WO2014015402A1 - Recovery of base metals from sulphide ores and concentrates - Google Patents
Recovery of base metals from sulphide ores and concentrates Download PDFInfo
- Publication number
- WO2014015402A1 WO2014015402A1 PCT/BR2013/000262 BR2013000262W WO2014015402A1 WO 2014015402 A1 WO2014015402 A1 WO 2014015402A1 BR 2013000262 W BR2013000262 W BR 2013000262W WO 2014015402 A1 WO2014015402 A1 WO 2014015402A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- base metals
- concentrates
- recovery
- sulphide ores
- pulp
- Prior art date
Links
- 239000010953 base metal Substances 0.000 title claims abstract description 36
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000012141 concentrate Substances 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 241000237519 Bivalvia Species 0.000 claims 1
- 235000020639 clam Nutrition 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 25
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 16
- 238000000605 extraction Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005188 flotation Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000282372 Panthera onca Species 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- -1 Collector Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005456 ore beneficiation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
Definitions
- This invention relates to the recovery of base metals from sulphide ores and concentrates.
- US3,919,079 describes a process of flotation of sulphide minerals from sulphide bearing ore.
- the disadvantage of this process consists in the flotation process which use complex reagents: Dispersant, Collector, Alkali, Floculants.
- the complex reagents used in the flotation can cause environmental impact due to chemical oxygen demand for the decomposition of these reagents.
- the present invention does not requires complex reagents.
- US5,281,252 describes a conversion of non-ferrous sulfides which requires the insufflation of the copper sulphide particles and this process requires a complex control of agitation levels and contact of solid / liquid. Further, it requires the control of the internal atmosphere to ensure the reduction of the copper and the power supply for the reaction.
- US4,308,058 describes a process for the oxidation of molten low-iron metal matte to produce raw metal. This process, however, requires multiple furnace operations as well as high temperatures (> 1000 °C) which involves high energy consumption. However these conventional processes become very expensive when dealing with low grade material and ores with high impurities content like chlorine and fluorine. Another problem with pyrometallurgical processing is the high capital of costs of a new plant, environmental, issues and high energy consumption.
- the gases resulting (dust; C0 2 ; NOx; H 2 0) from the process must be treated before sending the S0 2 to a sulphuric acid plant.
- Alternative methods comprise burning the concentrate.
- the present invention provides an advantageous and effective a process of indirect and selective sulfation of base metals in the form of sulfides.
- This process can be applied for both concentrates or for low-grade sulfide ores; the greater focus being on the latter.
- Low-grade sulfide ores usually do not reach the desired content in the concentrate; and when they hit it, big losses happen. Impurities are the major problem. For this reason, the process described herein had been proposed.
- the present invention discloses a recovery of base metals from sulphide ores and concentrates, which comprises mixing the base metal's ore with ferric salts whose ratios are between 50% and 200% to base metals, heating the said mixture to temperatures between 400°C and 600°C for a period of 2 to 8 hours; adding water to form a pulp, then stirring and filtering the pulp.
- the process of the present invention involves mixing the ore, concentrate or other sulphide material containing base metals with ferric sulfate or chloride in a screw mixer.
- the salt can come in a hydrated or anhydrous form.
- the mixture may have a ratio of 1 :0.001 to 1 : 1000 of the sulphide material and the anhydrous salt. If a hydrated salt is used, the ratios may be changed proportionally.
- Preferred ratios are between 50% and 200% to base metals considering the stoichiometry, preferably between 90 and 120% for the anhydrous form. It is a particularly attractive process once the deposit of the sulphide content is low and the concentration by flotation does not produce a concentrate of good quality. It is also effective if the concentration of fluorine and chlorine are above the specification limits.
- This final mixture is later taken to a kiln, a furnace or any other equipment known by those skilled in the art, providing enough heat to reach temperatures preferably between 400°C and 600°C, more preferably between 400°C and 500 °C at atmospheric pressure in any kind of mixing apparatus. At that temperature, the following reaction occurs for a generic base metal sulphide:
- Base metals are preferably copper, nickel and zinc, more preferably nickel.
- Ferric sulfate is used as an example, as ferric chloride may also be used, changing reaction stoichiometry.
- Residence time is estimated to be preferably between 2 and 8 hours, more preferably for a period of 5 to 6 hours.
- ferric sulfate can be done in several ways by those skilled in the art.
