＭを含有するＰＧＭ合金（１０）を得るまでの工程が「酸化溶錬工程」であり、鉄鋼製錬において銑鉄中の炭素，ケイ素，リンなどの不純物を酸化して除去するのと類似の工程である。 The process until the PGM alloy (10) containing concentrated PGM is obtained in the oxidation furnace (9) as described above is the "oxidation smelting process". This process is similar to removing impurities such as phosphorus by oxidation.
［３］従来の技術に係る還元溶錬の課題
従来の技術に係る還元溶錬工程においては、電気炉内の電気炉メタル（６）層と溶融スラグ（７）層との状態を目視しながら、電気炉（５）における電極の電力調整を行うことで、温度制御をしていた。すると、被処理物（２）の溶け残りが発生する場合があることが知見された。そして本発明者らは、当該溶け残りが発生するとＰＧＭが溶融スラグ（７）層へ移動してしまい、ＰＧＭの回収率が低下することを知見した。
[3] Problems of reduction smelting according to conventional technology In the reduction smelting process according to conventional technology, while visually observing the state of the electric furnace metal (6) layer and the molten slag (7) layer in the electric furnace , the temperature was controlled by adjusting the power of the electrodes in the electric furnace (5). As a result, it has been found that undissolved material (2) may be left undissolved. The inventors of the present invention have found that when the undissolved residue is generated, the PGM moves to the molten slag (7) layer, resulting in a decrease in the recovery rate of the PGM.
上述の知見と、エネルギーコストの上昇や電気炉（５）の炉壁の劣化を抑制する観点とから、本発明者らは電気炉（５）の炉内温度の把握とその制御の重要性に想到した。
しかしながら、電気炉（５）内には、被処理物（２）、溶融スラグ（７）層、および、電気炉メタル（６）層等が存在し、かつ高温であることから、炉内温度の直接的で正確な測温は困難であった。
そこで、電気炉（５）の外壁側より測温が行われていたが、当該炉壁は、当該炉壁の劣化を抑制する観点から冷却手段を備えており、炉内温度の正確な測温は困難であった。
From the above findings and from the viewpoint of suppressing the increase in energy cost and the deterioration of the furnace wall of the electric furnace (5), the present inventors have recognized the importance of grasping and controlling the temperature inside the electric furnace (5). I thought of it.
However, in the electric furnace (5), the object to be treated (2), the molten slag (7) layer, the electric furnace metal (6) layer, etc. exist and are at a high temperature. Direct and accurate temperature measurement was difficult.
Therefore, the temperature was measured from the outer wall side of the electric furnace (5). was difficult.
［４］本発明に係る還元溶錬
ここで、本発明者らは研究の結果、電気炉（５）の炉頂温度を測温することにより、間接的ながら炉内温度の把握が可能になることに想到した。
尚、本発明に係る「炉頂」とは、電気炉（５）の炉頂部上面にある、被処理物（２）等の投入用の蓋部分のことである。
そして炉頂温度の測温は、蓋部の形状を円型としたとき、当該円の中心部を中心とする円周上の１点と、当該点と反対側の円周上１点の２ヵ所に温度計を設けたり、当該円周上に等間隔にて、複数の温度計を設ければよいことも判明した。
炉頂に設置する当該温度計としては、熱電対や赤外線センサー等が使用できる。
[4] Reduction smelting according to the present invention Here, as a result of research by the present inventors, it is possible to indirectly grasp the temperature inside the furnace by measuring the furnace top temperature of the electric furnace (5). I thought about it.
Incidentally, the "furnace top" according to the present invention is a lid portion for charging the object to be processed (2), etc., on the upper surface of the furnace top of the electric furnace (5).
When the shape of the lid is circular, the temperature at the top of the furnace is measured at two points: one point on the circumference centered on the center of the circle and one point on the circumference opposite to the point. It has also been found that thermometers may be provided at various locations, or a plurality of thermometers may be provided at equal intervals on the circumference.
A thermocouple, an infrared sensor, or the like can be used as the thermometer installed on the furnace top.
