WO1989012700A1 - Recuperation de selenium de grande purete a partir de minerais, de boues de lavage, de depots de boues anodiques et de debris metalliques - Google Patents

Recuperation de selenium de grande purete a partir de minerais, de boues de lavage, de depots de boues anodiques et de debris metalliques Download PDF

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Publication number
WO1989012700A1
WO1989012700A1 PCT/AU1989/000264 AU8900264W WO8912700A1 WO 1989012700 A1 WO1989012700 A1 WO 1989012700A1 AU 8900264 W AU8900264 W AU 8900264W WO 8912700 A1 WO8912700 A1 WO 8912700A1
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WO
WIPO (PCT)
Prior art keywords
selenium
process according
solution
sulphide
reaction
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Application number
PCT/AU1989/000264
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English (en)
Inventor
Edward Davis
Lakshman Jayaweera
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Fmc Technologies Limited
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Publication date
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Publication of WO1989012700A1 publication Critical patent/WO1989012700A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals

Definitions

  • This invention relates to an improved process for extraction of high purity selenium from various smelter sludges and selenium ore using a hydrometallurgical process.
  • the main raw materials for selenium recovery are the anode slimes of electrolytic copper and nickel refineries and sludges collected from the dust generating from the lead zinc smelters.
  • the feed is roasted and the selenium is volatalized and scrubbed into either water or solutions of sodium hydroxide or soda ash. Once the selenium is dissolved in the water it is reduced to selenium by passing sulpher dioxide.
  • Roasting of the sludge is carried out under various conditions and it would vary according to the nature of the feed including the impurities. Roasting is carried out either under neutral, acidic or alkaline conditions.
  • the major disadvantages of such a prometallurgical process are the control of pollution, longer residence time and contamination of the waste gases with other impurities such as mercury, arsenic, antimony and lead.
  • the present invention seeks to ameliorate these disadvantages by providing a process of treating selenium bearing materials containing mercury, lead, antimony, and copper, to recover the selenium comprising the steps of: reacting the selenium bearing materials with a solution of alkaline metals/ammonium sulphide or sulphite or combination thereof with a catalyst above atmospheric pressure and at a temperature at or above 100°c; continuing the reaction at a controlled pH to reduce dissolution of other impurities to a minimum; seperating the undissolved residuals from the lead solution; and recovering the selenium from the leach solution by reducing the temperature to ambient temperature.
  • the catalyst is thiourea, and the reaction temperature is 100-150oC, with the reaction pressure between 1 atmos to 10 atmos.
  • FIG. 1 A flow diagram of one embodiment of the present invention is shown in figure 1.
  • the metal is transferred from the solid phase to a liquid phase by a complex reaction with sodium sulphide or sulphite in the presence of a catalyst.
  • the typical complexing agent used in the process is sodium sulphide, ammonium sulphide or sodium sulphite, and the activator or the catalyst is usually Thiourea.
  • Other conditions which usually favour the leaching kinetics are elevated temperature, preferably over 100°c under pressure.
  • the process of this invention can be used to leach selenium from either metal sulphide containing selenide or selenium in elemental form present in anode slimes, smelter sludge or scrap.
  • the reaction will take place without oxidation, and sulphide or sulphite of sodium or ammonium salts complexes with selenium according to the following equation:
  • the recovery of selenium is carried out by decreasing the temperature aided with seeding. Previously prepared fine powder of selenium improves the kinetics of precipitation by reducing the induction period and also controls the desired particle size of the product. The selenium so produced is washed in hot water to achieve the purity over 99%. In order to achieve the purity of 99.9% the product is redissolved in the same leaching system and reprecipitated as selenium.
  • the steps of recovery of selenium as shown in figure 1 are as follows: 1. The process of crushing to a suitable size selenium bearing materials containing mercury, lead, antimony, arsenic and copper for the separate recovery of selenium
