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GB2125019A - Process for dressing sulphide- containing ores - Google Patents

Process for dressing sulphide- containing ores Download PDF

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Publication number
GB2125019A
GB2125019A GB08223048A GB8223048A GB2125019A GB 2125019 A GB2125019 A GB 2125019A GB 08223048 A GB08223048 A GB 08223048A GB 8223048 A GB8223048 A GB 8223048A GB 2125019 A GB2125019 A GB 2125019A
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GB
United Kingdom
Prior art keywords
process according
gaseous stream
chlorine
raw material
sulphides
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Withdrawn
Application number
GB08223048A
Inventor
Marco Vian
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.)
SAMIM SOC AZIONARIA MINERO MET
Original Assignee
SAMIM SOC AZIONARIA MINERO MET
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 SAMIM SOC AZIONARIA MINERO MET filed Critical SAMIM SOC AZIONARIA MINERO MET
Priority to GB08223048A priority Critical patent/GB2125019A/en
Priority to NL8203176A priority patent/NL8203176A/en
Priority to DE19823230252 priority patent/DE3230252A1/en
Publication of GB2125019A publication Critical patent/GB2125019A/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/06Halides
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B15/00Other processes for the manufacture of iron from iron compounds
    • C21B15/006By a chloride process
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • C22B1/08Chloridising roasting

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treating Waste Gases (AREA)

Abstract

Sulphide-containing ore is chlorinated by a gaseous stream of chlorine and O2 e.g. as air, optionally containing ferric chloride vapour, at a temperature of from 700 DEG C to 1200 DEG C and under a pressure of from 1 to 5 atm, the volatile chlorides of non-ferrous metals (e.g. Zn, Cu, Pb, Ni, Co, Au, Ag) being recovered from the fumes, sulphur dioxide being formed and optionally converted into sulphuric acid and the ash being leached to recover iron.