本発明者らは、還元溶錬工程において測定された炉頂温度を参照し、電気炉（５）における電極の電力調整を行うことによる電気炉（５）の最適な温度制御について検討した。その結果、炉頂温度を、温度低下により被処理物の溶け残りが増加し始める温度より２０℃以上高めに制御することで、被処理物（２）の溶け残りの発生を解消できることに想到した。 The present inventors examined the optimum temperature control of the electric furnace (5) by adjusting the electric power of the electrodes in the electric furnace (5) with reference to the furnace top temperature measured in the reduction smelting process. As a result, it was conceived that by controlling the furnace top temperature to be 20° C. or more higher than the temperature at which the undissolved material to be processed begins to increase due to the temperature drop, the occurrence of undissolved material (2) to be processed can be eliminated. .
そして、温度以外は同一の条件で行う前記還元溶錬工程において、溶融スラグ（７）抽出のタイミングの炉頂温度を制御することを実施した。その結果、温度低下により被処理物の溶け残りが多くなり始める炉頂温度より１２０～４２０℃高い温度、さらに好ましくは１５０～４００℃高い温度、一層好ましくは１８０～３５０℃高い温度に炉頂温度を設定することにより、ＰＧＭの溶融スラグ（７）層への移動を低減できることに想到した。 Then, in the reduction smelting process, which is performed under the same conditions except temperature, the furnace top temperature is controlled at the timing of extraction of the molten slag (7). As a result, the furnace top temperature is 120 to 420° C. higher, more preferably 150 to 400° C. higher, and still more preferably 180 to 350° C. higher than the furnace top temperature at which the material to be processed begins to remain undissolved due to the temperature drop. By setting , it is possible to reduce the migration of PGM to the molten slag (7) layer.
さらに具体的には、電気炉（５）の炉頂温度を、溶融スラグ（７）の抽出、排出時に９００℃以上１２００℃以下に調整すればよいことに想到した。
これは、炉頂温度を９００℃以上に調整することで被処理物の溶け残りを解消し、スラグ側へ移行するＰＧＭ量を抑制し、さらに炉頂温度を１２００℃以下に調整することで、電気炉（５）の炉壁の劣化を抑制することになるからである。
More specifically, the inventors have come up with the idea that the furnace top temperature of the electric furnace (5) should be adjusted to 900° C. or higher and 1200° C. or lower during the extraction and discharge of the molten slag (7).
This is because by adjusting the furnace top temperature to 900°C or higher, the undissolved material to be processed is eliminated, the amount of PGM that migrates to the slag side is suppressed, and the furnace top temperature is adjusted to 1200°C or lower. This is because deterioration of the furnace wall of the electric furnace (5) is suppressed.
これに対し、従来の技術に係る還元溶錬を、電気炉（５）の炉頂温度の測定結果から評価してみると、炉頂温度は７８０～８８０℃である場合が多く、この温度設定が被処理物の溶け残りの原因であると考えられた。 On the other hand, when the reduction smelting according to the conventional technology is evaluated from the measurement results of the furnace top temperature of the electric furnace (5), the furnace top temperature is often 780 to 880 ° C., and this temperature setting was considered to be the cause of undissolved material to be processed.
また、電気炉（５）の炉頂温度の測定から、当該還元溶錬工程において電気炉メタル（６）抽出時の１～３時間前に、電気炉（５）の加熱を停止することが好ましいことにも想到した。
当該時点での電気炉（５）の加熱停止により、溶融スラグ（７）を抽出し排出する時に、溶融物の温度が１３００～１４００℃になり得るからである。これにより、被処理物（２）の溶け残りを解消でき、溶融スラグ（７）側へのＰＧＭ移動を低減できるのでＰＧＭの回収率が高まる。また、電気炉（５）内の温度が上がり過ぎて炉壁が劣化することを抑制することができる。
In addition, from the measurement of the furnace top temperature of the electric furnace (5), it is preferable to stop heating the electric furnace (5) 1 to 3 hours before the extraction of the electric furnace metal (6) in the reduction smelting process. I also thought about it.
This is because the temperature of the melt can reach 1300-1400° C. when the molten slag (7) is extracted and discharged by stopping the heating of the electric furnace (5) at that time. As a result, unmelted portions of the object (2) to be processed can be eliminated, and PGM migration to the molten slag (7) side can be reduced, thereby increasing the recovery rate of PGM. In addition, it is possible to prevent deterioration of the furnace wall due to excessive temperature rise in the electric furnace (5).