  • the process according to steps 10-12 allow the plant end solution to be recycled back to the leach tank after making up for some of the decomposed reagents, and after a purification stage.
  • the purification stage comprises of an adjustment of slightly acidic conditions close to 8 and then subjecting the solution to a solvent extration stage with diethyl 2 phosphoric acid (D2 EHPA) diluted to 5% in Kerosine.
  • D2 EHPA diethyl 2 phosphoric acid
  • impurities such as arsenic, antimony, mercury and lead is extracted into the organic phase leaving the selenium in the aqueous phase.
  • the process has been developed almost into a closed system of the reagent whereby practically almost all the reagent is recycled. Examples of tests carried out using the present invention are as follows.
  • EXAMPLE 1 This example illustrates the results obtained in leaching a selenium bearing residue under varying conditions of temperature, sulphide, sulphite and Thiourea concentrations.
  • Selenium bearing residue contained by weight approximately 50% selenium, 10% lead, 5%-arsenic, 3% mercury, 2% antimony, 20% moisture and 2% sulphuric acid.
  • EXAMPLE 2 The example illustrates the operation of the precipitation step.
  • the leach solution contained 30g/l of selenium and 120g/l of sodium sulphite solution.
  • the precipitation was carried out by lowering the temperature of the solution from 100°C TO 30°C BY COOLING.
  • previously prepared fine selenium powder less than 20m particle size was added to the leach at a rate of 5g/l.
  • This example illustrates that the lowering of the temperature reduced the solubility of selenium in the sodium sulphite solution and furthermore, the addition of previously prepared fine powder of selenium has reduced the induction period of precipitation.
  • the following example illustrates the results of the purification step developed for the plant end liquor enabling it to be recycled back to the leaching system.
  • the plant end liquor was mixed with a solution of Diethyl 2 phosphoric acid (D2EHPA) diluted to 5% shellsol.
  • Aqueous and organic ratio was 1:1 allowing a mixing time and the phase settlement time of 3 and 10 minutes respectively.
  • Table 3 shows the selective separation of most of the impurities while selenium being un extracted.
  • the present invention provides an efficient process for the recovery of selenium with a large reduction in pollution and a large recycling of reactants. It should be obvious to people skilled in the art that variations and modifications can be made to the above description without departing from the scope or spirit of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Le sélénium est obtenu naturellement à partir de divers pyrites avec son analogue sulfuré. Le sélénium est en outre présent en grandes concentrations dans des boues extraites de laveurs dans des rampants, dans des dépôts de boues anodiques et dans des débris métalliques. Le matériau portant le sélénium est concassé jusqu'à présenter une granulométrie appropriée et est ensuite lessivé (20) dans une solution de métal alcalin (par exemple du Na), de sulfure ou du sulphite d'ammonium ou de combinaisons de ces composés sur le base de 2 à 6 moles de sulfure/sulphite par mole de Se, à des températures élevées supérieures au égales à 100°C et à des pressions élevées dans un autoclave, de préférence en présence d'un activateur/catalyseur, constitué par exemple par de la thio-urée. La température préférée est comprise entre 100 et 150°C et la pression entre 1 et 10 atmosphères. Le lessivage se poursuit à un pH régulé (de 9 à 10), de façon à maintenir la dissolution des impuretés à un niveau minimum. Les résidus non dissous sont ensuite séparés (4) et la solution est refroidie à une température ambiante pour permettre sa germination avec le Se, preparée au prélable (5, 6). La poudre de Se récupérée à ce stade est séparée de la solution de lessivage (7) et est ensuite soumise à un lavage dans de l'eau bouillante (8) et à un séchage (9), donnant ainsi un produit fini pur à 99,5 %. La solution de lessivage en (7) contient toujours un peu de Se, elle est ajustée à un pH de 8 (10) et elle est soumise à une extraction liquide-liquide, au moyen par exemple de 5 % d'acide diéthyl-2-phosphorique dissous dans de la kérosine comme phase organique. Les composés d'As, de Sb, d'Hg et d'Bb sont extraits dans la phase organique et entraînés par stripping de cette phase au moyen d'HCl (12). Le Se reste dans la phase aqueuse, dont le pH est réajusté à 10 (3), puis est recyclé, le processus commençant au stade du lessivage.
PCT/AU1989/000264 1988-06-17 1989-06-16 Recuperation de selenium de grande purete a partir de minerais, de boues de lavage, de depots de boues anodiques et de debris metalliques WO1989012700A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPI885288 1988-06-17
AUPI8852 1988-06-17

