WO1979000055A1 - A method for the manufacture of an additive material for the production of crude iron - Google Patents

A method for the manufacture of an additive material for the production of crude iron Download PDF

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Publication number
WO1979000055A1
WO1979000055A1 PCT/SE1978/000018 SE7800018W WO7900055A1 WO 1979000055 A1 WO1979000055 A1 WO 1979000055A1 SE 7800018 W SE7800018 W SE 7800018W WO 7900055 A1 WO7900055 A1 WO 7900055A1
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WO
WIPO (PCT)
Prior art keywords
iron
furnace
smelting
production
oxide material
Prior art date
Application number
PCT/SE1978/000018
Other languages
French (fr)
Inventor
S Petersson
B Eriksson
Original Assignee
Boliden Ab
S Petersson
B Eriksson
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 Boliden Ab, S Petersson, B Eriksson filed Critical Boliden Ab
Publication of WO1979000055A1 publication Critical patent/WO1979000055A1/en

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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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B15/00—Other processes for the manufacture of iron from iron compounds
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/02—General features in the manufacture of pig-iron by applying additives, e.g. fluxing agents

Definitions

  • the present invention relates to a method for the manufacture of iron raw material from sulphidic iron-containing materials, preferably pyrite and pyrrhotite.
  • Pyrite, FeS 2 are mainly used as a sulphur raw material in the production of sulphuric acid and liquid sulphurdioxide, by combusting the sulphur content of the said raw materials with an oxygen-containing gas during a so-called roasting process.
  • sulphur dioxide is formed and is passed to a plant for the production of sulphuric acid or liquid sulphur dioxide.
  • the iron content of the pyrite is converted to iron oxides in the form of hematite or magnetite or mixtures thereof, depending upon the roasting method applied.
  • the iron oxides or pyrite cinders have had a low sales value, mainly because they are extremely fine and dust creatinc and therefore difficult to handle. Further, the quantities in which they are produced are so small, in the order of magnitude of 100.000 tons/year, that it is not sufficiently rewarding for a sintering plant to be erected on the premises of conventional sulphuric acid factory, in which plant the fine-grain material could be converted to agglomerates of the size required for charging to, for example, blast furnaces. Further, the pyrite cinders may be somewhat contaminated with, for example, copper, zink, lead, cobalt, nickel, arsenic, sulphur and noble metals.
  • impurities primarily copper, zink and arsenic, also render the deposition or dumping of cinders expensive, since it must be ensured that these metals are not leached from the dumping cinders by, for example, rainwater.
  • the present invention relates to a method of manufacturing an additive material for the production of crude iron and is characterized in that iron-sulphide containing material is charged to a furnace space together with oxygen and silicate- containing material in relative proportions such that subsequent to autogenous smelting taking place there is obtained an iron silicate melt containing approximately 60-90 percent by weight iron, calculated as iron(II)oxice, said melt then being granulated and permitted to solidify, and then crushed to a size suitable for charging to a furnace unit for the production of crude iron.
  • the method according to the invention enables pyrite to be used directly, not only as a raw material for the production of sulphur dioxide and sulphuric acid, but also as a raw material for the production of iron, by charging pyrite to a smelter, such as a flash smelter, for example a smelter such as that described in US Patent No 3 790 366, together with silica, e.g. quartz sand, and by smelting the pyrites autogenously by charging to the furnace oxygen-gas or oxygen enriched air, thereby to form substantially an iron-silicate melt.
  • a smelter such as a flash smelter, for example a smelter such as that described in US Patent No 3 790 366
  • silica e.g. quartz sand
  • non-ferrous metals having a greater affinity than iron has to sulphur will form a matte, such non-ferrous metals normally being present in pyrite as impurities.
  • the matte is more dense than the oxidic-iron silica melt and is insoluble therein, and hence it can be readily separated and tappec-off separately.
  • the major part of the melt comprising iron oxide- silica also known as fayalite slag, corresponds approximately to a composition of 2FeO.SiO 2 , which contains 60-90% iron calculated as iron (I ⁇ )oxide, is then used as an additive material in the production of iron according to conventional processes and thus comprises a silica and an iron raw material.
