JP2002241866A - Method for recovering tellurium - Google Patents
Method for recovering telluriumInfo
- Publication number
- JP2002241866A JP2002241866A JP2001034228A JP2001034228A JP2002241866A JP 2002241866 A JP2002241866 A JP 2002241866A JP 2001034228 A JP2001034228 A JP 2001034228A JP 2001034228 A JP2001034228 A JP 2001034228A JP 2002241866 A JP2002241866 A JP 2002241866A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- product
- sulfur
- tellurium
- hydrochloric acid
- 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.)
- Withdrawn
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅（Ｃｕ）の電解
精錬において、陽極泥から脱銅処理の際に副産物として
発生するテルル化銅（Ｃｕ2 Ｔｅ）からテルル（Ｔｅ）
を回収する方法に関するものである。The present invention relates to a copper in the electrolytic refining of (Cu), tellurium from tellurium copper (Cu 2 Te) generated as a byproduct when the anode mud copper removal treatment (Te)
And a method for collecting the same.
【０００２】[0002]
【従来の技術】Ｔｅは単独で製錬の対象となる鉱石はな
く、一般にＣｕの電解精錬の副産物として製造される。
Ｃｕの電解精錬の際に陽極から陽極泥が発生するが、Ｔ
ｅは他の金属と化合物を形成して陽極泥中に沈積する。
陽極泥は硫酸を添加した後、焙焼してセレン（Ｓｅ）の
大部分を揮発させることにより焙焼物中に酸に可溶の亜
テルル酸が濃縮される。焙焼物は硫酸を含む銅電解液で
浸出し、その浸出液にＣｕ粉を加えると、ＴｅはＣｕ2
Ｔｅとして沈殿する。ただし、浸出液に銀（Ａｇ）、セ
レン（Ｓｅ）が含まれている場合には、Ｃｕ2 Ｔｅと共
にＡｇ2 Ｔｅ、Ｓｅが沈殿する。2. Description of the Related Art Te has no ore to be smelted alone and is generally produced as a by-product of electrolytic refining of Cu.
During the electrolytic refining of Cu, anode mud is generated from the anode.
e forms a compound with another metal and deposits in the anode mud.
After adding sulfuric acid, the anode mud is roasted to volatilize most of selenium (Se), whereby the acid soluble tellurous acid is concentrated in the roasted product. The roasted product is leached with a copper electrolytic solution containing sulfuric acid, and when Cu powder is added to the leached solution, Te becomes Cu 2
Precipitates as Te. However, when silver (Ag) and selenium (Se) are contained in the leaching solution, Ag 2 Te and Se are precipitated together with Cu 2 Te.
【０００３】従来行われていたＣｕ2 ＴｅからのＴｅの
回収は、Ｃｕ2 Ｔｅの分離採取後、チリ硝石およびソー
ダ灰と混合して分銀炉に投入し、Ａｇを金属として分離
した後、ＴｅおよびＳｅはソーダガラスとする。ソーダ
ガラスは熱湯で浸出し、生成した亜セレン酸ソーダおよ
び亜テルル酸ソーダ溶液を希硫酸で中和するとＴｅＯ 2
の沈殿が得られる。[0003] Conventional CuTwoTe from Te
Recovery is CuTwoAfter separation and extraction of Te, Chile saltpeter and saw
Mix with Da Ash and put into silver separator, separate Ag as metal
After that, Te and Se are soda glass. soda
The glass is leached with boiling water to form the sodium selenite and
And sodium tellurite solution are neutralized with diluted sulfuric acid to obtain TeO Two
Is obtained.
【０００４】ＴｅＯ2 を水酸化ナトリウム溶液に溶解さ
せ、電解採取でカソードにＴｅを析出させ回収する。ま
た、特開昭６１−５３１０３号には、ＴｅＯ2 の水酸化
ナトリウム溶液に硫化ナトリウムを添加することで不純
物を沈澱除去した後、酸化剤を添加することでテルル酸
ナトリウムを沈澱分離し、次にそのテルル酸ナトリウム
を希塩酸に溶解させた後、亜硫酸ナトリウムや亜硫酸ガ
スなどの還元剤を添加して、Ｔｅを液から析出させる方
法が開示されている。[0004] TeO 2 is dissolved in a sodium hydroxide solution, and Te is deposited on the cathode by electrowinning to collect. JP-A-61-53103 discloses that sodium sulfide is added to a sodium hydroxide solution of TeO 2 to precipitate and remove impurities, and then an oxidizing agent is added to precipitate and separate sodium tellurate. Discloses a method of dissolving the sodium tellurate in dilute hydrochloric acid, and then adding a reducing agent such as sodium sulfite or sulfur dioxide to precipitate Te from the liquid.
【０００５】その他、Ｔｅを回収する方法としては、Ｔ
ｅＯ2 をほう砂で覆って、小麦粉または微粉炭と共に加
熱する直接還元法などが報告されている。上述の通り、
従来のＴｅの回収方法では、Ｃｕ2 Ｔｅに含まれる不純
物元素を除去しながら中間物としてＴｅＯ2 を生成さ
せ、次にＴｅＯ2 を電気化学的あるいは化学的に還元す
る手法が一般に用いられてきた。[0005] Other methods for recovering Te include T
A direct reduction method in which eO 2 is covered with borax and heated together with flour or pulverized coal has been reported. As mentioned above,
In the conventional method of recovering Te, a technique of generating TeO 2 as an intermediate while removing impurity elements contained in Cu 2 Te and then electrochemically or chemically reducing TeO 2 has been generally used. .
