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WO2006042898A1 - Procédé de retraitement de sous-produits oxydants contenant de l’arsenic - Google Patents

Procédé de retraitement de sous-produits oxydants contenant de l’arsenic Download PDF

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Publication number
WO2006042898A1
WO2006042898A1 PCT/FI2004/000628 FI2004000628W WO2006042898A1 WO 2006042898 A1 WO2006042898 A1 WO 2006042898A1 FI 2004000628 W FI2004000628 W FI 2004000628W WO 2006042898 A1 WO2006042898 A1 WO 2006042898A1
Authority
WO
WIPO (PCT)
Prior art keywords
products
arsenic
oxidic
copper
dust
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.)
Ceased
Application number
PCT/FI2004/000628
Other languages
English (en)
Inventor
Cesar ACUÑA ROJAS
Luis Bernal Venegas
Björn Lindqvist
Gunnar Berg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Outokumpu Oyj
Metso Corp
Original Assignee
Outokumpu Oyj
Outokumpu Technology Oyj
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Outokumpu Oyj, Outokumpu Technology Oyj filed Critical Outokumpu Oyj
Priority to PCT/FI2004/000628 priority Critical patent/WO2006042898A1/fr
Priority to CNB2004800442764A priority patent/CN100432247C/zh
Priority to EA200700588A priority patent/EA011214B1/ru
Publication of WO2006042898A1 publication Critical patent/WO2006042898A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0054—Slag, slime, speiss, or dross treating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/08—Dry methods smelting of sulfides or formation of mattes by sulfides; Roasting reaction methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • C22B5/14—Dry methods smelting of sulfides or formation of mattes by gases fluidised material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • 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