尚、本発明に係る還元溶錬では、被処理物（２）に対して、質量換算で０．３倍以上１．０倍以下の抽出剤（３）を投入することが好ましい。これは抽出剤（３）が０．３倍以上投入されれば、溶融スラグ（７）のＰＧＭ含有率を抑制してＰＧＭロスを低減することができるからである。一方、抽出剤（３）の投入が１．０倍以下であれば処理できる被処理物（２）量を担保できる為、効率的だからである。 In addition, in the reduction smelting according to the present invention, it is preferable to add the extractant (3) in an amount of 0.3 to 1.0 times as much as the material to be treated (2) in terms of mass. This is because the PGM loss can be reduced by suppressing the PGM content of the molten slag (7) when the extractant (3) is added 0.3 times or more. On the other hand, if the input of the extraction agent (3) is 1.0 times or less, it is efficient because the amount of the object (2) that can be processed can be ensured.
［５］本発明に係る酸化溶錬工程
本発明に係る酸化溶錬工程におけるＣｕ２Ｏスラグ（１１）とＰＧＭ合金（１０）との間の白金、ロジウム、パラジウムの分配比は、還元溶錬工程における溶融スラグ（７）と電気炉メタル（６）間の分配比の値に比べ、１００倍程度大きな値を示す。この為、電気炉メタル（６）中のＰＧＭを濃縮する過程で発生するＣｕ２Ｏスラグ（１１）中へ、相当量のＰＧＭが分配されてしまう。即ち、ＰＧＭ合金（１０）としてのＰＧＭの回収率は抑制される。
[5] Oxidative smelting process according to the present invention The distribution ratio of platinum, rhodium, and palladium between the Cu 2 O slag (11) and the PGM alloy (10) in the oxidative smelting process according to the present invention is It shows a value about 100 times larger than the value of the distribution ratio between the molten slag (7) and the electric furnace metal (6) in the process. Therefore, a considerable amount of PGM is distributed into the Cu 2 O slag (11) generated in the process of concentrating the PGM in the electric furnace metal (6). That is, the recovery rate of PGM as the PGM alloy (10) is suppressed.
そこで、当該相当量のＰＧＭが分配されたＣｕ２Ｏスラグ（１１）を、再び、以降実施される還元溶錬工程へ抽出剤（３）として繰り返し、投入することが好ましい。当該構成により、Ｃｕ２Ｏスラグ（１１）中へ分配された相当量のＰＧＭは、還元溶錬工程と酸化溶錬工程との系内を循環することになり、結果として高効率でＰＧＭを回収できる。 Therefore, it is preferable to repeatedly feed the Cu 2 O slag (11) in which a considerable amount of PGM has been distributed as an extractant (3) to the reduction smelting process to be performed thereafter. With this configuration, a considerable amount of PGM distributed in the Cu 2 O slag (11) circulates within the system of the reduction smelting process and the oxidation smelting process, resulting in highly efficient PGM recovery. can.
また、酸化溶錬工程の際に酸化物（８）を添加し、前記溶融した電気炉メタル（６）を撹拌した後、静置することが好ましい。これにより、Ｃｕ２Ｏスラグ（１１）へのＰＧＭの分配を低減することができる。 Moreover, it is preferable to add the oxide (8) during the oxidative smelting process, stir the molten electric furnace metal (6), and then leave it at rest. This can reduce the distribution of PGM to the Cu 2 O slag (11).
［６］本発明に係るＰＧＭ回収方法例
本発明に係るＰＧＭの回収工程について、一例を挙げながら説明する。
セラミックス製自動車触媒等のＰＧＭを含有する被処理物（２）と、抽出剤（３）であるＣｕおよび／またはＣｕ２Ｏと、フラックス（１）であるＣａＯおよび／またはＳｉＯ２と、そして還元剤（４）であるＳｉＣ等のＣ含有材料とを、電気炉（５）に装填して加熱する。このとき、電気炉（５）の炉頂温度の昇温速度から溶融スラグ（７）を抽出し排出するタイミングを決定し、その３時間前の炉頂温度が９００℃以上１２００℃以下になるように、電気炉（５）内の電極へ加える電力の調整を行う。
[6] Example of PGM recovery method according to the present invention The PGM recovery process according to the present invention will be described with an example.
An object to be treated (2) containing PGM such as a ceramic automotive catalyst, Cu and/or Cu 2 O as an extractant (3), CaO and/or SiO 2 as a flux (1), and reduction An electric furnace (5) is loaded with a C-containing material such as SiC as the agent (4) and heated. At this time, the timing of extracting and discharging the molten slag (7) is determined from the heating rate of the furnace top temperature of the electric furnace (5), and the furnace top temperature three hours before that is determined to be 900 ° C. or higher and 1200 ° C. or lower. Then, the power applied to the electrodes in the electric furnace (5) is adjusted.