  • the excess heat generated when smelting pyrite aouto-genously can be utilized to smelt other raw products, such as iron oxides, pyrite cinders, iron-containing slags - e.g. slag obatined from lead and copper smelters - and leaching residues containing substantial quantities of iron.
  • Smelting to fayalite slag can be effected in a flash smelter, whereafter the resultant fayalite slag is conveniently transferred to moulds and cooled therein.
  • the slag can be granulated.
  • the lower limit to which iron can be present in the slag, calculated as iron(II)oxide, is determined by the fact that the melting point rises very quickly when the content of iron is less than 60 percent by weight, while the upper limit is determined by the fact that the amount of iron(Ill)oxide formed, and therewith the extent to which magnetite is formed, becomes excessively high when the slag contains more than 90 percent by weight iron, calculated as iron(II)oxide.
  • sul- phur dioxide and an iron-silica raw material can be produced from pyrite and other iron-sulphidic materials with a relatively small energy consumption and whilst simultaneously recovering other valuable non-ferrous metals.
  • iron-silicate slag e.g. slags obtained from lead and copper smelters or plants, to be used as iron rawmaterials, since it contains both SiO 2 and FeO which are normally present in various crude iron processes.
  • a further advantage afforded by the process is that fine- grain iron material can be charged to a flash smelter in that state it obtained upon being concentrated, which provides for considerable saving in comparison with, for example, shaft furnaces in which only agglomerated sintered iron raw material can be used.
  • the method according to the invention also permits the temperatures to be kept relatively low during the process, for example in the range of 1250-1350oC, which is favourable with respect to the furnace lining.
  • the temperature within the furnace should be increased by some hundred degrees.
  • Pyrite and silica are charged to a furnace together with other iron raw materials, such as iron-ore concentrates, fayalite slag obtained from copper and lead plants, or pyrite cinders in the form of hematite or magnetite, in such quantities that a liquid fayalite slag is formed.
  • the furnace is conveniently a flash smelter, although other types of furnaces may be used. Among those furnaces which can be used in this context ore rotary furnaces and furnaces of a type to which a fine-grain material can be charged and which permit a smelt to be formed.
  • the process may be a continuous process or an intermittent process, depending upon the type of furnace used.
  • ironsulphidic material normally contains non-ferrous metals, such as copper, nickel and cobalt, which form a sulphide phase in which any noble metals present will be refound.
  • the sulphide phase which is not soluble in the oxidic fayalite slag and which has a higher specific gravity than said slag, is settled on the bottom of the flash smelter and may be tapped therefoom at uniform intervals. Part of the arsenic, antimony and bismuth present will be driven off during the smelting process while the remainder will be dissolved in the sulphide phase.
  • the fayalite slag is suitably tapped into moulds and allowed to solidify therein, whereafter the solidified mass is crushed to pieces of a size suitable for charging as addition material to raw-iron processes carried out in shaft furnaces, such as blast furnaces.
  • shaft furnaces such as blast furnaces.
  • Sulphur dioxide containing gas formed during the autogenous smelting process is passed out of the furnace and is suitably led to a plant for the production of sulphuric acid or a plant for the production of liquid sulphur dioxide, subsequent to having been subjected to a heat exchange process and cleaned from dust in a conventional manner.
  • the heat of formation liberated by splitting off pyrite (FeS is not included) is 1380 MJ per ton, which provides a net heat development for the process when 100% oxygen gas is used corresponding to 2 174 + 4 750 + 99 - 1 380 MJ, which is equal to 5 643 MJ calculated per ton of pyrite.
  • the method according to the invention enables pyrite concentrates to be used as raw materials for the recovery of sulphur dioxide and the recovery of iron, since it is possible to produce lumps of iron raw-material suitable charging directly to shaft furnaces, such as blast furnaces.
  • the source of energy comprises mostly the sulphur present in the pyrite concentrates, which sulphur is far less expensive than the higher grade fuels such as coal, oil and gas.
  • a further, significant advantage is that fine-grain iron raw materials can be used.
  • Iron raw materials containing impurities such as Cu and Pb can be used in known processes only when they have been purified in a special process step or if the impurities are diluted by relatively large quantities of pure iron raw material. In this latter case valuable metals cannot be recovered.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

