JP3436176B2 - Method for concentrating gallium from sediment containing gallium compound, abrasive grains and cutting oil - Google Patents
Method for concentrating gallium from sediment containing gallium compound, abrasive grains and cutting oilInfo
- Publication number
- JP3436176B2 JP3436176B2 JP07688499A JP7688499A JP3436176B2 JP 3436176 B2 JP3436176 B2 JP 3436176B2 JP 07688499 A JP07688499 A JP 07688499A JP 7688499 A JP7688499 A JP 7688499A JP 3436176 B2 JP3436176 B2 JP 3436176B2
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- JP
- Japan
- Prior art keywords
- gallium
- abrasive grains
- solvent
- cutting oil
- fine powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リン化ガリウム等
ガリウムを含む化合物半導体結晶ウエハの製造過程で発
生するガリウム化合物、砥粒および切削油を含む澱物か
らガリウム分を濃縮して回収するガリウム分の濃縮方法
に係り、特に、大型の乾燥炉や集塵機を用いることなく
簡便・小型の装置でかつ砥粒の吸湿性の影響を受けるこ
となく安定してガリウム分の濃縮が図れる濃縮方法の改
良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gallium for concentrating and recovering gallium from a gallium compound generated in the process of manufacturing a compound semiconductor crystal wafer containing gallium such as gallium phosphide, abrasive grains and cutting oil. Concentration of gallium content is improved, especially with a simple and compact device without using a large drying oven or dust collector, and stable concentration of gallium content can be achieved without being affected by the hygroscopicity of the abrasive grains. It is about.
【０００２】[0002]
【従来の技術】リン化ガリウム等ガリウムを含む化合物
半導体結晶ウエハの製造過程で、ガリウムを含む化合物
半導体結晶（以下、ガリウム化合物という）を切断する
際には、従来、ダイヤモンド内周刃切断装置が用いられ
ていた。この際に切削屑として発生する澱物はガリウム
化合物の切削粉がほとんどであり、金属ガリウム回収の
ための原料として有効利用されていた。2. Description of the Related Art In the process of manufacturing a compound semiconductor crystal wafer containing gallium such as gallium phosphide, when cutting a compound semiconductor crystal containing gallium (hereinafter referred to as a gallium compound), a diamond inner peripheral blade cutting device is conventionally used. Was used. Most of the starch generated as cutting waste at this time is a cutting powder of a gallium compound, and was effectively used as a raw material for recovering metallic gallium.
【０００３】ところで、近年、切断ロス低減による低コ
スト化のため、ガリウム化合物の切断方法については、
切断しろのより少ないワイヤーソー切断による方法に置
き換わってきた。このワイヤーソー切断による方法では
砥粒を分散させた切削油を用いるため、ワイヤーソー切
断の際に発生する澱物は、微細な切削粉（細粉）、より
粗大な砥粒（粗粉）および切削油を含む混合物として捕
集される。そして、ワイヤーソー切断では砥粒の使用量
が多いため、上記澱物中のガリウム化合物含有量は１０
重量％以下となりガリウム濃度は低かった。By the way, in recent years, in order to reduce the cost by reducing the cutting loss, the cutting method of the gallium compound is as follows.
It has replaced the method of cutting with a wire saw, which has less cutting margin. In this method of cutting with a wire saw, cutting oil in which abrasive particles are dispersed is used, so the precipitates generated during cutting with a wire saw are fine cutting powder (fine powder), coarser abrasive particles (coarse powder) and Collected as a mixture containing cutting oil. Since the amount of abrasive grains used in wire saw cutting is large, the gallium compound content in the above-mentioned starch is 10
The gallium concentration was low, since it was less than wt%.
【０００４】そして、ワイヤーソー切断の際に発生した
上記澱物からガリウム分を回収しようとした場合、ガリ
ウム濃度の低い澱物に対して回収処理を施す必要がある
ことから回収効率が悪く、また、上記澱物には切削油が
含まれているため回収される金属ガリウムに不純物が多
く含まれるといった問題を有していた。When the gallium content is to be recovered from the above-mentioned starch generated during the cutting with a wire saw, the recovery efficiency is poor because the recovery treatment needs to be performed on the starch having a low gallium concentration. However, since the above-mentioned starch contains cutting oil, there is a problem that the recovered metallic gallium contains a large amount of impurities.