その後、酸化物（ＣａＯ－ＳｉＯ２－Ａｌ２Ｏ３）主体の溶融スラグ（７）層の下方にＣｕ合金の溶融メタルを沈降させ、当該Ｃｕ合金中にＰＧＭが濃縮した電気炉メタル（６）を得る。一方、Ｃｕ含有量が３．０質量％以下にまで低下した溶融スラグ（７）は当該電気炉から抽出し排出する。 After that, the molten metal of Cu alloy is allowed to settle below the layer of molten slag ( 7 ) mainly composed of oxides ( CaO-- SiO.sub.2 --Al.sub.2O.sub.3), and electric furnace metal (6) in which PGM is concentrated in the Cu alloy. get On the other hand, the molten slag (7) in which the Cu content has decreased to 3.0% by mass or less is extracted from the electric furnace and discharged.
そして、ＰＧＭが濃縮した電気炉メタル（６）を抽出し、溶融状態のまま酸化炉（９）に移し替える。溶融した電気炉メタル（６）を酸化溶錬する際、上述した酸化物（８）としてＳｉＯ２、ＣａＯ、Ｎａ２Ｏから選択される１種以上を添加できる。電気炉メタル（６）へＳｉＯ２等の酸化物（８）を添加する際は、添加量の全量を一挙に添加するのではなく、少量ずつ添加することが好ましい。これは電気炉メタル（６）へ、添加する酸化物（８）の全量を一挙に添加すると、溶融している電気炉メタル（６）の溶体温度が低下し、添加された酸化物（８）が溶解出来なくなる為である。従って、酸化物（８）の添加時間は、溶融している電気炉メタル（６）量にも依るが、２０分間以上かけて添加することが好ましい。 Then, the electric furnace metal (6) enriched with PGM is extracted and transferred to the oxidation furnace (9) in a molten state. When oxidizing and smelting the molten electric furnace metal (6), one or more selected from SiO 2 , CaO and Na 2 O can be added as the oxide (8) described above. When adding the oxide (8) such as SiO 2 to the electric furnace metal (6), it is preferable to add the oxide little by little rather than adding the entire amount at once. This is because when the entire amount of the oxide (8) to be added is added to the electric furnace metal (6) at once, the solution temperature of the molten electric furnace metal (6) decreases, and the added oxide (8) This is because it becomes impossible to dissolve Therefore, the addition time of the oxide (8) depends on the amount of the molten electric furnace metal (6), but it is preferable to add the oxide (8) over 20 minutes or longer.
酸化物（８）添加後に電気炉メタル（６）を撹拌し、酸化物（８）を溶解させるが、溶体の撹拌方法としては、空気および／または酸素によるエアレーションが好ましい。 After the addition of the oxide (8), the electric furnace metal (6) is stirred to dissolve the oxide (8). As a method of stirring the solution, aeration with air and/or oxygen is preferred.
酸化物（８）が溶解後、溶体を静置する。このとき、酸化炉（９）内の溶融物の中心近傍が１２００～１５００℃になっていると推察できる。そして、酸化物主体のＣｕ２Ｏスラグ（１１）層と、ＰＧＭがさらに濃縮したＰＧＭ合金（１０）層とに分離し、ＰＧＭ合金（１０）を得る。得られたＰＧＭ合金（１０）から、適宜な回収方法（主に、湿式法）により、ＰＧＭを得る。 After the oxide (8) has dissolved, the solution is allowed to stand. At this time, it can be inferred that the vicinity of the center of the melt in the oxidation furnace (9) has reached 1200 to 1500°C. Then, it is separated into a Cu 2 O slag (11) layer mainly composed of oxides and a PGM alloy (10) layer in which PGM is further concentrated to obtain a PGM alloy (10). PGM is obtained from the obtained PGM alloy (10) by an appropriate recovery method (mainly a wet method).