A method for the manufacture an additive material for the production of crude iron which comprises charging an iron sulphidic material to a furnace space together with oxygen and a silicate-containing material in relative proportions such that it is possible to obtain an iron silicate melt containing 60-90% by weight iron, calculated as iron (11) oxide when melting. The melt is granulated or permitted to solidify and then crushed to pieces of a size suitable to charge to a furnace unit for the production of crude iron.

Description

A METHOD FOR THE MANUFACTURE OF AN ADDITIVE MATERIAL FOR THE PRODUCTION' OF CRUDE IRON
The present invention relates to a method for the manufacture of iron raw material from sulphidic iron-containing materials, preferably pyrite and pyrrhotite.
Pyrite, FeS2, are mainly used as a sulphur raw material in the production of sulphuric acid and liquid sulphurdioxide, by combusting the sulphur content of the said raw materials with an oxygen-containing gas during a so-called roasting process. During the roasting process, sulphur dioxide is formed and is passed to a plant for the production of sulphuric acid or liquid sulphur dioxide. During the roasting process, the iron content of the pyrite is converted to iron oxides in the form of hematite or magnetite or mixtures thereof, depending upon the roasting method applied. Hitherto, the iron oxides or pyrite cinders have had a low sales value, mainly because they are extremely fine and dust creatinc and therefore difficult to handle. Further, the quantities in which they are produced are so small, in the order of magnitude of 100.000 tons/year, that it is not sufficiently rewarding for a sintering plant to be erected on the premises of conventional sulphuric acid factory, in which plant the fine-grain material could be converted to agglomerates of the size required for charging to, for example, blast furnaces. Further, the pyrite cinders may be somewhat contaminated with, for example, copper, zink, lead, cobalt, nickel, arsenic, sulphur and noble metals. In the majority of cases the presence of such impurities is not desirable when manufacturing iron and steel. The impurities, primarily copper, zink and arsenic, also render the deposition or dumping of cinders expensive, since it must be ensured that these metals are not leached from the dumping cinders by, for example, rainwater.
For the purpose of reducing the level of impurities in steel, in those cases where pyrite cinders are included as raw materials, it is common practice to simply dilute the cinders with iron-ore concentrates, which normally do not con- tain these impurities, although in this case valuable metals such as copper, nickel, cobalt and, in certain cases, also noble metals, cannot be recovered from the cinders.
Consequently, during recent years various processes have been developed which permit the pyrite cinders to be purified and agglomerated, thereby rendering them more suitable as an iron raw-material, whilst at the same time permitting other valuable metals to be recovered. One normal method of procedure in this respect is to treat the cinders with chlorine or a chlorine-containing material, thereby to convert the impurities to chlorides, which, by heating or leaching, can be separated from each other and then recovered. Processes of this type have many disadvantages. Among other things the plants are expensive to operate because of the high investments necessary and because of the considerable quantities of chemicals consumed and the corrosion to which the apparatus are subjected. Further, the use of chlorine incurs costs in the protection of the environment. The viability of said chlorinating refining processes is also dependent upon the presence of relatively large quantities of contaminating and recoverable valuable metals.
The present invention relates to a method of manufacturing an additive material for the production of crude iron and is characterized in that iron-sulphide containing material is charged to a furnace space together with oxygen and silicate- containing material in relative proportions such that subsequent to autogenous smelting taking place there is obtained an iron silicate melt containing approximately 60-90 percent by weight iron, calculated as iron(II)oxice, said melt then being granulated and permitted to solidify, and then crushed to a size suitable for charging to a furnace unit for the production of crude iron.
Thus, the method according to the invention enables pyrite to be used directly, not only as a raw material for the production of sulphur dioxide and sulphuric acid, but also as a raw material for the production of iron, by charging pyrite to a smelter, such as a flash smelter, for example a smelter such as that described in US Patent No 3 790 366, together with silica, e.g. quartz sand, and by smelting the pyrites autogenously by charging to the furnace oxygen-gas or oxygen enriched air, thereby to form substantially an iron-silicate melt. When large quantities of non-ferrous metals are present, it is possible in the aforementioned method to ensure that the combustion of sulphur is not carried to completion so that non-ferrous metals having a greater affinity than iron has to sulphur will form a matte, such non-ferrous metals normally being present in pyrite as impurities. The matte is more dense than the oxidic-iron silica melt and is insoluble therein, and hence it can be readily separated and tappec-off separately. The major part of the melt comprising iron oxide- silica, also known as fayalite slag, corresponds approximately to a composition of 2FeO.SiO2, which contains 60-90% iron calculated as iron (IΙ)oxide, is then used as an additive material in the production of iron according to conventional processes and thus comprises a silica and an iron raw material. The excess heat generated when smelting pyrite aouto-genously can be utilized to smelt other raw products, such as iron oxides, pyrite cinders, iron-containing slags - e.g. slag obatined from lead and copper smelters - and leaching residues containing substantial quantities of iron.