- oxide material can also be added to this mixture, providing the following reaction:
- Base metals are preferably copper, nickel and zinc, more preferably nickel.
- the above reaction would capture S0 2 , avoiding gas scrubbing.
- a borate source such as, for example, boric acid, amorphous silica or any other reagent known by those skilled in the art can be added.
- the final product from the kiln is taken to a dissolution stage, in order to solubilize most or all of the base metal salts. It is mixed with water to form a pulp of 10%-33% solids, preferably between 20% and 30%.
- the pulp should be kept under stirring for a period of 1-5 hours, preferably between 2 and 4 hours. From that point, any downstream choice, also known by those skilled in the art, can be selected for further processing and purification of the base metals.
- aspects of the process of the present invention involve mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate at a temperature between 400°C and 600°C and for a period of 2 to 8 hours.
- the salt e.g. ferric chloride or sulfate
- mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate is at a temperature between 400°C and 500 °C and for a period of 5 to 6 hours, obtaining the Ni sulfates or chlorides that are taken to the dissolution stage.
- the Ni sulfates and chlorides may be taken directly to the dissolution stage. The process enables the achievement of a very stable residue (hematite) and the rapid dissolution of salts. It is estimated that the efficiency is between 80 and 95%
- the user sets whether to produce a high purity, such as electrolytic nickel, or an intermediate product as MHP.
- a high purity such as electrolytic nickel, or an intermediate product as MHP.
- These options are not exhaustive, but only examples of downstream. This downstream would be greatly simplified, since the step of removing impurities from solution (such as Fe and Al) is no longer necessary.
- the advantages of the process of the present invention are numerous and may include: better deposit exploration including deposits of low-sulfide which would not be economically viable for conventional flotation processes;
- the acidity of the solution obtained is low, reducing the need for neutralization.
- NiS+ 3NiO + Fe2(S04)3+ 202(g) ; 4NiS04+ Fe203
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a new recovery of base metals from sulphide ores and concentrates, which comprises mixing the base metal's ore with ferric salts, heating the said mixture; adding water to form a pulp, stirring and filtering the pulp.
Description
RECOVERY OF BASE METALS FROM SULPHIDE ORES AND
CONCENTRATES
This application claims priority from U.S. Patent Application No. 61/674,624, titled "Recovery of Base Metals from Sulphide Ores and Concentrates," filed on July 23, 2012, and which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION
This invention relates to the recovery of base metals from sulphide ores and concentrates.
Conventional processing of base metals sulphide ores includes flotation and pyrometallurgical techniques as smelting of concentrates. US4,283,017 describes a selective flotation of cubanite and chalcopyrite from copper/nickel mineralized rock. The disadvantage of this process consists in the ore beneficiation process, which requires high energy consume in order to reach very fine particles. The present invention can be fed with coarse particles.
US3,919,079 describes a process of flotation of sulphide minerals from sulphide bearing ore. The disadvantage of this process consists in the flotation process which use complex reagents: Dispersant, Collector, Alkali, Floculants. The complex reagents used in the flotation can cause environmental impact due to chemical oxygen demand for the decomposition of these reagents. The present invention does not requires complex reagents. US5,281,252 describes a conversion of non-ferrous sulfides which requires the insufflation of the copper sulphide particles and this process requires a complex control of agitation levels and contact of solid / liquid. Further, it requires the control of the internal atmosphere to ensure the reduction of the copper and the power supply for the reaction. US4,308,058 describes a process for the oxidation of molten low-iron metal matte to produce raw metal. This process, however, requires multiple furnace operations as well as high temperatures (> 1000 °C) which involves high energy consumption.
However these conventional processes become very expensive when dealing with low grade material and ores with high impurities content like chlorine and fluorine. Another problem with pyrometallurgical processing is the high capital of costs of a new plant, environmental, issues and high energy consumption.
Usually, when dealing with low grade material and ores with high impurities content, the gases resulting (dust; C02; NOx; H20) from the process must be treated before sending the S02 to a sulphuric acid plant. Alternative methods comprise burning the concentrate.
BRIEF DESCRIPTION OF THE INVENTION
In light of the above described problems and unmet needs, the present invention provides an advantageous and effective a process of indirect and selective sulfation of base metals in the form of sulfides. This process can be applied for both concentrates or for low-grade sulfide ores; the greater focus being on the latter. Low-grade sulfide ores usually do not reach the desired content in the concentrate; and when they hit it, big losses happen. Impurities are the major problem. For this reason, the process described herein had been proposed.