【０００５】このようにワイヤーソー切断の際に発生し
た澱物からガリウム分を回収することは経済的に見合わ
ないと共に不純物も多く含むことから、従来、上記澱物
は産業廃棄物として処分されていた。Thus, it is economically unprofitable to recover the gallium component from the starch generated during the wire saw cutting, and it also contains a large amount of impurities. Therefore, the above-mentioned starch is conventionally disposed as industrial waste. Was there.
【０００６】しかし、不足しがちなガリウム資源を有効
に利用するという観点から、ワイヤーソー切断の際に発
生した澱物から経済的に有利にかつ不純物も多く含まな
いガリウム分を回収する方法が強く要望されていた。However, from the viewpoint of effectively utilizing the gallium resource which tends to be insufficient, there is a strong method for recovering gallium content which is economically advantageous and does not contain a large amount of impurities from the precipitate generated during the wire saw cutting. It was requested.
【０００７】この様な技術的背景の下、本出願人は、ガ
リウム化合物、砥粒および切削油を含む澱物からのガリ
ウム分を簡便に、かつ、著しく濃縮して回収する方法を
既に提案している（特願平１０−２４２５２３号明細書
参照）。Under such a technical background, the present applicant has already proposed a method for simply and remarkably concentrating and recovering gallium content from a precipitate containing a gallium compound, abrasive grains and cutting oil. (See Japanese Patent Application No. 10-242523).
【０００８】すなわち、出願人が提案した上記方法は、
ガリウム化合物、砥粒および切削油を含む澱物から切削
油を除去するためにガリウム化合物の熱分解温度未満の
温度で澱物を加熱することにより乾燥物を得る第一工程
と、得られた乾燥物を粉砕する第二工程、および、上記
砥粒を除去するために粉砕された乾燥物についてガリウ
ム分を主に含む細粉と上記砥粒を主に含む粗粉とに分級
して上記細粉を回収する第三工程から成ることを特徴と
するものであった。That is, the above method proposed by the applicant is
A first step of obtaining a dried product by heating the starch at a temperature below the thermal decomposition temperature of the gallium compound to remove the cutting oil from the starch containing the gallium compound, abrasive grains and cutting oil, and the resulting drying Second step of crushing the product, and the fine powder that is classified into a fine powder mainly containing gallium content and a coarse powder mainly containing the abrasive grains of the dried product crushed to remove the abrasive grains It was characterized by comprising a third step of recovering.
【０００９】[0009]
【発明が解決しようとする課題】ところで、この方法で
は、上述したようにガリウム化合物含有量が１０重量％
以下の低濃度澱物に対し、第一工程においてその全量を
加熱して乾燥物を得ていることから大型の乾燥炉が必要
となり、かつ、第三工程においてガリウム分を主に含む
細粉を風力分級によって回収していることから大型の集
塵機が必要であった。By the way, in this method, as described above, the gallium compound content is 10% by weight.
For the following low-concentration starch, a large drying furnace is required because the whole amount is heated in the first step to obtain a dried product, and fine powder containing mainly gallium is used in the third step. A large dust collector was necessary because it was collected by wind power classification.
【００１０】また、第二工程において粉砕された乾燥物
についてこれを長時間大気中に放置した場合、粉砕後の
砥粒が吸湿性を有していることに起因して、第三工程に
おける風力分級の際に乾燥物の分散性が悪化しガリウム
化合物の回収率を低下させる問題点を有していた。When the dried product crushed in the second step is left in the atmosphere for a long time, the abrasive grains after crushing have a hygroscopic property, which causes a wind force in the third step. There was a problem that the dispersibility of the dried product deteriorated during classification and the recovery rate of the gallium compound decreased.
【００１１】本発明はこのような問題点に着目してなさ
れたもので、その課題とするところは、大型の乾燥炉や
集塵機を用いることなく簡便・小型の装置でかつ砥粒の
吸湿性の影響を受けることなく安定してガリウム分の濃
縮が図れる澱物からのガリウム分の濃縮方法を提供する
ことにある。The present invention has been made by paying attention to such a problem, and its object is to provide a simple and small apparatus without using a large drying furnace or a dust collector and to improve the hygroscopicity of abrasive grains. It is an object of the present invention to provide a method for concentrating gallium content from a precipitate that can stably concentrate gallium content without being affected.