【０００６】一方で、ＴｅＯ2 を経由しない方法とし
て、Ｃｕ2 Ｔｅと硫黄（Ｓ）とを反応させて、Ｃｕ2 Ｓ
とＴｅにする方法が提案されているが、この方法は、Ｃ
ｕ2 Ｔｅに付着したビスマス（Ｂｉ）の一部がＴｅと結
合するため、不純物としてＢｉが混入しやすいという欠
点があった。On the other hand, as a method not passing through TeO 2 , Cu 2 Te is reacted with sulfur (S) to form Cu 2 S
And Te, a method has been proposed.
Since a part of bismuth (Bi) attached to u 2 Te is bonded to Te, there is a disadvantage that Bi is easily mixed as an impurity.
【０００７】[0007]
【発明が解決しようとする課題】Ｃｕ2 ＴｅからＴｅを
回収するときに、ＴｅＯ2 の生成を経由する従来のＴｅ
の回収方法では、工程数が多いだけでなく、湿式法を主
体とした処理であるため大量の廃水処理が必要であり、
ＴｅＯ2 を経由しないＴｅの回収方法では、Ｂｉを低減
するためにＴｅの精製処理工程が必要とされ、結果とし
てコストが高くなるという問題があった。When recovering Te from Cu 2 Te, conventional Te via the production of TeO 2 is used.
The recovery method requires not only a large number of steps but also a large amount of wastewater treatment because it is a treatment mainly based on the wet method.
In the method of recovering Te that does not pass through TeO 2 , there is a problem that a Te purification treatment step is required to reduce Bi, resulting in an increase in cost.
【０００８】本発明は、Ｔｅの回収における上記問題を
解決するものであって、Ｃｕ2 ＴｅからＴｅを回収する
ときに、中間物としてＴｅＯ2 の生成を経由せず、少な
い工程数でＢｉなどの不純物を含まない高純度Ｔｅを低
コストで回収する方法を提供することを目的とする。The present invention solves the above-mentioned problem in the recovery of Te. When recovering Te from Cu 2 Te, Bi or the like is produced in a small number of steps without passing through the production of TeO 2 as an intermediate. It is an object of the present invention to provide a method of recovering high-purity Te containing no impurities at low cost.
【０００９】[0009]
【課題を解決するための手段】本発明のＴｅの回収方法
は、Ｃｕの電解精錬で発生するＣｕ2 Ｔｅを重量比で
０．２６〜１．２０倍量のＳと共に一定時間加熱処理し
て得られた生成物から過剰のＳを蒸発分離し、次いでＳ
分離後の生成物を減圧下で２００〜１０００℃に加熱す
ることによってＴｅとＣｕＳを得るＴｅの回収方法にお
いて、Ｃｕ2 Ｔｅを予め塩酸で洗浄処理することにより
上記課題を解決している。According to the method of recovering Te of the present invention, Cu 2 Te generated by electrolytic refining of Cu is subjected to heat treatment for a certain period of time together with 0.26 to 1.20 times the amount of S in weight ratio. The excess S is evaporated off from the product obtained,
In a method of recovering Te in which Te and CuS are obtained by heating the separated product to 200 to 1000 ° C. under reduced pressure, the above-mentioned problem is solved by previously washing Cu 2 Te with hydrochloric acid.
【００１０】本発明のＴｅの回収方法では、ＴｅＯ2 と
Ｓを反応させるのに先立って、原料であるＣｕ2 Ｔｅを
塩酸で洗浄処理することで原料中のＢｉが除去されるの
で、ＴｅへのＢｉの混入が阻止される。Ｃｕの電解精錬
で発生するＣｕ2 Ｔｅは、粒子の中心部のＣｕ濃度が高
いため実際にはＣｕ2+x Ｔｅで示される組成と考えられ
るが、一般的にはＣｕ2 Ｔｅと記述されるので、本明細
書中でもＣｕ2 Ｔｅとしている。In the method of recovering Te of the present invention, Bi in the raw material is removed by washing the raw material Cu 2 Te with hydrochloric acid prior to reacting TeO 2 with S, so that Bi in the raw material is removed. Bi is prevented from being mixed. Cu 2 Te generated by electrolytic refining of Cu is considered to be actually a composition represented by Cu 2 + x Te due to a high concentration of Cu in the center of the particle, but is generally described as Cu 2 Te. Therefore, it is referred to as Cu 2 Te in this specification.
【００１１】Ｃｕ2 Ｔｅは、溶融状態のＳと接触させる
と下記の（１）式に従って容易にＣｕＳを形成し、Ｔｅ
は金属Ｔｅとして遊離してくる。ＳとＴｅは化合物を形
成するという報告もあるが定かではない。また、ＣｕＳ
は高温でＳの一部が解離し、Ｃｕ9 Ｓ5 、Ｃｕ8 Ｓ5 、
Ｃｕ7 Ｓ4 、Ｃｕ39Ｓ28、Ｃｕ9 Ｓ8 、Ｃｕ1.96Ｓなど
を形成するが、本文中ではすべてを総称してＣｕＳとす
る。When Cu 2 Te is brought into contact with S in a molten state, CuS easily forms CuS according to the following equation (1).
Is released as metal Te. There are reports that S and Te form compounds, but it is not clear. Also, CuS
At high temperature, a part of S is dissociated, Cu 9 S 5 , Cu 8 S 5 ,
Cu 7 S 4 , Cu 39 S 28 , Cu 9 S 8 , Cu 1.96 S, etc. are formed, but all are collectively referred to as CuS in the text.