More specifically, the present invention discloses a recovery of base metals from sulphide ores and concentrates, which comprises mixing the base metal's ore with ferric salts whose ratios are between 50% and 200% to base metals, heating the said mixture to temperatures between 400°C and 600°C for a period of 2 to 8 hours; adding water to form a pulp, then stirring and filtering the pulp.
Additional advantages and novel features of these aspects of the invention will be set forth in part in the description that follows, and in part will become more apparent to those skilled in the art upon examination of the following or upon learning by practice of the invention. DETAILED DESCRIPTION OF THE INVENTION
The following detailed description does not intend to, in any way, limit the scope, applicability or configuration of the invention. More exactly, the following description provides the necessary understanding for implementing the exemplary modalities. When using the teachings provided herein, those skilled in the art will
recognize suitable alternatives that can be used, without extrapolating the scope of the present invention.
The process of the present invention involves mixing the ore, concentrate or other sulphide material containing base metals with ferric sulfate or chloride in a screw mixer. The salt can come in a hydrated or anhydrous form. The mixture may have a ratio of 1 :0.001 to 1 : 1000 of the sulphide material and the anhydrous salt. If a hydrated salt is used, the ratios may be changed proportionally.
Preferred ratios are between 50% and 200% to base metals considering the stoichiometry, preferably between 90 and 120% for the anhydrous form. It is a particularly attractive process once the deposit of the sulphide content is low and the concentration by flotation does not produce a concentrate of good quality. It is also effective if the concentration of fluorine and chlorine are above the specification limits.
This final mixture is later taken to a kiln, a furnace or any other equipment known by those skilled in the art, providing enough heat to reach temperatures preferably between 400°C and 600°C, more preferably between 400°C and 500 °C at atmospheric pressure in any kind of mixing apparatus. At that temperature, the following reaction occurs for a generic base metal sulphide:
3 MS + Fe2(S04)3 + 4.5 02 = 3 NiS04 + Fe203 + 3 S02
(where M represents a base metal).
Base metals are preferably copper, nickel and zinc, more preferably nickel. Ferric sulfate is used as an example, as ferric chloride may also be used, changing reaction stoichiometry. Residence time is estimated to be preferably between 2 and 8 hours, more preferably for a period of 5 to 6 hours.
The production of ferric sulfate can be done in several ways by those skilled in the art. Alternatively, oxide material can also be added to this mixture, providing the following reaction:
MS + 3 MO + Fe2(S04)3 + 2 02 = 4 NiS04 + Fe203
(where M represents a base metal).
Base metals are preferably copper, nickel and zinc, more preferably nickel.
The above reaction would capture S02, avoiding gas scrubbing. To capture fluorine or chlorine in solid form, a borate source such as, for example, boric acid, amorphous silica or any other reagent known by those skilled in the art can be added. The final product from the kiln is taken to a dissolution stage, in order to solubilize most or all of the base metal salts. It is mixed with water to form a pulp of 10%-33% solids, preferably between 20% and 30%. The pulp should be kept under stirring for a period of 1-5 hours, preferably between 2 and 4 hours. From that point, any downstream choice, also known by those skilled in the art, can be selected for further processing and purification of the base metals.
Therefore, aspects of the process of the present invention involve mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate at a temperature between 400°C and 600°C and for a period of 2 to 8 hours.
In a preferred embodiment of the present invention, mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate is at a temperature between 400°C and 500 °C and for a period of 5 to 6 hours, obtaining the Ni sulfates or chlorides that are taken to the dissolution stage. According to various aspects, the Ni sulfates and chlorides may be taken directly to the dissolution stage. The process enables the achievement of a very stable residue (hematite) and the rapid dissolution of salts. It is estimated that the efficiency is between 80 and 95%
Optionally, conventional downstream processes such as production of MHP and electrolysis can be used after the present process in view to obtain the product of any kind of interest.
The user sets whether to produce a high purity, such as electrolytic nickel, or an intermediate product as MHP. These options are not exhaustive, but only examples of downstream. This downstream would be greatly simplified, since the step of removing impurities from solution (such as Fe and Al) is no longer necessary.