Description

SPECIFICATION Process for dressing suiphide-containing ores This invention relates to the treatment of sulphide-containing ores.
There are a number of processes for the commercial exploitation of ores which consist of metallic sulphides, such as pyrites, chalcopyrites and the like.
These known processes can be divided into three main groups. The first group. to which roasting processes in air belong, results in the conversion of the sulphur into sulphur dioxide and all of the metals which are present into oxides, all of them forming an ash. If the ash which is formed is pure enough, it can be directly used in iron metallurgy. The second group comprises direct treatment processes in which the ores are treated with gaseous chlorine. Sulphur is converted into sulphur chlorides or elemental sulphur and all of the metals which are contained in the ore are converted to volatile metallic chlorides. The large quantities of ferric chloride which are formed are subsequently oxidized to form oxides and chlorine is recovered and subsequently the oxides are reduced to iron.
When the ores which form the raw material contain a high percentage of sulphides of nonferrous metals, the processes of the first group result in the production of ash which is polluted by high contents of oxides of nonferrous metals, such as zinc oxide, so that the ash cannot be used as the raw material in iron metallurgy. The presence of arsenic in the ash in arsenate from is particularly detrimental.
In some processes, such as the Montedison process and the Kowa-Seiko process, the polluted ash obtained from the processes of the first group is subjected to chlorinating in an oxidizing environment. Chlorine in gaseous form admixed with air, or chlorides (such as NaCI and Cacti2) together with air, can be used for this purpose.
The non-ferrous metals which are contained in the ash are converted into volatile metallic chlorides, whereas the ferric oxide Fe2O3, remains in the ash, so that the latter can be purified and used as a raw material in iron metallurgy.
According to the present invention there is provided a process for the treatment (integral dressing) of a raw material comprising one or more sulphides of non-ferrous metals, which comprises treating the material with a gaseous stream comprising gaseous chlorine and oxygen.
The process according to the present invention is suitable for the treatment of metallic ores in which the metals are present essentially in the form of metallic sulphides, such as pyrites, chalcopyrites, galenas, blendes, chalcocite, and others.
The process according to the present invention is particularly effective whenever the ore to be treated is a complex ore, i.e. one which consists of an admixture of metallic sulphides in various proportions, such as for example a pyrite which also contains sulphides of nonferrous metals, such as sulphides of Zn, Cu, Pb, Ni, Co, Au and Ag, or a pyrite admixed with chalcopyrite and with sulphides of other metals and like ores.
The starting ore, which can be one of the ores aforementioned, or a mixture of such ores or like materials, may first be ground, floated and dried until it has a particle size which is compatible with the treatment in accordance with the invention, for example from 50 microns to 1 mm.
The most satisfactory results are obtained if the particle size is fine enough as to make possible a quick and complete reaction between the ore and the gaseous stream. The ore so prepared, which is the raw material, is introduced into an appropriate apparatus such as a rotary kiln or a fluid-bed reactor. In this apparatus, the raw material is contacted by the gaseous stream which contains the reactants.
Essentially, the reactants are chlorine and oxygen admixed together in the appropriate proportions, to which a certain quantity of ferric chloride, FeCI3, may be added in the form of a vapour.
The gaseous stream may thus consist of oxygen, chlorine and ferric chloride in vapour form, or it may consist of chlorine, ferric chloride in vapour form, and air which has been enriched with oxygen in various proportions.
The oxygen contained in the gaseous stream reacts with the sulphides of, for example, iron and manganese which are present in the raw material and produces ferric oxide, manganese oxide and sulphur dioxide.
The ferric oxide and manganese oxide remain in the reactor interior in solid form and, together with gangue, form an ash or slag. The sulphur dioxide is exhausted frm the reactor in gaseous form, together with fumes.
The chlorine which is present in the gaseous stream reacts with the sulphides of the other non-ferrous metals which are present, such as the sulphides of Cu, Pb, Zn, Ni, Co and others, to produce metallic chlorides which are mainly volatile and are thus withdrawn from the reactor in vapour form together with the fumes.
The ferric chloride in vapour form which is contained in the gaseous stream prevents the formation of further ferric chloride and is also capable of reacting with the sulphides of the non-ferrous metals which are present so as to produce the corresponding chlorides of these non-ferrous metals.
The chlorides of the ferrous metals which have been formed and which are not volatile, are withdrawn from the reactor in either liquid or solid form together with the ash.
In order that the best results may be obtained, i.e. in order to obtain a quick and thorough reaction of the ore and, above all, to prevent the sulphides of iron and manganes which are present in the ore from being converted into chlorides rather than into oxides, it is essential that the gaseous stream which contains the reactants has a well defined chemical composition, to be calculated in each individual case as a function of the chemical composition of the ore.
More particualrly, it is vital that the oxygen, the chlorine and the vapour of ferric chloride should not be present in the gaseous stream in such amounts as not to have fixed and preselected ratios; thus, it is necessary that the respective amounts of the chlorine, oxygen and ferric chloride be calculated for each individual case as a function of the chemical composition of the raw material to be treated.
In more detail, it is required that the total quantity of the chlorine which is contained in the gaseous stream be calculated in terms of the sum of the quantity of chlorine which is stoichiometrically necessary to convert all of the non-ferrous metals, excluding manganese, which are present in the raw materials in the form of sulphides, into their respective chlorides, and that such a quantitity be multiplied by a coefficient which takes into account the actual efficiency of the reaction so as to render the latter complete. The best results are obtained by adopting a coefficient which is from 1 to 2, and more particularly is 1.5.
A similar approach is necessary in respect of the oxygen which is required to convert in a complete way the sulphides of iron and manganese which are contained in the raw material, into ferric oxide, Fe203, and manganese oxide, MnO, respectively, and all of the sulphur which is present in the raw material in the form of sulphides of iron and of nonferrous metals, into sulphur dioxide, SO2. As outlined above, the oxygen can be introduced in the gaseous stream in the form of air, or of oxygen-enriched air, or of pure oxygen. The quantity of ferric chloride in the form of vapour to be added to the gaseous stream must be determined from time to time as a function of the overall quantity of iron which is present in the raw material in sulphide form and must be, at any rate, such as to prevent the formation of ferric chloride.
In the latter connection, the best results are obtained if the quantity of ferric chloride vapour is from 0.1% to 5% relative to the volume of the gaseous stream.
The ferric chloride, in the quantity indicated above, can be added to the gaseous stream in the form of vapour, or it can be added in solid form directly to the raw material to be treated prior to feeding it to the reactor.
In the latter case, the ferric chloride admixed in solid form with the raw material to be treated, is directly vaporized in the reactor interior by the comparatively large quantity of heat evolved by the reaction.
According to the process of the present invention, the reaction may take place at a temperature of from 700'C to 1 200etc, so that the reaction velocity is very high, the best results being obtained at a temperature in the range of from 900 C to 950'C.
According to the process of the present invention, the reaction may take place under a pressure of from 1 to 5 atmospheres.
Inasmuch as the reaction is strongly exothermic and a large quantity of heat is evolved thereby, the reactor should be equipped with an adequate cooling system so as to keep the temperature constant in the reactor interior as far as practicable.
The best results are achieved by inserting at an appropriate location within the reactor an appropriate tube bundle through which pressurized water is caused to flow. Due to the effect of the large quantity of heat evolved by the reaction, the water in the interior of the tube bundle is heated and converted into high-temperature steam which can be collected and used to produce electrical power.
According to the process of the present invention, the reaction produces a solid residue, i.e. ash and a stream consisting of gases and vapours which make up the fumes.
The ash consists of ferric oxide (Fe203) and gangue (CaO, SiO2 and the like). Small quantities of chlorides of non-ferrous metals are occasionally present.
The fumes essentially consist of volatile chlorides of non-ferrous metals, unreacted chlorine and oxygen. Nitrogen and small amounts of ferric chloride may be present.
According to the process of this invention, the ash may be leached with water to recover the metallic chloride which may possibly be present, and may subsequently be treated so as to make them suitable for being used as a raw material in iron metallurgy. By fractional condensation, the chlorides of metals which are possibly present in vapour form can be stripped from the fumes.
The residual gaseous stream can be used directly for producing sulphuric acid.
As an alternative, sulphur dioxide can be stripped by liquefaction under a suitable pressure. In such a case the residual gaseous stream which still contains chlorine, oxygen and possibly nitrogen, can be directly recycled to the reactor.
The mixture of metallic chlorine which is recovered from the gaseous stream by fractional condensation can be treated conventionally by hydrometallurgical processes for separating the individual metallic chlorides which can subsequently be reduced to pure metals by hydrometallurgical or electrolytical methods.
As an alternative, the metallic chlorides which form the mixture separated from the gaseous stream of the fumes can be separated in an anhydrous form by fractional distillation and condensation, and can subsequently be reduced to metals by the direct electrolysis of the fused salts.
The chlorine which has been recovered by reducing the metallic chlorides to metals may be directly recycled to the reactor.