【００１２】 Ｃｕ2 Ｔｅ＋２Ｓ→２ＣｕＳ＋Ｔｅ・・・・（１） Ｃｕ2 Ｔｅは、Ｃｕの電解製錬で陽極泥の脱銅処理の際
に副産物として発生するが、このＣｕ2 Ｔｅには陽極泥
に含有されていたＢｉがＣｕＳＯ4 と共に大量に付着し
ている。（１）式の反応においては、ＢｉがＣｕＳとＴ
ｅの両方に分配されるため、Ｃｕ2 Ｔｅの段階でＢｉ除
去処理を行わないとＴｅにＢｉが入り、Ｔｅの純度低下
を引き起こす。ＢｉはＣｕ2 ＴｅにＢｉ2 Ｏ3 もしくは
Ｂｉ2 （ＳＯ4 ）3 の形態で付着していると予想され
る。[0012] Cu 2 Te + 2S → 2CuS + Te ···· (1) Cu 2 Te is generated as a by-product during the copper removal treatment of the anode mud electrolytic smelting Cu, the anode mud into the Cu 2 Te The contained Bi is attached in large quantities together with CuSO 4 . In the reaction of the formula (1), Bi is CuS and T
Therefore, if Bi is not removed at the stage of Cu 2 Te, Bi enters Te and causes a decrease in Te purity. Bi is expected to be attached to Cu 2 Te in the form of Bi 2 O 3 or Bi 2 (SO 4 ) 3 .
【００１３】Ｂｉを除去するためにＣｕ2 ＴｅはＨＣｌ
で洗浄し、その後純水で過剰のＨＣｌを洗い流した後、
Ｓとの反応工程に移る。洗浄にＨＣｌを用いるのは、洗
浄用の酸としてＨＣｌがＢｉ2 Ｏ3 もしくはＢｉ2 （Ｓ
Ｏ4 ）3 に対して最も高い溶解度を示すからである。Ｈ
2 ＳＯ4 は溶解度が小さく、仮にＨ2 ＳＯ4 の濃度を高
濃度にしてもＴｅの溶解損失が増加し、非効率的であ
る。ＨＮＯ3 はＣｕ2 Ｔｅを酸化させてしまうためＴｅ
がＴｅＯ2となり、Ｂｉ2 Ｏ3 もしくはＢｉ2 （Ｓ
Ｏ4 ）3 の除去も十分行われない。その他、王水等も洗
浄用の酸として考えられるが、ＨＮＯ3 の場合と同様に
ＴｅＯ2が生成し適切でない。In order to remove Bi, Cu 2 Te is replaced with HCl.
After washing with excess water with pure water,
Move on to the reaction step with S. HCl is used for cleaning because HCl is used as a cleaning acid when Bi 2 O 3 or Bi 2 (S
This is because it shows the highest solubility for O 4 ) 3 . H
2 SO 4 has a low solubility, and even if the concentration of H 2 SO 4 is increased, the dissolution loss of Te increases, which is inefficient. HNO 3 oxidizes Cu 2 Te, so Te
Becomes TeO 2 , and Bi 2 O 3 or Bi 2 (S
O 4 ) 3 is not sufficiently removed. In addition, aqua regia and the like are also considered as cleaning acids, but TeO 2 is generated as in the case of HNO 3 and is not suitable.
【００１４】洗浄処理には、濃度が０．５〜３ｍｏｌ／
ＬのＨＣｌを使用することが好ましい。ＨＣｌ濃度が
０．５ｍｏｌ／Ｌより低い場合、Ｂｉ2 Ｏ3 もしくはＢ
ｉ2 （ＳＯ4 ）3 の溶解度が小さく殆ど除去できない。
３ｍｏｌ／Ｌより濃度が高い場合、Ｔｅの溶出損出が増
加するばかりでなく、Ｂｉ洗浄後に行う過剰ＨＣｌの水
洗に手間が掛かり、その結果廃水量が増えるため処理費
用が嵩むことになる。In the cleaning treatment, the concentration is 0.5 to 3 mol /
It is preferred to use L HCl. When the HCl concentration is lower than 0.5 mol / L, Bi 2 O 3 or B
The solubility of i 2 (SO 4 ) 3 is so small that it can hardly be removed.
When the concentration is higher than 3 mol / L, not only does the elution loss of Te increase, but also it takes time and effort to wash the excess HCl after the Bi washing, and as a result, the amount of wastewater increases, thereby increasing the processing cost.
【００１５】Ｃｕ2 Ｔｅは少なからず表面が酸化されて
おり、Ｓと反応させるときにＳＯ2の発生を伴うことが
あるので、Ｃｕ2 ＴｅとＳを反応させる前に水素還元あ
るいは炭素還元を行っておくと良い。還元処理を行った
Ｃｕ2 Ｔｅに重量比で０．２６〜１．２０倍のＳを添加
した後、一定時間加熱処理する。Ｃｕ2 Ｔｅに対するＳ
の重量比が０．２６より小さい場合には、Ｔｅの生成に
よってＣｕ2 ＴｅとＳの混合物に流動性が失われるのみ
ならず、反応に関与するＳが不足し反応速度を著しく低
下させる。逆に、Ｃｕ2 Ｔｅに対するＳの重量比が１．
２０より大きい場合は、過剰に仕込んだＳの分離、回収
に長時間を要し生産性が低下する。Ｃｕ2 ＴｅとＳの反
応速度を早くするために、撹拌混合を行うことが効果的
である。Since the surface of Cu 2 Te is not less than oxidized and SO 2 may be generated when reacting with S, hydrogen reduction or carbon reduction is performed before reacting Cu 2 Te with S. Good to keep. After adding 0.26 to 1.20 times by weight of S to the reduced Cu 2 Te, heat treatment is performed for a certain period of time. S for Cu 2 Te
If the weight ratio is less than 0.26, not only does the mixture of Cu 2 Te and S lose the fluidity due to the formation of Te, but also the S involved in the reaction becomes insufficient and the reaction rate is remarkably reduced. Conversely, the weight ratio of S to Cu 2 Te is 1.