【００１２】[0012]
【課題を解決するための手段】すなわち、請求項１に係
る発明は、ガリウム化合物、砥粒および切削油を含む澱
物からのガリウム分の濃縮方法を前提とし、切削油と相
溶しかつガリウム化合物の熱分解温度より低い沸点を有
する溶媒に上記澱物内の切削油を溶解させると共に澱物
内のガリウム化合物と砥粒を分散させる第一工程と、上
記ガリウム化合物と砥粒が分散された溶媒から砥粒を除
去するためにガリウム分を主に含む細粉と砥粒を主に含
む粗粉に湿式分級して上記細粉が分散された溶媒を得る
第二工程と、上記細粉が分散された溶媒から溶媒を分離
して細粉を得る第三工程と、得られた上記細粉をガリウ
ム化合物の熱分解温度未満の温度で加熱して残留する上
記溶媒を細粉から除去する第四工程を具備することを特
徴とするものである。That is, the invention according to claim 1 is premised on a method for concentrating gallium content from a gallium compound, abrasive grains and a precipitate containing cutting oil, and is compatible with cutting oil and gallium. The first step of dissolving the cutting oil in the starch in a solvent having a boiling point lower than the thermal decomposition temperature of the compound and dispersing the gallium compound and the abrasive grains in the starch, and the gallium compound and the abrasive grains were dispersed. A second step of obtaining a solvent in which the fine powder is dispersed by wet classification into a fine powder mainly containing gallium content and a coarse powder mainly containing abrasive grains in order to remove the abrasive grains from the solvent, and the fine powder is A third step of separating the solvent from the dispersed solvent to obtain fine powder, and heating the obtained fine powder at a temperature below the thermal decomposition temperature of the gallium compound to remove the residual solvent from the fine powder. It is characterized by comprising four steps .
【００１３】そして、請求項１記載の発明に係るガリウ
ム分の濃縮方法によれば、第二工程において砥粒を除去
してガリウム分を濃縮し、かつ、第三工程において大部
分の溶媒とこれに溶解された切削油を除去しているた
め、第四工程での処理量の低減が図れ、大型の乾燥炉を
必要とすることがない。According to the method for concentrating gallium according to the first aspect of the invention, the gallium is concentrated by removing the abrasive grains in the second step, and most of the solvent and the solvent are concentrated in the third step. Since the cutting oil dissolved in is removed, the processing amount in the fourth step can be reduced and a large drying furnace is not required.
【００１４】また、第一工程、第二工程および第三工程
とも、いわゆる湿式工程であるめ、ガリウム分を主に含
む細粉回収のための大型集塵機も必要とすることがな
い。Further, since the first step, the second step and the third step are so-called wet steps, a large dust collector for recovering fine powder mainly containing gallium is not required.
【００１５】更に、ガリウム分を主に含む細粉と砥粒を
主に含む粗粉とを分級する第二工程は、これ等細粉と粗
粉が溶媒に分散された状態で行われるため、その分級精
度が砥粒における空気からの吸湿性の影響を受けること
もない。Further, the second step of classifying the fine powder mainly containing gallium and the coarse powder mainly containing the abrasive grains is carried out in the state where these fine powder and coarse powder are dispersed in the solvent. The classification accuracy is not affected by the hygroscopicity of the abrasive grains from the air.
【００１６】[0016]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.
【００１７】まず、本発明に係るガリウム分の濃縮方法
は、以下の第一工程から第四工程を具備することを特徴
とするものである。First, the method for concentrating gallium according to the present invention is characterized by comprising the following first to fourth steps.
【００１８】（１）第一工程
この方法の第一工程では、切削油と相溶しかつガリウム
化合物の熱分解温度より低い沸点を有する溶媒に上記澱
物内の切削油を溶解させると共に澱物内のガリウム化合
物と砥粒を分散させる。(1) First Step In the first step of this method, the cutting oil in the above-mentioned starch is dissolved in a solvent which is compatible with the cutting oil and has a boiling point lower than the thermal decomposition temperature of the gallium compound, and Disperse the gallium compound and the abrasive grains in the inside.