Smelting to fayalite slag can be effected in a flash smelter, whereafter the resultant fayalite slag is conveniently transferred to moulds and cooled therein. Alternatively the slag can be granulated. The lower limit to which iron can be present in the slag, calculated as iron(II)oxide, is determined by the fact that the melting point rises very quickly when the content of iron is less than 60 percent by weight, while the upper limit is determined by the fact that the amount of iron(Ill)oxide formed, and therewith the extent to which magnetite is formed, becomes excessively high when the slag contains more than 90 percent by weight iron, calculated as iron(II)oxide.
When practising the method according to the invention sul- phur dioxide and an iron-silica raw material can be produced from pyrite and other iron-sulphidic materials with a relatively small energy consumption and whilst simultaneously recovering other valuable non-ferrous metals. Further, the process enables iron-silicate slag, e.g. slags obtained from lead and copper smelters or plants, to be used as iron rawmaterials, since it contains both SiO2 and FeO which are normally present in various crude iron processes.
A further advantage afforded by the process is that fine- grain iron material can be charged to a flash smelter in that state it obtained upon being concentrated, which provides for considerable saving in comparison with, for example, shaft furnaces in which only agglomerated sintered iron raw material can be used.
The method according to the invention also permits the temperatures to be kept relatively low during the process, for example in the range of 1250-1350ºC, which is favourable with respect to the furnace lining. When the conditions are such that magnetite is liable to be formed and deposited on the walls of the furnace, the temperature within the furnace should be increased by some hundred degrees.
The method will now. be described with reference to a preferred embodiment thereof.
Pyrite and silica are charged to a furnace together with other iron raw materials, such as iron-ore concentrates, fayalite slag obtained from copper and lead plants, or pyrite cinders in the form of hematite or magnetite, in such quantities that a liquid fayalite slag is formed. The furnace is conveniently a flash smelter, although other types of furnaces may be used. Among those furnaces which can be used in this context ore rotary furnaces and furnaces of a type to which a fine-grain material can be charged and which permit a smelt to be formed. The process may be a continuous process or an intermittent process, depending upon the type of furnace used.
By charging oxygen or air enriched in oxygen to the furnace, the sulphur content and the iron content of the pyrite are combusted suitably in the shaft of a flash smelter, whilst generating large quantities of heat the iron-containing material charged to the furnace being smelted down autggenously and, together with an dddition of silica, forms a molten bath comprising mainly a fayalite slag. As beformentioned, ironsulphidic material normally contains non-ferrous metals, such as copper, nickel and cobalt, which form a sulphide phase in which any noble metals present will be refound. The sulphide phase, which is not soluble in the oxidic fayalite slag and which has a higher specific gravity than said slag, is settled on the bottom of the flash smelter and may be tapped therefoom at uniform intervals. Part of the arsenic, antimony and bismuth present will be driven off during the smelting process while the remainder will be dissolved in the sulphide phase.
The fayalite slag is suitably tapped into moulds and allowed to solidify therein, whereafter the solidified mass is crushed to pieces of a size suitable for charging as addition material to raw-iron processes carried out in shaft furnaces, such as blast furnaces. Thus, the process enables the separation and recovery of the non-ferrous metal content of the starting materials, the presence of such non-ferrous metals normally being undesirable in iron products.
Sulphur dioxide containing gas formed during the autogenous smelting process is passed out of the furnace and is suitably led to a plant for the production of sulphuric acid or a plant for the production of liquid sulphur dioxide, subsequent to having been subjected to a heat exchange process and cleaned from dust in a conventional manner.
If, when carrying out the method according to the invention, cinders Containing 'Fe(III), obtained from conventional roasting processes, are charged to the furnace, it should be ensured during the smelting process that magnetite is not formed in quantities exceeding approximately 5 percent by weight of the total amount of slag formed. The magnetite has a higher melting point and will impart to the slag a higher viscosity, which renders it difficult to tap-off the slag. By adding coke to the molten bath in the furnace, it is possible to provide reducing conditions which are sufficient to reduce Fe(III) to Fe(II).
The combustion of pyrite with air results in a signicicant excess of heat, which can be utilized to smelt oxidic-iron raw-materials of the type previously mentioned. This excess of heat can be increased considerably by using pre-heated material, air enriched with oxygen or oxygengas when combusting pyrite.
When 1000 kgs of pyrite is oxidized to form iron(II)oxide and sulphur dioxide the heat of formation will be 2 174 MJ and 4 750 MJ respectively. When adding SiO2 in quantities such that the compound fayalite (2FeO.SiO2) is formed, the heat of formation required herefor is only 99 MJ.
The heat of formation liberated by splitting off pyrite (FeS is not included) is 1380 MJ per ton, which provides a net heat development for the process when 100% oxygen gas is used corresponding to 2 174 + 4 750 + 99 - 1 380 MJ, which is equal to 5 643 MJ calculated per ton of pyrite.
The method according to the invention enables pyrite concentrates to be used as raw materials for the recovery of sulphur dioxide and the recovery of iron, since it is possible to produce lumps of iron raw-material suitable charging directly to shaft furnaces, such as blast furnaces. When carrying out the method, the source of energy comprises mostly the sulphur present in the pyrite concentrates, which sulphur is far less expensive than the higher grade fuels such as coal, oil and gas. A further, significant advantage is that fine-grain iron raw materials can be used.
Iron raw materials containing impurities such as Cu and Pb can be used in known processes only when they have been purified in a special process step or if the impurities are diluted by relatively large quantities of pure iron raw material. In this latter case valuable metals cannot be recovered.