If it is larger than 20, it takes a long time to separate and recover excessively charged S, and the productivity is reduced. It is effective to perform stirring and mixing in order to increase the reaction rate of Cu 2 Te and S.
【００１６】加熱温度は、Ｓの蒸気圧および酸化を考慮
して１１２〜４４５℃が最も適している。加熱処理を行
う雰囲気は、アルゴンまたは窒素気流中もしくは減圧下
で行うことでＳの空気酸化で起こるＳＯ2 の発生が抑制
できるが、２５０℃以下の場合は大気中でもＳＯ2 の発
生量は少なく、大きな支障なく加熱処理を行うことが可
能である。また、オートクレーブ等の密閉容器を使用
し、高いＳ蒸気圧下で反応を進める手法もあるが、４４
５℃より高温の場合はオートクレーブ等の容器材質の耐
圧強度、耐硫化性および耐テルル化性を維持しながら反
応を進めるのは難しい。The heating temperature is most preferably 112 to 445 ° C. in consideration of the vapor pressure and oxidation of S. Atmosphere in which the heat treatment can suppress the generation of SO 2 that by performing at or under reduced pressure in an argon or nitrogen stream occurs in the air oxidation of S is, the amount of SO 2 in the atmosphere in the case of 250 ° C. or less is small, The heat treatment can be performed without any great trouble. There is also a method in which the reaction is carried out under a high S vapor pressure using a closed vessel such as an autoclave.
When the temperature is higher than 5 ° C., it is difficult to proceed with the reaction while maintaining the pressure resistance, the sulfidation resistance and the tellurium resistance of the container material such as an autoclave.
【００１７】ＣｕＳとＴｅを生成させた後、過剰に仕込
んだＳを蒸発分離する。過剰のＳを分離するために生成
物を加熱し、Ｓのみを蒸発させる。このときの加熱温度
は３００〜４４５℃が適温である。Ｓを蒸発分離するに
は、減圧下で加熱する方法もあるが、Ｓの沸点が４４５
℃と低いためアルゴン気流中もしくは窒素気流中で行う
のが好ましい。After producing CuS and Te, the excessively charged S is separated by evaporation. The product is heated to separate excess S and only S is evaporated. The appropriate heating temperature at this time is 300 to 445 ° C. In order to evaporate and separate S, there is a method of heating under reduced pressure, but the boiling point of S is 445.
Since the temperature is as low as ° C., it is preferable to carry out the reaction in an argon stream or a nitrogen stream.
【００１８】次にＣｕＳとＴｅの混合物からＴｅを分離
するため、減圧下で２００〜１０００℃に加熱する。Ｔ
ｅの沸点は９８９．８℃であるので、減圧下で２００〜
１０００℃に加熱するとＴｅは速やかに蒸発し、反応容
器に接続したコンデンサーに凝集、固化するので、加熱
終了後コンデンサーから剥離、回収する。一方反応容器
内にはＣｕＳが残留する。真空度は、加熱温度によって
変える必要があるが、通常はコンデンサーを必要以上に
大きくしないために１５０Ｐａ以下が好ましい。Next, in order to separate Te from the mixture of CuS and Te, the mixture is heated to 200 to 1000 ° C. under reduced pressure. T
e has a boiling point of 989.8 ° C.
When heated to 1000 ° C., Te evaporates quickly and aggregates and solidifies in the condenser connected to the reaction vessel. On the other hand, CuS remains in the reaction vessel. The degree of vacuum needs to be changed depending on the heating temperature, but is usually preferably 150 Pa or less so as not to make the condenser larger than necessary.
【００１９】加熱温度が２００℃未満では、Ｔｅの蒸発
速度が非常に遅く回収効率が低い。一方１０００℃より
高温では、Ｔｅの蒸発速度が速すぎるため蒸発損失が大
きくなるだけでなく、沸点の比較的低い不純物の混入が
懸念される。ＣｕＳ中には不純物としてＭｎ（沸点２１
５０℃）、Ｐｂ（沸点１７４０℃）、Ｓｉ（沸点２３３
５℃）、Ｆｅ（沸点３０００℃）、Ｍｇ（沸点１１０７
℃）もしくはこれらの硫化物が残留すると予想される
が、１０００℃より高温で加熱した場合には特にＢｉお
よびＭｇがＴｅに混入する可能性が高くなる。If the heating temperature is lower than 200 ° C., the evaporation rate of Te is very slow, and the recovery efficiency is low. On the other hand, if the temperature is higher than 1000 ° C., the evaporation rate of Te is too high, so that not only the evaporation loss is increased, but also impurities having a relatively low boiling point may be mixed. Mn (boiling point 21
50 ° C), Pb (boiling point 1740 ° C), Si (boiling point 233)
5 ° C), Fe (boiling point 3000 ° C), Mg (boiling point 1107)
° C) or these sulfides are expected to remain, but when heated at a temperature higher than 1000 ° C, Bi and Mg are particularly likely to be mixed into Te.