【００１９】ここで、澱物内のガリウム化合物と砥粒を
上記溶媒に分散させるのは以下の理由による。すなわ
ち、ワイヤーソー切断時における砥粒は、通常、切削油
に高濃度に分散されていることから上記澱物が高粘度で
あるため、澱物内のガリウム化合物と砥粒を溶媒に分散
させないと、第二工程における湿式分級による砥粒の除
去が不十分になる場合があるからである。Here, the gallium compound and the abrasive grains in the precipitate are dispersed in the above solvent for the following reason. That is, the abrasive grains at the time of cutting with a wire saw are usually high in viscosity because the above-mentioned starch is dispersed in cutting oil at a high concentration, so the gallium compound in the starch and the abrasive grains must be dispersed in a solvent. This is because the removal of abrasive grains by wet classification in the second step may be insufficient.
【００２０】尚、湿式分級による砥粒の除去が可能なら
ば、本来、澱物内のガリウム化合物と砥粒を切削油自身
を用いて分散させてもよく、本発明においては上記溶媒
として切削油を適用してもよい。但し、第二工程におけ
る湿式分級による砥粒除去の徹底を図るためには上記切
削油より低粘度の溶媒が適している。また、切削油より
低粘度の溶媒を適用することにより第三工程における溶
媒の分離も容易となる。また、切削油よりも低沸点の溶
媒を適用した場合には、第四工程における溶媒除去時の
加熱負担を軽減させることも可能である。If the abrasive particles can be removed by wet classification, the gallium compound in the precipitate and the abrasive particles may be originally dispersed by using the cutting oil itself. In the present invention, the cutting oil is used as the solvent. May be applied. However, a solvent having a viscosity lower than that of the cutting oil is suitable for thorough removal of abrasive grains by wet classification in the second step. Further, by applying a solvent having a viscosity lower than that of the cutting oil, the solvent can be easily separated in the third step. When a solvent having a boiling point lower than that of the cutting oil is applied, it is possible to reduce the heating load when removing the solvent in the fourth step.
【００２１】そして、上記溶媒に対するこれ等の要求お
よび経済的観点から、本発明者等は、溶媒として灯油が
最も適していることを見出だしている（請求項２）。
尚、切削油や灯油の沸点には温度範囲が通常あるが、温
度範囲のある沸点の高低をいう場合に用いる沸点は『沸
点の上限』を本明細書では意味する。From the above-mentioned demands on the solvent and the economical point of view, the present inventors have found that kerosene is most suitable as the solvent (claim 2).
Although the boiling point of cutting oil or kerosene usually has a temperature range, the boiling point used when referring to a high or low boiling point having a temperature range means "upper limit of boiling point" in this specification.
【００２２】ここで、上記溶媒として切削油以外の低粘
度溶媒を適用した場合、この溶媒を用いて澱物内の切削
油を溶解させかつ澱物内のガリウム化合物と砥粒とを分
散させる第一工程の際、ガリウム化合物、砥粒および切
削油を含む澱物を放置・自然沈降させかつ上澄み切削油
について事前に除去する処理を施すことにより、第二工
程における湿式分級、第三工程における溶媒分離、およ
び、第四工程における溶媒除去をより効果的に行うこと
が可能となる。When a low-viscosity solvent other than cutting oil is applied as the solvent, the solvent is used to dissolve the cutting oil in the starch and to disperse the gallium compound and the abrasive grains in the starch. In the one step, the precipitation including the gallium compound, the abrasive grains and the cutting oil is left to stand and is allowed to spontaneously sediment, and the supernatant cutting oil is removed in advance to perform wet classification in the second step and solvent in the third step. Separation and solvent removal in the fourth step can be performed more effectively.
【００２３】（２）第二工程
第二工程では、ガリウム化合物と砥粒が分散された溶媒
から砥粒を除去するためにガリウム分を主に含む細粉と
砥粒を主に含む粗粉に湿式分級して上記細粉が分散され
た溶媒を得る。(2) Second Step In the second step, in order to remove the abrasive particles from the solvent in which the gallium compound and the abrasive particles are dispersed, fine powder containing mainly gallium content and coarse powder containing mainly abrasive particles are prepared. Wet classification is performed to obtain a solvent in which the fine powder is dispersed.