The advantages of the process of the present invention are numerous and may include: better deposit exploration including deposits of low-sulfide which would not be economically viable for conventional flotation processes;
reduced acid consumption;
better settling properties of pulp;
reduced consumption of flocculants;
high levels of fluorine and chlorine would be no problem in the process of the present invention;
This process is selective for the base metals. Thus, impurities such as iron and aluminum are not dissolved and these impurities in the conventional process downstream produce hydroxides which are very bulky and hard to decanting. As these elements are stable oxides (in the case of iron, are expected to stabilize as hematite), both the amount of solids formed would be lower as the ease of decanting of solid would be faster, thereby reducing the consumption of flocculants;
The acidity of the solution obtained is low, reducing the need for neutralization.
Below, are shown the thermodynamic data of the reactions proposed (for nickel and copper).
3CuS + Fe2(S04)3+4.502(g) = 3CuS04+ Fe203 +
3S02(g)
T deltaH deltas deltaG K Log(K) c kcal cal/K kcal
0.000 -304.425 -64.106 -286.915 3.820E+229 229.582
100.000 -304.796 -65.321 -280.422 1.793E+164 164.254
200.000 -304.640 -64.969 -273.900 3.357E+126 126.526
300.000 -304.226 -64.181 -267.440 9.707E+101 101.987
400.000 -303.612 -63.198 -261.071 5.863E+084 84.768
500.000 -302.857 -62.154 -254.803 1.077E+072 72.032
600.000 -301.954 -61.058 -248.641 1.739E+062 62.240
700.000 -300.882 -59.895 -242.596 3.066E- )54 54.487
800.000 -300.560 -59.577 -236.625 1.561E+048 48.193
900.000 -300.441 -59.470 -230.674 9.473E+042 42.976
1000.000 -300.432 -59.462 -224.728 3.803E+O38 38.580
NiS+ 3NiO + Fe2(S04)3+ 202(g) ; = 4NiS04+ Fe203
T deltaH deltas deltaG K Log(K)
C kcal cal/K kcal
0.000 -220.408 -93.107 -194.976 1.034E+156 156.015
100.000 -220.330 -92.921 -185.656 5.570E+108 108.746
200.000 -220.086 -92.330 -176.400 3.066E O81 81.487
300.000 -219.978 -92.150 -167.162 5.578E+063 63.746
400.000 -220.766 -93.311 -157.954 1.935E+051 51.287
500.000 -219.711 -91.854 -148.695 1.086E+042 42.036
600.000 -218.366 -90.221 -139.589 8.751E+034 34.942
700.000 -216.651 -88.363 -130.660 2.219E+ 29 29.346
800.000 -215.462 -87.199 -121.884 6.669E+024 24.824
900.000 -214.234 -86.106 -113.219 1.241E+021 21.094
1000.000 -220.102 -90.782 -104.524 8.792E+017 17.944
CuS + 3CuO + Fe2(S04)3+ 202(g) i = 4CuS04+ Fe203
T deltaH deltas deltaG K Log(K)
C kcal cal/K kcal
0.000 -191.154 -92.312 -165.939 6.034E+132 132.781
100.000 -191.055 -92.055 -156.704 6.132E+091 91.788
200.000 -190.411 -90.547 -147.568 1.472E-K)68 68.168
300.000 -189.440 -88.694 -138.605 7.182E 052 52.856
400.000 -188.215 -86.730 -129.833 1.432E+042 42.156
500.000 -186.776 -84.740 -121.260 1.905E 034 34.280
600.000 -185.114 -82.721 -112.886 1.810E4O28 28.258
700.000 -183.215 -80.662 -104.719 3.309E+023 23.520
800.000 -181.998 -79.469 -96.716 4.989E-KD19 19.698
900.000 -180.917 -78.506 -88.818 3.528E+016 16.548
1000.000 -179.881 -77.658 -81.011 8.082E+013 13.907
As can be seeing, the data above show that the reactions are thermodynamically favorable.
EXAMPLE 1. Jaguar ore, having the composition described in the table below, was mixed to ferric sulfate in the proportion of 200 grams of ore to 2.5 grams of anhydrous ferric sulfate (stoichiometric). After proper homogenization, the mixture was subjected to temperatures of 500 °C for 3 hours. After complete cooling of the material, water was added to form a pulp of 30% solids and the mixture was stirred for 1 hour.