【００２０】加熱条件によっては、ＴｅにＳが混入する
が、再度減圧下２５０〜４００℃で加熱することでＳの
分離ができ、高純度のＴｅの回収が可能である。以上の
工程によって、Ｃｕ2 Ｔｅから９４％以上の収率でＴｅ
の回収を行うことができる。また、副生成物のＣｕＳは
乾式銅製錬用の原料とし、回収されたＳは循環使用す
る。Depending on the heating conditions, S is mixed into Te, but by heating again at 250 to 400 ° C. under reduced pressure, S can be separated, and high-purity Te can be recovered. By the above steps, Te is obtained from Cu 2 Te with a yield of 94% or more.
Can be collected. The by-product CuS is used as a raw material for dry copper smelting, and the recovered S is recycled.
【００２１】[0021]
【発明の実施の形態】Ｃｕの電解精錬の際に発生する陽
極泥を硫酸で浸出した液にＣｕ粉を投入しセメンテーシ
ョンによって生成したＣｕ2 Ｔｅをポリプロピレン製の
容器に入れ、０．５〜３ｍｏｌ／Ｌ−ＨＣｌを添加し、
攪拌機にてスラリー化する。洗浄に使うＨＣｌの液量
は、Ｃｕ2 Ｔｅに付着するＢｉ等の不純物量によって変
化させなければならないが、通常Ｃｕ2 Ｔｅ1kg 当り１
０〜３０Ｌが適当である。BEST MODE FOR CARRYING OUT THE INVENTION Cu powder is introduced into a liquid obtained by leaching an anode mud generated during electrolytic refining of Cu with sulfuric acid, and Cu 2 Te produced by cementation is placed in a polypropylene container. 3 mol / L-HCl was added,
Slurry with a stirrer. Liquid volume of HCl used for washing, but must be changed by the amount of impurities Bi, etc. adhering to the Cu 2 Te, usually Cu 2 Te1kg per
0 to 30 L is appropriate.
【００２２】このスラリーをフィルタープレスなどで固
液分離した後、Ｃｕ2 Ｔｅに付着しているＨＣｌを純水
で洗浄し、温風循環乾燥機を用い７０℃で６ｈ乾燥す
る。ＨＣｌ洗浄と純水洗浄は、２〜３回繰り返し行うの
が効果的である。乾燥が終わったＣｕ2 Ｔｅ２００〜１
０００ｇを石英製の流動層に入れ、水素１〜１０Ｌ／ｍ
ｉｎの気流中で２００〜１０００℃で加熱してＣｕ2 Ｔ
ｅ表面に形成された酸化物を還元除去し、Ｃｕ2 Ｔｅと
Ｓの反応時のＳＯ2 発生が原因で起こる原料の容器外へ
の溢出を回避する。加熱時間は、還元の進行状態を測定
し決定すればよいが、一般に１〜３ｈが適当であり、Ｈ
2 は脱水しながら循環使用することで利用率を上げるこ
とができる。After the slurry is separated into solid and liquid by a filter press or the like, HCl adhering to Cu 2 Te is washed with pure water, and dried at 70 ° C. for 6 hours using a hot air circulating drier. It is effective to repeat the HCl washing and the pure water washing two to three times. The dried Cu 2 Te 200-1
000 g in a fluidized bed made of quartz, and 1 to 10 L / m of hydrogen
in a gas stream of 200 to 1000 ° C. to produce Cu 2 T
The oxide formed on the e-surface is reduced and removed to prevent the raw material from overflowing out of the container due to the generation of SO 2 during the reaction between Cu 2 Te and S. The heating time may be determined by measuring the progress of the reduction, but generally 1 to 3 h is appropriate.
2 can increase the utilization rate by circulating it while dewatering.
【００２３】また、炭素粉末で還元する場合には、内容
積２Ｌのアルミナ製ポットにＣｕ2Ｔｅ２００ｇ、カー
ボンブラック１０ｇ、φ１０の部分安定化ジルコニアボ
ール１．５ｋｇ、および水２００ｍＬの割合で入れ、１
２５ｒｐｍで１ｈ混合する。混合後内容物を取出し、ジ
ルコニアボールを取り除いた混合粉末スラリーをバット
に入れ、温風循環乾燥機で５０〜９０℃で１〜６ｈ乾燥
し、真空加熱炉で５００〜１０００℃、３ｈ加熱する。In the case of reduction with carbon powder, 200 g of Cu 2 Te, 10 g of carbon black, 1.5 kg of partially stabilized zirconia balls of φ10, and 200 mL of water are put into a 2 L alumina pot and put into a 2 L alumina pot.
Mix for 1 h at 25 rpm. After mixing, the contents are taken out, the mixed powder slurry from which the zirconia balls have been removed is put in a vat, dried at 50 to 90 ° C. for 1 to 6 hours by a hot air circulating drier, and heated at 500 to 1000 ° C. for 3 hours in a vacuum heating furnace.