【００２４】ここで、湿式分級としては、自然沈降法、
上記細粉よりも大きな開口径を有するフィルタを用いた
濾過法も適用できるが、連続処理が可能で経済的な液体
サイクロンを用いた方法（請求項３）が適している。
尚、液体サイクロンにおける分級点の設定に関しては、
以下のような設定方法が例示される。すなわち、上記澱
物の一部を資料として採取し、かつ、採取した澱物を乾
燥させた後、この乾燥させた澱物を、ガリウム化合物を
溶解するエッチング液、例えば王水等で処理し、処理前
後の澱物の各粒度分布の比較（すなわち、ガリウム化合
物と砥粒が含まれた処理前の澱物の粒度分布と、ガリウ
ム化合物が除去された処理後の澱物の粒度分布の比較）
から澱物内に含まれるガリウム化合物の粒度分布を事前
に測定し、ガリウム化合物の最大粒径程度に設定すると
よい。Here, as the wet classification, a natural sedimentation method,
A filtration method using a filter having an opening diameter larger than that of the fine powder can also be applied, but a method using a liquid cyclone that allows continuous treatment and is economical (claim 3) is suitable.
In addition, regarding the setting of the classification point in the liquid cyclone,
The following setting method is exemplified. That is, a part of the above-mentioned starch is collected as a material, and the collected starch is dried, and the dried starch is treated with an etching solution that dissolves a gallium compound, such as aqua regia, Comparison of each particle size distribution of the starch before and after the treatment (that is, comparison of the particle size distribution of the starch containing the gallium compound and abrasive grains before the treatment and the particle size distribution of the starch after removal of the gallium compound)
Therefore, it is advisable to measure the particle size distribution of the gallium compound contained in the precipitate in advance and set it to about the maximum particle size of the gallium compound.
【００２５】（３）第三工程
第三工程では、細粉が分散された溶媒から溶媒を分離し
てガリウム分を主に含む上記細粉を得る。(3) Third Step In the third step, the solvent is separated from the solvent in which the fine powder is dispersed to obtain the fine powder mainly containing gallium.
【００２６】ここで、細粉が分散された溶媒から溶媒を
分離する手段としては、自然沈降法、上記細粉よりも小
さな開口径を有するフィルタを用いた濾過法も適用でき
るが、連続処理が可能で経済的なデカンタ型遠心分離装
置を用いた方法（請求項４）が適している。尚、より経
済的な観点から、デカンタ型遠心分離装置により分離さ
れた溶媒については、第一工程の溶媒として再利用する
ことが好ましい。Here, as a means for separating the solvent from the solvent in which the fine powder is dispersed, a natural sedimentation method and a filtration method using a filter having an opening diameter smaller than that of the above fine powder can be applied, but continuous treatment is possible. A method using a decanter centrifuge which is possible and economical (claim 4) is suitable. From a more economical point of view, the solvent separated by the decanter type centrifugal separator is preferably reused as the solvent in the first step.
【００２７】（４）第四工程
第四工程では、第三工程で得られた上記細粉をガリウム
化合物の熱分解温度未満の温度で加熱して残留する溶媒
を細粉から除去する。(4) Fourth Step In the fourth step, the fine powder obtained in the third step is heated at a temperature lower than the thermal decomposition temperature of the gallium compound to remove the residual solvent from the fine powder.
【００２８】ここで、上記細粉の加熱温度をガリウム化
合物の熱分解温度未満の温度としている理由は、大気中
においてガリウム化合物の熱分解温度以上とした場合、
ガリウム化合物が熱分解あるいは酸化して目的とする金
属ガリウムの回収が困難となるからである。尚、上記細
粉の加熱温度を溶媒の沸点以上とした場合、残留する溶
媒を細粉から速やかに蒸発させることができるため好ま
しい（請求項５）。Here, the reason why the heating temperature of the fine powder is set to a temperature lower than the thermal decomposition temperature of the gallium compound is that when it is higher than the thermal decomposition temperature of the gallium compound in the atmosphere,
This is because the gallium compound is thermally decomposed or oxidized to make it difficult to recover the target metallic gallium. When the heating temperature of the fine powder is equal to or higher than the boiling point of the solvent, the residual solvent can be quickly evaporated from the fine powder, which is preferable.