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WO1989012700A1 true WO1989012700A1 (fr) 1989-12-28

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2534093C2 (ru) * 2013-03-12 2014-11-27 Открытое акционерное общество "Уралэлектромедь" Способ переработки медеэлектролитного шлама
US20150151966A1 (en) * 2013-12-03 2015-06-04 Korea Institute Of Science And Technology Separation method of tellurium and selenium, and preparation method of tellurium using the same
CN106744725A (zh) * 2016-12-19 2017-05-31 广东先导稀材股份有限公司 从硒化镉废料中浸出硒的方法
CN108502852A (zh) * 2018-03-13 2018-09-07 昆明理工大学 一种微波硫酸化焙烧回收铜阳极泥中硒的方法
JP2019203764A (ja) * 2018-05-23 2019-11-28 一般財団法人電力中央研究所 重金属類の還元方法及びそれを利用した重金属類溶出量の測定方法
CN110817811A (zh) * 2019-12-12 2020-02-21 昆明冶金研究院有限公司 一种粒度分布均匀的高纯硒粉的制备方法
CN112430739A (zh) * 2020-11-30 2021-03-02 中南大学 一种有色冶炼固体废弃物中汞的回收方法

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US3848069A (en) * 1972-11-14 1974-11-12 Kennecott Copper Corp Process for recovering selenium values from aqueous solutions containing molybdenum,rhenium and selenium values
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JPS57179004A (en) * 1981-04-28 1982-11-04 Asahi Glass Co Ltd Refining method for metallic selenium
SU979517A1 (ru) * 1981-06-01 1982-12-07 Ленинградский Ордена Ленина,Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Горный Институт Им.Г.В.Плеханова Способ извлечени селена из медеэлектролитных шламов
EP0102754A1 (fr) * 1982-08-02 1984-03-14 Xerox Corporation Procédé de récupération du sélénium, du tellure et de l'arsenic de haute pureté à partir de déchets d'alliages
EP0103383A1 (fr) * 1982-08-02 1984-03-21 Xerox Corporation Procédé pour la purification du sélénium
AU536775B2 (en) * 1980-09-30 1984-05-24 Inco Ltd. Hydrometallurgical processing of precious metals
EP0157514A2 (fr) * 1984-03-29 1985-10-09 Xerox Corporation Procédé de régénération de sélenium de haute pureté
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SU177621A1 (ru) * Способ обработки селенсодержащих отходов и лома
SU231830A1 (ru) * 1967-06-19 1975-10-15 Ленинградский ордена Ленина и ордена Трудового Красного Знамени горный институт им. Г.В. Плеханова Способ разделени селена и теллура
SU396071A1 (ru) * 1971-02-01 1975-07-05 Ленинградский Ордена Ленина И Ордена Трудового Красного Знамени Институт Им. Г.В.Плеханова Способ очистки селеносодержащих растворов от теллура
US3848069A (en) * 1972-11-14 1974-11-12 Kennecott Copper Corp Process for recovering selenium values from aqueous solutions containing molybdenum,rhenium and selenium values
US4163046A (en) * 1977-05-24 1979-07-31 The International Nickel Company, Inc. Recovery of selenium
JPS5622609A (en) * 1979-07-30 1981-03-03 Sumitomo Metal Mining Co Ltd Manufacture of low sulfur metallic selenium
JPS5645811A (en) * 1979-09-21 1981-04-25 Furukawa Kinzoku Kogyo Kk Manufacture of metallic selenium
AU536775B2 (en) * 1980-09-30 1984-05-24 Inco Ltd. Hydrometallurgical processing of precious metals
JPS57179004A (en) * 1981-04-28 1982-11-04 Asahi Glass Co Ltd Refining method for metallic selenium
SU979517A1 (ru) * 1981-06-01 1982-12-07 Ленинградский Ордена Ленина,Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Горный Институт Им.Г.В.Плеханова Способ извлечени селена из медеэлектролитных шламов
EP0102754A1 (fr) * 1982-08-02 1984-03-14 Xerox Corporation Procédé de récupération du sélénium, du tellure et de l'arsenic de haute pureté à partir de déchets d'alliages
EP0103383A1 (fr) * 1982-08-02 1984-03-21 Xerox Corporation Procédé pour la purification du sélénium
EP0157514A2 (fr) * 1984-03-29 1985-10-09 Xerox Corporation Procédé de régénération de sélenium de haute pureté
SU1348702A1 (ru) * 1985-06-25 1987-10-30 Научно-Исследовательский И Проектный Институт Цветной Металлургии Способ извлечени селена из концентратов

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2534093C2 (ru) * 2013-03-12 2014-11-27 Открытое акционерное общество "Уралэлектромедь" Способ переработки медеэлектролитного шлама
US20150151966A1 (en) * 2013-12-03 2015-06-04 Korea Institute Of Science And Technology Separation method of tellurium and selenium, and preparation method of tellurium using the same
CN106744725A (zh) * 2016-12-19 2017-05-31 广东先导稀材股份有限公司 从硒化镉废料中浸出硒的方法
CN108502852A (zh) * 2018-03-13 2018-09-07 昆明理工大学 一种微波硫酸化焙烧回收铜阳极泥中硒的方法
JP2019203764A (ja) * 2018-05-23 2019-11-28 一般財団法人電力中央研究所 重金属類の還元方法及びそれを利用した重金属類溶出量の測定方法
CN110817811A (zh) * 2019-12-12 2020-02-21 昆明冶金研究院有限公司 一种粒度分布均匀的高纯硒粉的制备方法
CN112430739A (zh) * 2020-11-30 2021-03-02 中南大学 一种有色冶炼固体废弃物中汞的回收方法

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