Definitions

  • This invention relates to a process for reprocessing oxidic by-products containing arsenic, such as dust and the like, obtained in processes for pyrometallurgical copper production, such that the arsenic content is reduced to a level that permits the products to be further treated in the process, while copper and other metal values present remain in the products.
  • the invention is concerned with dust and other by-products obtained in autogenous copper smelting processes, such as flash smelting.
  • copper smelting plants today operate according to the standard autogenous smelting processes, that is, smelting of sulphide materials, converting, and refining in an anode furnace (so-called fire refining), in which substances or compounds having high partial pressures are partially removed through a gas phase during the smelting and the converting.
  • fire refining smelting of sulphide materials, converting, and refining in an anode furnace
  • a substantial proportion of these are ultimately contained in the anode copper, which is then usually further refined by electrolysis, in which the presence of impurities such as arsenic (As), antimony (Sb) and bismuth (Bi) causes major problems.
  • impurities such as arsenic (As), antimony (Sb) and bismuth (Bi) causes major problems.
  • an ore concentrate containing 0.4 % to 0.65 % As results in an "average dust" containing 5 % to 10 % As. Recycling of such dusts to the smelting process can only take place to a limited extent, because otherwise the arsenic in dust will result in products, that is, matte and eventually an anode copper having elevated arsenic contents. To have the chemical quality that is required for the anode copper in the electrolytic refining process, these products then have to undergo special processing by expensive lime- soda treatments and/or time-consuming slag treatments.
  • oxidic by-products discussed above also have substantial contents of sulphur in the form of sulphates and other, complex oxidic sulphur compounds.
  • the dust formed during the smelting is to be recycled to the process, it therefore has to be reprocessed by leaching, but leaching gives an inadequate yield of metal.
  • leaching of smelter dust is practised at present, the yield of the copper extraction process is relatively low, generally around 50 percent, which necessitates recycling of the waste sludge to the smelter in order to keep the copper recovery within acceptable limits.
  • smelter dust has to be extracted from the smelter circuit and transferred to a disposal site. Increased arsenic input to the smelter probably will lead to more frequent extraction of the smelter dust, and increased dust extraction will result in lower copper recovery.
  • the other process which is described in US patent 5,397,380, is directed to the treatment of complex sulphide materials and comprises a first leaching step in which sulphide sulphur is converted into sulphate and the oxidising iron and the compounds present, such as arsenic, are dissolved, and in which the leaching residue is treated in conventional pyrometallurgical steps aiming at producing the metal values there from.
  • these prior art processes cannot be applied to a copper process, because, among other things, the first process results in production of new dusts and thus cannot be integrated in a copper process, and the second process cannot be applied to autogenous smelting processes, because it is necessary that a substantial content of sulphur remains in the input material.
  • the object of the invention is to devise such a surprisingly efficient and simple way of substantially avoiding the above-indicated problems related to the arsenic-containing by-products, which always result from modern autogenous copper smelting processes.
  • the oxidic by-products are treated at a temperature of 670 °C to 770 0 C in a fluidised bed under reducing conditions in which the arsenic contained in the products is vaporised.
  • the arsenic is thus transferred to the gas phase present in the bed, and the gas is then purified in respect of arsenic in a suitable manner in gas purification systems.
  • the gas is cooled such that arsenic trioxide is formed and removed from the process, while the treated products are returned to the process at a suitable point for recovering their metal content.
  • the reducing conditions which are thus required, can be maintained by mixing a sulphide, suitably one containing metal values.
  • a sulphide suitably one containing metal values.
  • the relationship between the oxidic by-product and the sulphide is selected to be between 5:95 and 50:50 in mass percent.
  • Addition of a reducing gas, such as LPG (liquefied petroleum gas) or the like, to the bed is also suitable, advantageously in combination with addition of a sulphide. The addition is controlled such that adequate heat energy is supplied to the bed to ensure the required decomposition of present oxidic sulphur compounds, for example.
  • the substantially arsenic-free roasted product obtained can be melted using standard processes for pyrometallurgical copper production.
  • Required precise roasting conditions such as oxygen potential, bed temperature, heat balance, roasting time etc., can be efficiently set and controlled in a fluidised bed.
  • the apparatus used for the tests comprises a roasting shaft, in which oxidic dust materials with high arsenic content or mixtures with copper sulphide ore concentrate and oxidic materials are fed through a tube connected to a container holding the materials. Because of its fine graininess, the dust admixed with copper ore concentrate, which had been dried to a moisture content of 0.2 %, was pelletized. However, no significant differences were observed when the mixture of dust and ore concentrate was supplied directly, without any previous steps having been taken. The fine material captured from the roasting gas was first separated in a cyclone separator and then the gas was transferred to an afterburner, in which the arsenic-containing gas was oxidised and arsenic trioxide was formed.
  • the arsenic trioxide was also separated and collected.
  • the material from the bed was extracted by means of a screw feeder having a water-cooled double tube at one end of which the roasted product was collected in a plastic bag to be weighed.
  • the material collected in the cyclone separator was taken care of in the same way as the bed material and these two fractions were to form the "process material".
  • the material collected in the filter was regarded as "roasting dust" to be offered for sale or, possibly, reprocessed.
  • equipment for injecting water at the level of the bed had been provided, and equipment for supplying oxygen and/or LPG or a different oxidising gas if such additions were made had also been provided.
  • the invention involves reprocessing of oxidic material containing metal values and having high arsenic content, such as dust from autogenous copper smelting processes, using a fluidised bed and an efficient gas purification system.
  • the reprocessing conditions such as oxygen potential and heat balance, are controlled by addition of LPG or other fuels, such as oil, to the fluidised bed.
  • Control of the oxygen potential and maintaining an optimal temperature are essential in order that desired degrees of vaporisation of arsenic and certain other compounds (Sb, Bi) as well as decomposition of sulphates and evaporation of liberated sulphur may be achieved.
  • heat may also occasionally be supplied to maintain the heat balance, primarily because of the heat consumption associated with the chemical decomposition of the sulphates present.
  • the roasted product has low contents of As, Sb, etc., and thus is suitable and attractive for the production of matte and white metal for conventional pyrometallurgical copper production.
  • the waste products obtained can be made more centred and/or more stable in comparison with the added dust materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention a pour objet un procédé de retraitement de sous-produits oxydants contenant de l’arsenic, tels que des poussières et des substances du même type. Lesdits sous-produits sont issus de procédés pyrométallurgiques de production de cuivre. Lesdits procédés pyrométallurgiques doivent impliquer des teneurs réduites en arsenic de façon à ce que les sous-produits formés puissent être traités de plus par le procédé décrit dans la présente invention, alors que le cuivre et les autres métaux de valeur restent dans les produits directs du procédé de pyrométallurgie. Ladite méthode est caractérisée en ce que les sous-produits oxydants sont traités à une température comprise entre 670 °C et 770 °C dans un lit fluidifié et dans des conditions réductrices. L’arsenic contenu dans lesdits sous-produits est alors vaporisé et transféré dans la phase gazeuse présente dans le lit fluidifié. L’arsenic est ensuite extrait du gaz de la façon appropriée, alors que les produits résultant du traitement sont réengagés dans le procédé à l'étape adéquate, afin de récupérer leur contenu en métaux.
PCT/FI2004/000628 2004-10-22 2004-10-22 Procédé de retraitement de sous-produits oxydants contenant de l’arsenic Ceased WO2006042898A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/FI2004/000628 WO2006042898A1 (fr) 2004-10-22 2004-10-22 Procédé de retraitement de sous-produits oxydants contenant de l’arsenic
CNB2004800442764A CN100432247C (zh) 2004-10-22 2004-10-22 一种对含砷的氧化物副产品进行再处理的方法
EA200700588A EA011214B1 (ru) 2004-10-22 2004-10-22 Способ переработки оксидных побочных продуктов, содержащих мышьяк