【００２９】また、上記澱物中にワイヤーソーのワイヤ
ー片など磁性物が含まれている場合には、この磁性物を
除去することが好ましい。具体的には、第一工程、第二
工程および第三工程の少なくとも一つの工程時に、溶媒
内に含まれるワイヤー片などの磁性物を磁石を用いて除
去する（請求項６）。この除去処理により、金属ガリウ
ムとして回収するまでに必要でかつ繁雑な脱Ｆｅ処理を
省略することが可能となる。When the above-mentioned sediment contains a magnetic substance such as a wire piece of a wire saw, it is preferable to remove this magnetic substance. Specifically, at least one of the first step, the second step, and the third step, a magnetic substance such as a wire piece contained in the solvent is removed using a magnet (claim 6). By this removal process, it becomes possible to omit the complicated and necessary Fe removal process before recovering as metallic gallium.
【００３０】このように本発明に係る濃縮方法によれ
ば、大型の乾燥炉や集塵機を用いることなく簡便・小型
の装置でかつ砥粒の吸湿性の影響を受けることなくガリ
ウム分の濃縮が図れるため、安定してガリウム化合物の
回収が可能となる。As described above, according to the concentration method of the present invention, the gallium content can be concentrated with a simple and small apparatus without using a large drying furnace or a dust collector and without being affected by the hygroscopicity of the abrasive grains. Therefore, the gallium compound can be stably recovered.
【００３１】[0031]
【実施例】以下、本発明の実施例について具体的に説明
する。EXAMPLES Examples of the present invention will be specifically described below.
【００３２】リン化ガリウム単結晶（熱分解温度：６８
０℃）をワイヤーソーで切断した際に切削屑として発生
した澱物を以下のように処理した。尚、この澱物は、リ
ン化ガリウムの切削粉、ＳｉＣが主成分の砥粒、および
切削油（沸点：２００〜４００℃）を含む。この澱物を
分析した結果を以下の表１に示す。Gallium phosphide single crystal (pyrolysis temperature: 68
At 0 ° C.), a starch generated as cutting scraps when cut with a wire saw was treated as follows. The starch contains gallium phosphide cutting powder, abrasive grains containing SiC as a main component, and cutting oil (boiling point: 200 to 400 ° C.). The results of analysis of this starch are shown in Table 1 below.
【００３３】[0033]
【表１】
また、この澱物の一部を資料として採取し、かつ、採取
した澱物を乾燥させた後、この乾燥させた澱物を王水で
処理し、王水エッチング処理前後の澱物の粒度分布を図
１に示す。そして、図１に示されたリン化ガリウムと砥
粒が含まれたエッチング前の粒度分布と、リン化ガリウ
ムが除去されたエッチング後の粒度分布との比較から、
澱物内に含まれるリン化ガリウムは５μｍ以下の粒径で
あると推察される。[Table 1] In addition, a part of this starch is collected as a reference material, and the collected starch is dried, then the dried starch is treated with aqua regia, and the particle size distribution of the starch before and after the aqua regia etching treatment is used. Is shown in FIG. Then, from the comparison between the particle size distribution before etching containing gallium phosphide and abrasive grains shown in FIG. 1 and the particle size distribution after etching with gallium phosphide removed,
It is estimated that the gallium phosphide contained in the starch has a particle size of 5 μm or less.
【００３４】まず、上記澱物１２．０ｋｇ（ガリウム含
有量７６０ｇ）を灯油（沸点：１５０〜２８０℃）８０
リットル内に投入し、攪拌・分散後、永久磁石を入れ磁
石に吸着されたものを除去して分散液を得た。First, 12.0 kg of the above-mentioned starch (gallium content: 760 g) was added to kerosene (boiling point: 150-280 ° C.) 80
The mixture was placed in a liter, stirred and dispersed, and then a permanent magnet was put in to remove the matter adsorbed on the magnet to obtain a dispersion liquid.
【００３５】次に、得られた分散液を、液体サイクロン
により５μｍを境として分級し、ガリウム分を主に含む
上流分散液（細粉が含まれる）約７８リットルと、砥粒
を主に含む下流分散液（粗粉が含まれる）約６リットル
を得た。Next, the obtained dispersion liquid is classified by a liquid cyclone at a boundary of 5 μm, and about 78 liters of an upstream dispersion liquid (containing fine powder) mainly containing gallium is mainly contained. About 6 liters of the downstream dispersion liquid (including coarse powder) was obtained.