（実施例１）
実施例１に係る還元溶錬工程においては、電気炉中へ、フラックスとしてＣａＯを５０００ｋｇ、ＳｉＯ２を１００ｋｇ、被処理物としてセラミック製自動車触媒の粉砕物を８５００ｋｇ、還元剤としてＳｉＣを６００ｋｇ、抽出剤として前回工程から繰り返されたＣｕ２Ｏスラグを、被処理物に対して質量比で０．６倍量の５１００ｋｇ投入した。
(Example 1)
In the reduction smelting process according to Example 1, 5000 kg of CaO and 100 kg of SiO 2 as fluxes, 8500 kg of pulverized ceramic automobile catalysts as objects to be treated, 600 kg of SiC as reducing agents, and extraction 5,100 kg of Cu 2 O slag, which was repeated from the previous step, was added as an agent, which was 0.6 times the mass of the object to be treated.
溶融スラグを抽出し排出するタイミングに合わせて、電気炉の炉頂温度の昇温速度を制御し、溶融スラグを抽出するときの炉頂温度が１０００℃になるように電極へ加える電力を調整した。また、溶融スラグを抽出し排出する２時間前に通電を停止した。尚、前回工程から繰り返されたＣｕ２ＯスラグによりＣｕ量が充当されたので、抽出剤として新たな金属Ｃｕは投入しなかった。 The heating rate of the furnace top temperature of the electric furnace was controlled in accordance with the timing of extracting and discharging the molten slag, and the electric power applied to the electrodes was adjusted so that the furnace top temperature when extracting the molten slag was 1000°C. . In addition, electricity was stopped two hours before the molten slag was extracted and discharged. In addition, since the Cu amount was appropriated by the Cu 2 O slag repeated from the previous step, no new metallic Cu was added as an extractant.
実施例１に係る炉頂の温度推移を、図２のグラフに実線で示す。
尚、炉頂温度は、炉頂にある上蓋の４ヵ所に穿孔し、それぞれに熱電対を設けて測定したものの平均値である。
A solid line in the graph of FIG. 2 shows the temperature change at the furnace top according to the first embodiment.
The temperature at the top of the furnace is an average value measured by piercing four holes on the upper lid on the top of the furnace and installing thermocouples in each hole.
上述の還元溶錬工程で生成した溶融スラグであるＣａＯ－ＳｉＯ２－Ａｌ２Ｏ３スラグを、電気炉から抽出し排出した。溶融スラグ温度は１４５５℃であった。そして、電気炉メタルを電気炉から抽出し、酸化炉へ投入した。
次に、酸化炉へ、Ｃｕ２Ｏスラグ質量に対して５質量％に相当するＳｉＯ２を酸化剤として添加した。このとき電気炉メタルである溶体の急激な降温を回避する為、ＳｉＯ２は全量を一挙に投入するのではなく、２０分間かけて除々に添加した。
CaO-- SiO.sub.2 -- Al.sub.2O.sub.3 slag , which is molten slag produced in the above reduction smelting process, was extracted from the electric furnace and discharged. The molten slag temperature was 1455°C. Then, the electric furnace metal was extracted from the electric furnace and put into the oxidation furnace.
Next, SiO 2 corresponding to 5 mass % with respect to the Cu 2 O slag mass was added as an oxidizing agent to the oxidation furnace. At this time, in order to avoid a rapid temperature drop of the solution, which is the electric furnace metal, SiO 2 was added gradually over 20 minutes instead of adding the entire amount at once.
ＳｉＯ２の投入完了後、溶体を２時間エアレーションして撹拌し、ＳｉＯ２を溶体に溶解させた。エアレーションには空気と酸素との混合気体を使用し、酸素濃度２０質量％で５０Ｎｍ３／ｈの速度で吹込みを行った。
エアレーション終了後、溶融した溶体を静置し生成したＰＧＭ合金を回収した。
一方、生成したＣｕＯ２スラグを採取し、次回工程の還元溶錬工程へ繰り返した。
After the addition of SiO2 was completed, the solution was aerated and stirred for 2 hours to dissolve the SiO2 into the solution. A mixed gas of air and oxygen was used for aeration, and was blown at a rate of 50 Nm 3 /h with an oxygen concentration of 20% by mass.
After the aeration was completed, the PGM alloy formed by leaving the melted solution to stand was recovered.
On the other hand, the generated CuO 2 slag was collected and repeated to the next reduction smelting process.
尚、電気炉から排出した溶融スラグ中のＰＧＭロス率をＩＣＰにて定量分析したところ０．０６質量％であり、非常に小さい値であることが判明した。 Incidentally, when the PGM loss rate in the molten slag discharged from the electric furnace was quantitatively analyzed by ICP, it was found to be 0.06% by mass, which is a very small value.