【００２４】流動層または真空加熱炉から取出したＣｕ
2 Ｔｅは、水冷式の冷却トラップが取付けられた上蓋を
有し、雰囲気制御が可能な石英製容器に入れ、Ｃｕ2 Ｔ
ｅに対し重量比で０．２６〜１．２０倍のＳを添加後、
窒素１００〜１０００ｍＬ／ｍｉｎを容器内に流しなが
ら電気抵抗ヒーターで加熱を開始する。加熱温度は、硫
黄の蒸気圧が低く、反応温度が速い２００〜２５０℃が
最適である。加熱時間は１〜１０ｈの範囲で行うのがよ
いが、仕込み量、加熱温度およびＣｕ2 ＴｅとＳの混合
状態によって任意に変化させなければならない。冷却ト
ラップには、内側トラップの表面の温度が５０℃以下に
なるように冷却水を十分に流す必要がある。Cu removed from a fluidized bed or vacuum heating furnace
2 Te has a lid which water-cooled cold trap is attached, placed in a quartz container capable atmosphere control, Cu 2 T
After adding 0.26 to 1.20 times by weight of S to e,
Heating is started with an electric resistance heater while flowing 100 to 1000 mL / min of nitrogen into the container. The heating temperature is optimally 200 to 250 ° C. where the sulfur vapor pressure is low and the reaction temperature is fast. The heating time is preferably in the range of 1 to 10 h, but it must be arbitrarily changed depending on the charged amount, the heating temperature, and the mixed state of Cu 2 Te and S. In the cooling trap, it is necessary to sufficiently supply cooling water so that the temperature of the surface of the inner trap becomes 50 ° C. or less.
【００２５】次に、石英製容器を３００〜４４５℃に１
〜５ｈ保持する。過剰なＳは、冷却トラップに凝集し、
石英製容器内には、ＣｕＳとＴｅの混合物が残留する。
加熱温度および加熱時間は、Ｔｅの蒸発損失が防げる範
囲であれば任意に変更が可能である。石英製容器を室温
に冷却した後、冷却トラップが取付けられた上蓋を石英
製容器から取外し、同型の上蓋を新たに取付ける。Next, the quartz container is heated to 300 to 445 ° C. for 1 hour.
Hold for ~ 5h. Excess S aggregates in the cold trap,
A mixture of CuS and Te remains in the quartz container.
The heating temperature and the heating time can be arbitrarily changed as long as the evaporation loss of Te can be prevented. After cooling the quartz container to room temperature, the upper lid having the cooling trap attached thereto is removed from the quartz container, and a new upper lid of the same type is attached.
【００２６】冷却トラップに水を十分に流しながら、石
英製容器を油回転ポンプで１５０Ｐａ以下まで減圧した
後、石英製容器を電気抵抗ヒータで加熱し、２００〜１
０００℃、１〜５ｈ保持する。加熱温度は３００〜６０
０℃がより好ましい。ＣｕＳとＴｅの混合物からＴｅが
蒸発し、冷却トラップに凝集する。石英製容器を室温ま
で冷却後、冷却トラップに凝集したＴｅを剥離回収す
る。After sufficiently reducing the pressure of the quartz container to 150 Pa or less with an oil rotary pump while sufficiently flowing water through the cooling trap, the quartz container was heated by an electric resistance heater and then heated to 200 to 1 mm.
Hold at 000 ° C. for 1-5 h. Heating temperature is 300-60
0 ° C. is more preferred. Te evaporates from the mixture of CuS and Te and aggregates in the cooling trap. After cooling the quartz container to room temperature, the Te aggregated in the cooling trap is peeled and collected.
【００２７】ただし、ＴｅにＳが混入していた場合に
は、回収したＴｅを再度１５０Ｐａ以下、２５０〜４０
０℃で加熱し、Ｓのみを蒸発分離することで高純度Ｔｅ
回収する。However, when S is mixed in Te, the recovered Te is again reduced to 150 Pa or less, 250 to 40 Pa.
By heating at 0 ° C. and evaporating and separating only S, high purity Te is obtained.
to recover.
【００２８】[0028]
【実施例】〔実施例１〕Ｃｕ2 Ｔｅを３００ｇをポリプ
ロピレン製容器に入れ、そこに１ｍｏｌ／Ｌ−ＨＣｌ３
Ｌを添加し、撹拌でスラリー化した後、３ｈ撹拌を継続
し、Ｎｏ．５Ｂの濾紙で濾過することでスラリーからＣ
ｕ2 Ｔｅを分離、回収した。次にＣｕ2Ｔｅをポリプロ
ピレン製容器に入れ、そこに純水３Ｌを入れて撹拌する
ことで再度スラリー化させてから３ｈ撹拌を継続し、再
び濾過で固液分離を行なった。以上の操作を３回繰り返
した。[Example 1] 300 g of Cu 2 Te was placed in a polypropylene container, and 1 mol / L-HCl 3 was added thereto.
L was added, and the mixture was slurried with stirring. The slurry is filtered through 5B filter paper to remove C from the slurry.
u 2 Te was separated and recovered. Next, Cu 2 Te was placed in a polypropylene container, 3 L of pure water was added thereto, and the mixture was stirred to form a slurry again. Then, stirring was continued for 3 hours, and solid-liquid separation was performed again by filtration. The above operation was repeated three times.
【００２９】洗浄後のＣｕ2 Ｔｅを温風循環乾燥機を用
い７０℃で６ｈ乾燥した。乾燥が終了したＣｕ2 Ｔｅ２
００ｇを石英製の流動層に入れ、３Ｌ／ｍｉｎの水素気
流中において３００℃で３ｈ加熱した。流動層から取出
したＣｕ2 Ｔｅは、水冷式の冷却トラップが取付けられ
た上蓋を有し、雰囲気制御が可能な内容積２Ｌの石英製
容器に入れ、Ｃｕ2 Ｔｅに対し重量比で０．５倍のＳを
添加後、窒素１００ｍＬ／ｍｉｎを容器内に流しながら
電気抵抗加熱ヒーターで加熱した。加熱は２５０℃で３
ｈ行い、冷却トラップには、水を１００ｍＬ／ｍｉｎで
給水した。The washed Cu 2 Te was dried at 70 ° C. for 6 hours using a circulating hot air drier. Cu 2 Te2 after drying
00 g was put in a fluidized bed made of quartz and heated at 300 ° C. for 3 h in a hydrogen stream at 3 L / min. Cu 2 Te removed from the fluidized bed was placed in a quartz container having an inner volume of 2 L capable of controlling the atmosphere, having an upper lid equipped with a water-cooled cooling trap, and having a weight ratio of 0.5 to Cu 2 Te. After adding twice the amount of S, the mixture was heated with an electric resistance heater while flowing 100 mL / min of nitrogen into the vessel. Heating at 250 ° C 3
The cooling trap was supplied with water at a rate of 100 mL / min.