【００３６】この分級処理で得られた上流分散液約７８
リットルを、デカンタ型遠心分離装置を用いて遠心加速
度３２００Ｇ、滞留時間６０秒の条件で遠心分離し、約
２０６０ｇの固形物を得た。About 78 of the upstream dispersion obtained by this classification treatment
The liter was centrifuged using a decanter type centrifugal separator under the conditions of centrifugal acceleration of 3200 G and residence time of 60 seconds to obtain about 2060 g of solid matter.
【００３７】次に、この固形物を３００℃で加熱乾燥
し、１８５５ｇの乾燥物を得た。この乾燥物を分析した
結果を以下の表２に示す。Next, this solid substance was heated and dried at 300 ° C. to obtain 1855 g of a dried substance. The results of analysis of this dried product are shown in Table 2 below.
【００３８】[0038]
【表２】
次に、上記乾燥物１８５５ｇから従来方法により金属ガ
リウムを回収した。[Table 2] Next, metallic gallium was recovered from 1855 g of the dried product by a conventional method.
【００３９】すなわち、上記乾燥物を酸に溶解した後中
和して、ガリウムを一旦水酸化ガリウムとした。その
後、水酸化ガリウムをアルカリ性溶液に溶解し、電解に
て金属ガリウムを回収した。その結果、５６６ｇの金属
ガリウムが得られた。That is, the dried product was dissolved in an acid and then neutralized to once convert gallium into gallium hydroxide. Then, gallium hydroxide was dissolved in an alkaline solution, and metallic gallium was recovered by electrolysis. As a result, 566 g of metallic gallium was obtained.
【００４０】[0040]
【発明の効果】このように本発明に係る澱物からのガリ
ウム分の濃縮方法によれば、第二工程において砥粒を除
去してガリウム分を濃縮し、かつ、第三工程において大
部分の溶媒とこれに溶解された切削油を除去しているこ
とから、第四工程での処理量の低減が図れるため大型の
乾燥炉を必要とすることがない。As described above, according to the method for concentrating gallium content from the precipitate according to the present invention, the gallium content is concentrated by removing the abrasive grains in the second step, and most of the gallium content is concentrated in the third step. Since the solvent and the cutting oil dissolved therein are removed, the processing amount in the fourth step can be reduced, so that a large drying furnace is not required.
【００４１】また、第一工程、第二工程および第三工程
とも、いわゆる湿式工程であるめ、ガリウム分を主に含
む細粉回収のための大型集塵機も必要とすることがな
い。Further, since the first step, the second step and the third step are so-called wet steps, a large dust collector for recovering fine powder mainly containing gallium is not required.
【００４２】更に、ガリウム分を主に含む細粉と砥粒を
主に含む粗粉とを分級する第二工程は、これ等細粉と粗
粉が溶媒に分散された状態で行われるため、その分級精
度が砥粒における空気からの吸湿性の影響を受けること
もない。Further, the second step of classifying the fine powder mainly containing gallium and the coarse powder mainly containing the abrasive grains is carried out in the state where the fine powder and the coarse powder are dispersed in the solvent. The classification accuracy is not affected by the hygroscopicity of the abrasive grains from the air.
【００４３】従って、大型の乾燥炉や集塵機を用いるこ
となく、簡便・小型の装置で、かつ、砥粒の吸湿性の影
響を受けることなく澱物から安定してガリウム分を濃縮
できる効果を有する。Therefore, the gallium component can be stably concentrated from the precipitate without using a large drying oven or a dust collector, with a simple and small device and without being affected by the hygroscopicity of the abrasive grains. .