The pulp was filtered and samples of the residue and of the PLS were sent for chemical analysis. Results indicated 85% nickel extraction, 77% copper extraction and 88% of cobalt extraction. Iron and other impurities were below 1%, with the exception of manganese, which obtained 97% extraction.
Claims
1. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, wherein the recovery comprises mixing the base metal's ore with ferric salts whose ratios are between 50% and 200% to base metals, heating the said mixture to temperatures between 400°C and 600°C for a period of 2 to 8 hours; adding water to form a pulp; the said pulp is stirred and filtered.
2. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1 , wherein the base metals are preferably copper, nickel and zinc.
3. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claims 1 and 2, wherein the base metal is nickel.
4. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1, wherein the ferric salt comprises ferric sulphide, ferric chloride, or a mixture thereof.
5. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1, wherein the ratio between the ferric salt are between 90 and 120% to base metals.
6. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1, wherein the mixture is heated to temperatures between 400°C and 500°C for a period of 5 to 6 hours.
7. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1, wherein the water added to the mixture form a pulp of 10% to 33% solids.
8. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claims 1 and 7, wherein the water added to the mixture form a pulp of 20% to 30% solids.
9. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claim 1, wherein the pulp is under stirring for a period of 1 to 5 hours.
10. RECOVERY OF BASE METALS FROM SULPHIDE ORES AND CONCENTRATES, according to the claims 1 and 9, wherein the pulp is under stirring for a period 2 to 4 hours.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201380039461.3A CN105392907A (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
| AU2013296080A AU2013296080B2 (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
| EP13747955.6A EP2875160A1 (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
| JP2015523350A JP6169692B2 (en) | 2012-07-23 | 2013-07-22 | Method for recovering base metals from sulfide ores and concentrates |
| KR20157004351A KR20150036720A (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
| RU2015105799A RU2628183C2 (en) | 2012-07-23 | 2013-07-22 | Extraction of basic metals from sulfide ores and concentrates |
| BR112015001602A BR112015001602A2 (en) | 2012-07-23 | 2013-07-22 | RECOVERY OF BASE METALS FROM ORE AND SULPHIDE CONCENTRATES |
| IN973DEN2015 IN2015DN00973A (en) | 2012-07-23 | 2013-07-22 | |
| CA2879877A CA2879877A1 (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
| CUP2015000008A CU24204B1 (en) | 2012-07-23 | 2015-01-22 | PROCEDURE FOR THE RECOVERY OF BASE METALS FROM SULFIDE MINERALS AND CONCENTRATES |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261674624P | 2012-07-23 | 2012-07-23 | |
| US61/674,624 | 2012-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014015402A1 true WO2014015402A1 (en) | 2014-01-30 |
Family
ID=48979491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2013/000262 WO2014015402A1 (en) | 2012-07-23 | 2013-07-22 | Recovery of base metals from sulphide ores and concentrates |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US9169534B2 (en) |
| EP (1) | EP2875160A1 (en) |
| JP (1) | JP6169692B2 (en) |
| KR (1) | KR20150036720A (en) |
| CN (1) | CN105392907A (en) |
| AR (1) | AR091869A1 (en) |
| AU (1) | AU2013296080B2 (en) |
| BR (1) | BR112015001602A2 (en) |
| CA (1) | CA2879877A1 (en) |
| CL (1) | CL2015000180A1 (en) |
| CU (1) | CU24204B1 (en) |
| DO (1) | DOP2015000017A (en) |
| IN (1) | IN2015DN00973A (en) |
| RU (1) | RU2628183C2 (en) |
| TW (1) | TWI573879B (en) |