【００３０】次に、石英製容器を４４５℃で２ｈ保持し
た。過剰なＳは、冷却トラップに凝集し、石英製容器内
には、ＣｕＳとＴｅの混合物が残留した。石英製容器を
室温まで冷却した後、冷却トラップを取付けた上蓋を石
英製容器から取外し、同型の上蓋を新たに取付けた。冷
却トラップに水を１００ｍＬ／ｍｉｎ流しながら、石英
製容器を油回転ポンプで１５０Ｐａ以下まで減圧した
後、石英製容器を電気抵抗ヒータで加熱し、４００℃、
３ｈ保持した。ＣｕＳとＴｅの混合物からＴｅが蒸発
し、冷却トラップに凝集するので、室温まで冷却後、冷
却トラップに凝集したＴｅを剥離回収した。次に、回収
したＴｅを再度１５０Ｐａで２００℃、１ｈ加熱し、Ｃ
ｕＳの解離によって混入したＳを蒸発分離し高純度Ｔｅ
を得た。Next, the quartz container was kept at 445 ° C. for 2 hours. Excess S aggregated in the cooling trap, and a mixture of CuS and Te remained in the quartz container. After cooling the quartz container to room temperature, the upper lid equipped with the cooling trap was removed from the quartz container, and an upper lid of the same type was newly attached. While flowing water at a rate of 100 mL / min through the cooling trap, the quartz container was depressurized to 150 Pa or less with an oil rotary pump, and then the quartz container was heated with an electric resistance heater at 400 ° C.
Held for 3 h. Te evaporates from the mixture of CuS and Te and aggregates in the cooling trap. After cooling to room temperature, Te aggregated in the cooling trap was separated and collected. Next, the recovered Te was heated again at 150 ° C. and 200 ° C. for 1 hour,
S mixed by the dissociation of uS is separated by evaporation to obtain high purity Te.
I got
【００３１】この条件で回収したＴｅは、回収率が９８
％であり、純度は９９．９９％であった。 〔実施例２〕Ｃｕ2 Ｔｅに対し重量比で１．２倍のＳを
添加した以外は実施例１と同様に操作した。The Te recovered under these conditions has a recovery rate of 98.
% And the purity was 99.99%. Example 2 The same operation as in Example 1 was carried out except that S was added in a weight ratio of 1.2 times that of Cu 2 Te.
【００３２】この条件で回収したＴｅは、回収率が９９
％であり、純度は９９．９９％であった。 〔実施例３〕Ｃｕ2 ＴｅとＳを加熱処理し、Ｓ分離後、
ＣｕＳとＴｅが残留した石英製容器を電気抵抗加熱ヒー
タで加熱し、１０００℃、２ｈ保持する以外は実施例１
と同様に操作した。Te recovered under these conditions has a recovery rate of 99%.
% And the purity was 99.99%. [Example 3] Cu 2 Te and S were heat-treated, and after S separation,
Example 1 except that a quartz container in which CuS and Te remained was heated by an electric resistance heater and kept at 1000 ° C. for 2 hours.
The same operation was performed.
【００３３】この条件で回収したＴｅは、回収率が９４
％であり、純度は９９．９９％であった。 〔実施例４〕Ｃｕ2 Ｔｅ３００ｇをポリプロピレン製容
器に入れ、そこに２．５ｍｏｌ／Ｌ−ＨＣｌ３Ｌを添加
し、洗浄操作を行った以外は実施例１と同様に操作し
た。The Te recovered under these conditions has a recovery rate of 94
% And the purity was 99.99%. Example 4 The same operation as in Example 1 was performed except that 300 g of Cu 2 Te was placed in a polypropylene container, 3 L of 2.5 mol / L-HCl was added thereto, and a washing operation was performed.
【００３４】この条件で回収したＴｅは、回収率が９４
％であり、純度は９９．９９％であった。The Te recovered under these conditions has a recovery rate of 94
% And the purity was 99.99%.
【００３５】[0035]
【発明の効果】本発明のテルルの回収方法によれば、テ
ルル化銅からテルルを回収するときに、中間物として二
酸化テルルを経由せず、少ない工程数でビスマスなどの
不純物を含まない高純度テルルを回収することができ、
コスト低減が可能となる。また、副生成物である硫化銅
と硫黄は、銅の製錬原料としてあるいは反応原料として
再利用可能であり、資源の有効利用に貢献できる。According to the method for recovering tellurium of the present invention, when recovering tellurium from copper telluride, high purity which does not pass through tellurium dioxide as an intermediate and contains no impurities such as bismuth in a small number of steps. Tellurium can be recovered,
The cost can be reduced. Further, copper sulfide and sulfur, which are by-products, can be reused as a raw material for smelting copper or as a raw material for reaction, and can contribute to effective utilization of resources.