Claims (14)

1. A process for the treatment (integral dressing) of a raw material comprising one or more sulphides of non-ferrous metals, which comprises treating the material with a gaseous stream comprising gaseous chlorine and oxygen.
2. A process according to claim 1, wherein ferric chloride in solid form is added to the raw material, and wherein the raw material comprises iron sulphides and/or sulphides of non-ferrous metals.
3. A process according to claim 2, wherein the ferric chloride is added to the raw material in an amount of from 0. 1% to 5% by volume of the gaseous stream.
4. A process according to claim 1, 2 or 3, wherein the raw material, before being treated with the gaseous stream, is ground, floated and dried so that it has a particle size of from 50 microns to 1 mm.
5. A process according to any of claims 1 to 4, wherein the gaseous stream consists of chlorine and air, or of chlorine and oxygenenriched air, or of chlorine and pure oxygen.
6. A process according to claim 1, wherein the gaseous stream contains ferric chloride in vapour form in an amount of from 0. 1% to 5% by volume of the gaseous stream.
7. A process according to any of claims 1 to 3, wherein the chlorine and oxygen contents of the gaseous stream are determined as the sum of the amount of chlorine and oxygen which are respectively and stoichiometrically required to convert the sulphide(s) of the nonferrous metal contained in the raw material (excluding manganese sulphide) into the corresponding chlorides, and to convert the sulphides of iron and manganese into oxides and all of the sulphur contained in sulphide form into sulphur dioxide, the quantities so determined being multiplied by a coefficient of from 1 to 2.
8. A process according to any of claims 1 to 7, wherein the treatment is carried out in a fixed bed reactor, a fluid bed reactor or a rotary kiln.
9. A process according to claim 8, wherein the reactor or kiln has a cooling system.
1 0. A process according to any of claims 1 to 9, wherein the treatment is carried out at a temperature of from 700"C to 1 200 C.
11. A process according to claim 10, wherein the treatment is carried out at a temperature of about 950"C.
1 2. A process according to any of claims 1 to 11, wherein the non-ferrous metal chlorides are obtained in anhydrous form.
1 3. A process according to any of claims 1 to 12, wherein the treatment is carried out under a pressure of from 1 to 5 atmospheres.
14. A process according to any of claims 1 to 13, wherein there is obtained ash which consists of ferric oxide and gangues which are sufficiently pure as to be used in iron metallurgy as raw materials.
1 5. A process according to claim 1, substantially as hereinbefore described.
GB08223048A 1982-08-10 1982-08-10 Process for dressing sulphide- containing ores Withdrawn GB2125019A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB08223048A GB2125019A (en) 1982-08-10 1982-08-10 Process for dressing sulphide- containing ores
NL8203176A NL8203176A (en) 1982-08-10 1982-08-12 METHOD FOR PURIFYING SULFIDS CONTAINING ORES.
DE19823230252 DE3230252A1 (en) 1982-08-10 1982-08-13 METHOD FOR TREATING SULFIDE CONTAINING ORES