Claims

CLAIMS :-
1. A method for the manufacture of an addition material for the production of crude iron, characterized in that iron sulphidic material is charged to a furnace space together with oxygen and silicate-containing material in relative proportions such that subsequent to autogenous smelting there is obtained an iron silicate melt containing approximately 60-90 percent by weight iron, calculated as iron(II)-oxide, which melt is granulated or permitted to solidify and then crushed to pieces of a size suitable for charging to a furnace unit for the production of crude iron.
2. A method according to claim 1, characterized in that excess heat generated during the autogenous smelting process is used for smelting iron oxide material.
3. A method according to claim 2, characterized in that the iron oxide material is pyrite cinders.
4. A method according to claim 2, characterized in that the iron oxide material is iron ore concentrates.
5. A method according to claim 2, characterized in that the iron oxide material is slag obtained from a copper plant.
6. A method according to claim 2, characterized in that the iron oxide material is a slag obtained from a lead plant.
7. A method according to claim 1, characterized in that smelting is carried out in a flash smelter.
8. A method according to claim 1, characterized in that the smelting is effected by charging oxygen gas or air enriched in oxygen to said furnace.
9. A method according to claim 1, characterized in that the smelting process is carried out with a residual quantity of sulphur of such magnitude that, copper, nickel and cobalt can form together with sulphur a matte which can be tapped from said furnace.
10. A method according to claim 1, characterized in that the solidified slag is crushed to a size suitable for charging to a blast furnace.
PCT/SE1978/000018 1977-07-22 1978-07-13 A method for the manufacture of an additive material for the production of crude iron WO1979000055A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE7708461A SE407234B (en) 1977-07-22 1977-07-22 PROCEDURE FOR THE PRODUCTION OF AN ADDITIONAL MATERIAL FOR RAIL MANUFACTURE
SE7708461 1977-07-22