【００３６】テルル化銅を洗浄処理する塩酸として、
０．５〜３ｍｏｌ／Ｌの塩酸を使用すると、Ｂｉ2 Ｏ3
もしくはＢｉ2 （ＳＯ4 ）3 の溶解度が大きく、より効
果的な洗浄が可能となる。As hydrochloric acid for washing copper telluride,
When 0.5 to 3 mol / L hydrochloric acid is used, Bi 2 O 3
Alternatively, the solubility of Bi 2 (SO 4 ) 3 is large, and more effective cleaning can be performed.
Claims (2)
量比で０．２６〜１．２０倍量の硫黄と共に一定時間加
熱処理して得られた生成物から過剰の硫黄を蒸発分離
し、次いで硫黄分離後の生成物を減圧下で２００〜１０
００℃に加熱することによってテルルと硫化銅を得るテ
ルルの回収方法であって、テルル化銅を予め塩酸で洗浄
処理することを特徴とするテルルの回収方法。An excess sulfur is removed from a product obtained by heat-treating copper telluride generated by electrolytic refining of copper together with sulfur in a weight ratio of 0.26 to 1.20 times for a certain period of time. The product after sulfur separation is then reduced under reduced pressure to 200-10
A method for recovering tellurium, which obtains tellurium and copper sulfide by heating to 00 ° C., wherein copper telluride is washed with hydrochloric acid in advance.
０．５〜３ｍｏｌ／Ｌの塩酸を使用することを特徴とす
る請求項１記載のテルルの回収方法。2. Hydrochloric acid for washing copper telluride,
The method for recovering tellurium according to claim 1, wherein 0.5 to 3 mol / L hydrochloric acid is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001034228A JP2002241866A (en) | 2001-02-09 | 2001-02-09 | Method for recovering tellurium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001034228A JP2002241866A (en) | 2001-02-09 | 2001-02-09 | Method for recovering tellurium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002241866A true JP2002241866A (en) | 2002-08-28 |
Family
ID=18897874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001034228A Withdrawn JP2002241866A (en) | 2001-02-09 | 2001-02-09 | Method for recovering tellurium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002241866A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550611A (en) * | 2019-10-18 | 2019-12-10 | 江西理工大学 | Method for efficiently leaching tellurium from copper separating slag of copper anode slime enhanced by external field effect |
| CN112375917A (en) * | 2020-11-11 | 2021-02-19 | 昆明理工大学 | Method for recovering tellurium copper from copper telluride slag |
| CN114920208A (en) * | 2022-04-24 | 2022-08-19 | 中南大学 | Method for efficiently separating tellurium or tellurium and selenium from tellurium-containing material |
-
2001
- 2001-02-09 JP JP2001034228A patent/JP2002241866A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550611A (en) * | 2019-10-18 | 2019-12-10 | 江西理工大学 | Method for efficiently leaching tellurium from copper separating slag of copper anode slime enhanced by external field effect |
| CN112375917A (en) * | 2020-11-11 | 2021-02-19 | 昆明理工大学 | Method for recovering tellurium copper from copper telluride slag |
| CN114920208A (en) * | 2022-04-24 | 2022-08-19 | 中南大学 | Method for efficiently separating tellurium or tellurium and selenium from tellurium-containing material |
| CN114920208B (en) * | 2022-04-24 | 2023-08-15 | 中南大学 | Method for efficiently separating tellurium or separating tellurium and selenium from tellurium-containing material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5932086A (en) | Process for making manganese | |
| US20080124269A1 (en) | Purified molybdenum technical oxide from molybdenite | |
| JP2001316735A (en) | Method for treating anode slime | |
| CA1059771A (en) | Hydrometallurgical process for the recovery of valuable components from the anode slime produced in the electrolytical refining of copper | |
| CN112063854B (en) | Method for comprehensively recovering bismuth, silver and copper metals by taking precious lead as raw material | |
| CN105129839A (en) | Method for producing micron-grade zinc oxide with high fluorine and chlorine crude zinc oxide as raw material | |
| CN111575483A (en) | Method for separating selenium, tellurium, arsenic, copper, lead and silver and enriching gold from copper anode slime | |
| JP5146017B2 (en) | Chlorine leaching method for lead anode slime | |
| CN111621646A (en) | Zinc dross recycling method | |
| JPH10509212A (en) | Recovery of metal and chemical value | |
| JP6656709B2 (en) | Manufacturing method of zinc ingot | |
| CN106884093A (en) | A kind of thick aurin smelting method | |
| US4666514A (en) | Hydrometallurgical process for recovering silver from copper-electrolysis anode sludge | |
| JP4016680B2 (en) | Method for dissolving selenium platinum group element-containing material | |
| JPS6139383B2 (en) | ||
| JP4715598B2 (en) | Chloride leaching method of lead electrolysis slime | |
| JP2017178749A (en) | Method for producing manganese sulfate aqueous solution and method for producing manganese oxide | |
| JP4574826B2 (en) | How to recover tellurium | |
| JP2002241866A (en) | Method for recovering tellurium | |
| JP2000169116A (en) | Selectively leaching recovery process of selenium | |
| CA2278834A1 (en) | Improved tellurium extraction from copper electrorefining slimes | |
| JP4358594B2 (en) | Collection method of valuable materials | |
| AU2013220926B2 (en) | Process for zinc oxide production from ore | |
| CN111268655A (en) | Method for producing tellurium dioxide by self-purification of coarse tellurium powder | |
| JP4155177B2 (en) | Method for recovering silver from silver-lead-containing materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20080513 |