【図１】王水エッチング前後の澱物の粒度分布を示すグ
ラフ図。FIG. 1 is a graph showing the particle size distribution of a starch before and after aqua regia etching.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平10−140229（ＪＰ，Ａ) 特開 平９−118937（ＪＰ，Ａ) 特開 平９−31561（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22B 1/00 - 61/00 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-10-140229 (JP, A) JP-A-9-118937 (JP, A) JP-A-9-31561 (JP, A) (58) Field (Int.Cl. 7 , DB name) C22B 1/00-61/00
Claims (6)
澱物からのガリウム分の濃縮方法において、 切削油と相溶しかつガリウム化合物の熱分解温度より低
い沸点を有する溶媒に上記澱物内の切削油を溶解させる
と共に澱物内のガリウム化合物と砥粒を分散させる第一
工程と、上記ガリウム化合物と砥粒が分散された溶媒か
ら砥粒を除去するためにガリウム分を主に含む細粉と砥
粒を主に含む粗粉に湿式分級して上記細粉が分散された
溶媒を得る第二工程と、上記細粉が分散された溶媒から
溶媒を分離して細粉を得る第三工程と、得られた上記細
粉をガリウム化合物の熱分解温度未満の温度で加熱して
残留する上記溶媒を細粉から除去する第四工程を具備す
ることを特徴とするガリウム化合物、砥粒および切削油
を含む澱物からのガリウム分の濃縮方法。1. A method for concentrating a gallium component from a starch containing a gallium compound, abrasive grains and cutting oil, wherein a solvent having a boiling point lower than the thermal decomposition temperature of the gallium compound is dissolved in the above-mentioned starch. The first step of dissolving the cutting oil and dispersing the gallium compound and the abrasive grains in the precipitate, and the fine particles mainly containing gallium component for removing the abrasive grains from the solvent in which the gallium compound and the abrasive grains are dispersed. A second step of obtaining a solvent in which the fine powder is dispersed by wet classification into a coarse powder mainly containing powder and abrasive grains; and a step of obtaining a fine powder by separating the solvent from the solvent in which the fine powder is dispersed. Step, and a gallium compound characterized by comprising a fourth step of removing the remaining solvent from the fine powder by heating the resulting fine powder at a temperature below the thermal decomposition temperature of the gallium compound, abrasive grains and Gallium content from starch containing cutting oil Concentration method.
とを特徴とする請求項１記載のガリウム化合物、砥粒お
よび切削油を含む澱物からのガリウム分の濃縮方法。2. The method for concentrating gallium from a gallium compound, an abrasive grain and a precipitate containing cutting oil according to claim 1, wherein the solvent in the first step is kerosene.
ける湿式分級を行うことを特徴とする請求項１または２
記載のガリウム化合物、砥粒および切削油を含む澱物か
らのガリウム分の濃縮方法。3. The wet classification in the second step is performed by using a liquid cyclone.
A method for concentrating gallium content from a precipitate containing the described gallium compound, abrasive grains and cutting oil.
工程における溶媒の分離を行うことを特徴とする請求項
１〜３のいずれかに記載のガリウム化合物、砥粒および
切削油を含む澱物からのガリウム分の濃縮方法。4. The decanter-type centrifugal separator is used to separate the solvent in the third step, and the gallium compound according to any one of claims 1 to 3, an abrasive containing a grain and a cutting oil. Method for concentrating gallium from matter.
上記溶媒の沸点以上であることを特徴とする請求項１〜
４のいずれかに記載のガリウム化合物、砥粒および切削
油を含む澱物からのガリウム分の濃縮方法。5. The heating temperature of the fine powder in the fourth step is
The boiling point of the solvent or more, characterized in that
4. A method for concentrating gallium content from a precipitate containing the gallium compound, abrasive grains and cutting oil according to any one of 4 above.
くとも一つの工程時に、磁石を用いて上記澱物中に含ま
れる磁性物を除去することを特徴とする請求項１〜５の
いずれかに記載のガリウム化合物、砥粒および切削油を
含む澱物からのガリウム分の濃縮方法。6. The magnetic substance contained in the precipitate is removed by using a magnet in at least one of the first step, the second step and the third step. A method for concentrating gallium content from a starch containing any of the gallium compound, abrasive grains, and cutting oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07688499A JP3436176B2 (en) | 1999-03-19 | 1999-03-19 | Method for concentrating gallium from sediment containing gallium compound, abrasive grains and cutting oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07688499A JP3436176B2 (en) | 1999-03-19 | 1999-03-19 | Method for concentrating gallium from sediment containing gallium compound, abrasive grains and cutting oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000273558A JP2000273558A (en) | 2000-10-03 |
| JP3436176B2 true JP3436176B2 (en) | 2003-08-11 |
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ID=13618073
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|---|---|---|---|
| JP07688499A Expired - Fee Related JP3436176B2 (en) | 1999-03-19 | 1999-03-19 | Method for concentrating gallium from sediment containing gallium compound, abrasive grains and cutting oil |
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| JP5344376B2 (en) * | 2009-10-01 | 2013-11-20 | 住友電気工業株式会社 | Gallium recovery method |
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