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI2004/000628 WO2006042898A1 (fr) 2004-10-22 2004-10-22 Procédé de retraitement de sous-produits oxydants contenant de l’arsenic

Publications (1)

Publication Number Publication Date
WO2006042898A1 true WO2006042898A1 (fr) 2006-04-27

Family

ID=36202705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2004/000628 Ceased WO2006042898A1 (fr) 2004-10-22 2004-10-22 Procédé de retraitement de sous-produits oxydants contenant de l’arsenic

Country Status (3)

Country Link
CN (1) CN100432247C (fr)
EA (1) EA011214B1 (fr)
WO (1) WO2006042898A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130291684A1 (en) * 2010-12-14 2013-11-07 Outotec Oyj Process and plant for treating ore concentrate particles containing valuable metal
EP2545193B1 (fr) 2010-03-10 2016-06-01 Aurubis AG Procédé et dispositif de traitement de cendres volantes
US10081848B2 (en) 2013-10-02 2018-09-25 Outotec (Finland) Oy Method and plant for removing arsenic and/or antimony from flue dusts
CN115637322A (zh) * 2022-11-09 2023-01-24 昆明理工大学 一种氧气气泡联合超声波去除氧化锌烟尘浸出液中砷的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489046A (en) * 1980-03-10 1984-12-18 Boliden Aktiebolag Method for working-up arsenic-containing waste
EP0128887A1 (fr) * 1983-06-06 1984-12-19 Boliden Aktiebolag Procédé de préparation de concentré de cuivre ou analogues à haute teneur en arsenic et/ou antimoine
CA1314149C (fr) * 1987-12-11 1993-03-09 Jaroslav R. Derka Methodes de recuperation de valeurs d'arsenic dans des residus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489046A (en) * 1980-03-10 1984-12-18 Boliden Aktiebolag Method for working-up arsenic-containing waste
EP0128887A1 (fr) * 1983-06-06 1984-12-19 Boliden Aktiebolag Procédé de préparation de concentré de cuivre ou analogues à haute teneur en arsenic et/ou antimoine
CA1314149C (fr) * 1987-12-11 1993-03-09 Jaroslav R. Derka Methodes de recuperation de valeurs d'arsenic dans des residus

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2545193B1 (fr) 2010-03-10 2016-06-01 Aurubis AG Procédé et dispositif de traitement de cendres volantes
EP3064601B1 (fr) 2010-03-10 2022-03-02 Aurubis AG Procédé et dispositif de traitement de cendres volantes
US20130291684A1 (en) * 2010-12-14 2013-11-07 Outotec Oyj Process and plant for treating ore concentrate particles containing valuable metal
US9200345B2 (en) * 2010-12-14 2015-12-01 Outotec Oyj Process and plant for treating ore concentrate particles containing valuable metal
US10081848B2 (en) 2013-10-02 2018-09-25 Outotec (Finland) Oy Method and plant for removing arsenic and/or antimony from flue dusts
CN115637322A (zh) * 2022-11-09 2023-01-24 昆明理工大学 一种氧气气泡联合超声波去除氧化锌烟尘浸出液中砷的方法

Also Published As

Publication number Publication date
CN101048519A (zh) 2007-10-03
EA200700588A1 (ru) 2007-12-28
EA011214B1 (ru) 2009-02-27
CN100432247C (zh) 2008-11-12

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