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WO1979000055A1 true WO1979000055A1 (en) 1979-02-08

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JP (1) JPS5423015A (en)
ES (1) ES471834A1 (en)
GR (1) GR64980B (en)
IT (1) IT1099011B (en)
PT (1) PT68280A (en)
SE (1) SE407234B (en)
WO (1) WO1979000055A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6059207B2 (en) * 1981-03-13 1985-12-24 日東電工株式会社 Manufacturing method for complex preparations
JPS60233682A (en) * 1984-05-04 1985-11-20 大松化学工業株式会社 Label

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1458808A1 (en) * 1965-11-05 1969-02-06 Acieries Et Minieres De La Sam Method and device for granulating slag
DE1508172A1 (en) * 1965-07-23 1969-10-30 Fisons Ltd Process for the recovery of iron and / or phosphorus-enriched fractions from steel slag
DE2006662A1 (en) * 1969-02-14 1970-09-10 The International Nickel Company Of Canada, Ltd., Copper Cliff, Ontario (Kanada) Process for removing iron from sulphidic materials
US3790366A (en) * 1969-01-14 1974-02-05 Outokumpu Oy Method of flash smelting sulfide ores
DE2166728A1 (en) * 1971-02-01 1975-08-14 Noranda Mines Ltd PROCESS FOR CONTINUOUS SMELTING AND WIND REFRESHING OF COPPER CONCENTRATES
SE383900B (en) * 1968-12-07 1976-04-05 Mitsubishi Metal Mining Co Ltd PROCEDURE AND DEVICE FOR CONTINUOUS MANUFACTURE OF BLISTER METALS FROM SULPHIDE ORE
DE2710970A1 (en) * 1976-03-12 1977-09-15 Boliden Ab PROCESS FOR THE RECOVERY OF RAW OR. BUBBLE COPPER MADE FROM SULFIDE RAW COPPER MATERIAL

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1508172A1 (en) * 1965-07-23 1969-10-30 Fisons Ltd Process for the recovery of iron and / or phosphorus-enriched fractions from steel slag
DE1458808A1 (en) * 1965-11-05 1969-02-06 Acieries Et Minieres De La Sam Method and device for granulating slag
SE383900B (en) * 1968-12-07 1976-04-05 Mitsubishi Metal Mining Co Ltd PROCEDURE AND DEVICE FOR CONTINUOUS MANUFACTURE OF BLISTER METALS FROM SULPHIDE ORE
US3790366A (en) * 1969-01-14 1974-02-05 Outokumpu Oy Method of flash smelting sulfide ores
DE2006662A1 (en) * 1969-02-14 1970-09-10 The International Nickel Company Of Canada, Ltd., Copper Cliff, Ontario (Kanada) Process for removing iron from sulphidic materials
DE2166728A1 (en) * 1971-02-01 1975-08-14 Noranda Mines Ltd PROCESS FOR CONTINUOUS SMELTING AND WIND REFRESHING OF COPPER CONCENTRATES
DE2710970A1 (en) * 1976-03-12 1977-09-15 Boliden Ab PROCESS FOR THE RECOVERY OF RAW OR. BUBBLE COPPER MADE FROM SULFIDE RAW COPPER MATERIAL

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PT68280A (en) 1978-08-01
JPS5423015A (en) 1979-02-21
SE407234B (en) 1979-03-19
SE7708461L (en) 1979-01-23
IT1099011B (en) 1985-09-18
IT7825972A0 (en) 1978-07-21
GR64980B (en) 1980-06-11
ES471834A1 (en) 1979-02-01

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