（比較例１）
還元溶錬工程において電極へ加える電力量を一定とし、溶融スラグを抽出し排出するときの炉頂温度が８５０℃になるようにした以外は、実施例１と同様の操作を行った。
生成したＰＧＭ合金を回収し、ＣｕＯ２スラグを採取した。採取されたＣｕＯ２スラグは、次回工程の還元溶錬工程へ繰り返した。
(Comparative example 1)
The same operation as in Example 1 was performed except that the amount of electric power applied to the electrodes in the reduction smelting process was constant, and the top temperature of the furnace when extracting and discharging the molten slag was set to 850°C.
The PGM alloy produced was recovered and the CuO2 slag was taken. The collected CuO 2 slag was repeated to the next reduction smelting step.
比較例１に係る炉頂の温度推移を、図２のグラフに破線で示す。 The graph of FIG. 2 shows the transition of the furnace top temperature according to Comparative Example 1 by a broken line.
電気炉から排出した溶融スラグ中のＰＧＭロス率をＩＣＰにて定量分析しところ０．７８質量％であり、実施例１に比較して大きな値であることが判明した。 The PGM loss rate in the molten slag discharged from the electric furnace was quantitatively analyzed by ICP and found to be 0.78% by mass, which is a large value compared to Example 1.
（比較例２）
還元溶錬工程において電極へ加える電力量を一定とし、溶融スラグを抽出し排出するときの炉頂温度を、実施例１で説明した炉頂温度より下げた以外は、実施例１と同様の操作を行った。
すると、溶融スラグの排出時の０時間前、１時間前、２時間前における炉頂温度が７８０℃以下になると、被処理物の溶け残りが多く発生することが判明した。
(Comparative example 2)
The same operation as in Example 1 except that the amount of electric power applied to the electrodes in the reduction smelting process is constant, and the furnace top temperature when extracting and discharging molten slag is lower than the furnace top temperature described in Example 1. did
Then, it was found that when the furnace top temperature at 0, 1, and 2 hours before discharging the molten slag was 780° C. or less, a large amount of unmelted material was generated.
（まとめ）
以上、説明した実施例および比較例の結果より、本発明の方法によれば、ＰＧＭを含有する被処理物から高効率にＰＧＭ合金を回収することができることが判明した。
(summary)
From the results of the examples and comparative examples described above, it was found that according to the method of the present invention, a PGM alloy can be recovered from a PGM-containing object to be treated with high efficiency.
Claims (3)
電気炉メタル抽出時の１～３時間前に、前記電気炉の加熱を停止し、
前記溶融スラグを抽出し、ＰＧＭを含有する電気炉メタルを抽出して得る還元溶錬工程と、
前記電気炉メタルを酸化炉に移して酸化溶融し、Ｃｕ2Ｏスラグ層とＰＧＭ合金層とを形成した後に、Ｃｕ2Ｏスラグを抽出し、ＰＧＭが濃縮されたＰＧＭ合金を得る酸化溶錬工程と、を行うＰＧＭの回収方法であって、
前記還元溶錬工程における溶融スラグ抽出時に、前記電気炉の炉頂温度を９００℃以上１２００℃以下に制御することを特徴とするＰＧＭの回収方法。 An object to be treated containing PGM, Cu and/or Cu 2 O, flux, and a C (carbon)-containing material are placed in an electric furnace and heated to melt them to form a molten slag layer and an electric furnace metal layer. After forming and
1 to 3 hours before the electric furnace metal extraction, stop heating the electric furnace,
a reduction smelting step of extracting the molten slag and extracting an electric furnace metal containing PGM;
An oxidizing smelting process for transferring the electric furnace metal to an oxidation furnace and oxidizing and melting it to form a Cu 2 O slag layer and a PGM alloy layer, and then extracting the Cu 2 O slag to obtain a PGM-enriched PGM alloy. and a PGM recovery method comprising:
A method for recovering PGM, wherein the furnace top temperature of the electric furnace is controlled to 900° C. or more and 1200° C. or less when extracting molten slag in the reduction smelting step.
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| JP2017197786A (en) | 2016-04-25 | 2017-11-02 | 新日鐵住金株式会社 | Temperature estimation method and operation method for electric furnace |
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