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB08223048A GB2125019A (en) 1982-08-10 1982-08-10 Process for dressing sulphide- containing ores
NL8203176A NL8203176A (en) 1982-08-10 1982-08-12 METHOD FOR PURIFYING SULFIDS CONTAINING ORES.
DE19823230252 DE3230252A1 (en) 1982-08-10 1982-08-13 METHOD FOR TREATING SULFIDE CONTAINING ORES

Publications (1)

Publication Number Publication Date
GB2125019A true GB2125019A (en) 1984-02-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
GB08223048A Withdrawn GB2125019A (en) 1982-08-10 1982-08-10 Process for dressing sulphide- containing ores

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DE (1) DE3230252A1 (en)
GB (1) GB2125019A (en)
NL (1) NL8203176A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2178419A (en) * 1985-07-24 1987-02-11 Nat Res Dev Zinc recovery from furnace dust

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB348665A (en) * 1929-11-18 1931-05-18 Comstock & Wescott Improvements in processes of treating iron ores
GB374250A (en) * 1931-05-26 1932-06-09 James Yate Johnson Improvements in the recovery of molybdenum, tungsten and vanadium from ores or the like
GB389005A (en) * 1931-10-03 1933-03-09 Intermetal Corp Improvements in method of chlorinating sulphide ores
GB802037A (en) * 1955-08-20 1958-09-24 Basf Ag Improvements in the chloridising roasting of raw materials containing iron and non-ferrous metals
GB1186836A (en) * 1968-06-25 1970-04-08 Boliden Ab A process for the purification by chlorination of roasted iron sulphide materials
GB1229424A (en) * 1967-03-18 1971-04-21
GB1322195A (en) * 1969-12-09 1973-07-04 Montedison Spa Puri''ation or pyrites and pyrrhotites ashes

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE957789C (en) * 1957-01-17 "Sachtleben" Aktiengesellschaft fur Berg bau und chemische Industrie, Köln Process for the chlorinating volatilization of zinc from ores containing zinc sulfide, burning and the like
DE1115465B (en) * 1958-04-11 1961-10-19 Ferrolegeringar Trollhetteverk Process for the treatment of sulphidic materials containing molybdenum
DE1180946B (en) * 1963-07-25 1964-11-05 Metallgesellschaft Ag Process for the continuous removal of non-ferrous metals which form volatilizable chlorides from ores containing them
NL6910302A (en) * 1968-07-08 1970-01-12
NL143992B (en) * 1968-07-26 1974-11-15 Montedison Spa METHOD OF CLEANING ASH OF PYRITE OR PYRRHOTITE.
SE331364B (en) * 1968-12-31 1970-12-21 Boliden Ab

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB348665A (en) * 1929-11-18 1931-05-18 Comstock & Wescott Improvements in processes of treating iron ores
GB374250A (en) * 1931-05-26 1932-06-09 James Yate Johnson Improvements in the recovery of molybdenum, tungsten and vanadium from ores or the like
GB389005A (en) * 1931-10-03 1933-03-09 Intermetal Corp Improvements in method of chlorinating sulphide ores
GB802037A (en) * 1955-08-20 1958-09-24 Basf Ag Improvements in the chloridising roasting of raw materials containing iron and non-ferrous metals
GB1229424A (en) * 1967-03-18 1971-04-21
GB1186836A (en) * 1968-06-25 1970-04-08 Boliden Ab A process for the purification by chlorination of roasted iron sulphide materials
GB1322195A (en) * 1969-12-09 1973-07-04 Montedison Spa Puri''ation or pyrites and pyrrhotites ashes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2178419A (en) * 1985-07-24 1987-02-11 Nat Res Dev Zinc recovery from furnace dust
US4800069A (en) * 1985-07-24 1989-01-24 National Research Development Corporation Zinc recovery from furnace dust

Also Published As

Publication number Publication date
NL8203176A (en) 1984-03-01
DE3230252A1 (en) 1984-03-15

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