| WO (1) | WO2014015402A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111394571B (en) * | 2020-04-17 | 2022-02-15 | 包头稀土研究院 | Method for improving decomposition efficiency of rare earth mineral and sulfuric acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1943332A (en) * | 1930-12-30 | 1934-01-16 | Lafayette M Hughes | Method of chloridizing ores by means of ferric chloride |
| US3839013A (en) * | 1973-06-18 | 1974-10-01 | Steel Corp | Copper recovery from lean sulfide ores |
| US4144056A (en) * | 1978-05-04 | 1979-03-13 | Cato Research Corp. | Process for recovering nickel, cobalt and manganese from their oxide and silicate ores |
| WO1999063121A1 (en) * | 1998-06-04 | 1999-12-09 | Jussi Rastas | Melt and melt coating sulphation process |
| US20110142736A1 (en) * | 2009-07-14 | 2011-06-16 | Vale S.A. | Process of recovery of base metals from oxide ores |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919079A (en) | 1972-06-28 | 1975-11-11 | David Weston | Flotation of sulphide minerals from sulphide bearing ore |
| FI65088C (en) * | 1979-05-25 | 1984-03-12 | Pekka Juhani Saikkonen | FOERFARANDE FOER AOTERVINNING AV ICKE-JAERNMETALLER UR DERAS MINERALIER MINERALSLIG OXIDISKA ROSTNINGSPRODUKTER OCH SLAGG |
| FI64190C (en) | 1979-06-20 | 1983-10-10 | Outokumpu Oy | OXIDATION OF SMALL METAL METALS FOR RAW METAL |
| US4283017A (en) | 1979-09-07 | 1981-08-11 | Amax Inc. | Selective flotation of cubanite and chalcopyrite from copper/nickel mineralized rock |
| JPS5928533A (en) * | 1982-08-06 | 1984-02-15 | サミム・ソチエタ−・アヂオナ−リア・ミネ−ロ・メタルルジカ・エツセ・ピ・ア | Ore selection of sulfide-containing ore |
| CN1079207A (en) * | 1992-05-27 | 1993-12-08 | 何柱生 | The production technique of copper sulfate and fluidizing reactor thereof |
| US5281252A (en) | 1992-12-18 | 1994-01-25 | Inco Limited | Conversion of non-ferrous sulfides |
| US5650057A (en) * | 1993-07-29 | 1997-07-22 | Cominco Engineering Services Ltd. | Chloride assisted hydrometallurgical extraction of metal |
| US5709730A (en) * | 1995-01-23 | 1998-01-20 | Cashman; Joseph B. | Hydrometallurgical processing of flue dust |
| CN1237641A (en) * | 1999-06-15 | 1999-12-08 | 吉林省冶金研究院 | Technological process for extracting Ni, Cu, Co and Mg from nickel sulfide preparation concentrate and making nickelferrite |
| ZA200802808B (en) * | 2005-11-28 | 2009-10-28 | Anglo Operations Ltd | Leaching process in the presence of hydrochloric acid for the recovery of a value metal from an ore |
| CN100999787A (en) * | 2006-12-29 | 2007-07-18 | 金川集团有限公司 | Process of nickle cobait double salt sulfated baking acid immersion |
| CN100582264C (en) * | 2008-03-18 | 2010-01-20 | 贵研铂业股份有限公司 | Method for extracting metallic nickel cobalt from irony nickel mine |
| CN102181662A (en) * | 2011-04-21 | 2011-09-14 | 北京矿冶研究总院 | Smelting method of low-sulfur copper concentrate |
-
2013
- 2013-07-22 KR KR20157004351A patent/KR20150036720A/en not_active Application Discontinuation
- 2013-07-22 IN IN973DEN2015 patent/IN2015DN00973A/en unknown
- 2013-07-22 WO PCT/BR2013/000262 patent/WO2014015402A1/en active Application Filing
- 2013-07-22 BR BR112015001602A patent/BR112015001602A2/en not_active IP Right Cessation
- 2013-07-22 CN CN201380039461.3A patent/CN105392907A/en active Pending
- 2013-07-22 JP JP2015523350A patent/JP6169692B2/en not_active Expired - Fee Related
- 2013-07-22 EP EP13747955.6A patent/EP2875160A1/en not_active Withdrawn
- 2013-07-22 RU RU2015105799A patent/RU2628183C2/en not_active IP Right Cessation
- 2013-07-22 CA CA2879877A patent/CA2879877A1/en not_active Abandoned
- 2013-07-22 AU AU2013296080A patent/AU2013296080B2/en not_active Ceased
- 2013-07-23 US US13/948,929 patent/US9169534B2/en not_active Expired - Fee Related
- 2013-07-23 AR ARP130102611A patent/AR091869A1/en unknown
- 2013-07-23 TW TW102126363A patent/TWI573879B/en not_active IP Right Cessation
-
2015
- 2015-01-22 DO DO2015000017A patent/DOP2015000017A/en unknown
- 2015-01-22 CU CUP2015000008A patent/CU24204B1/en active IP Right Grant
- 2015-01-23 CL CL2015000180A patent/CL2015000180A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1943332A (en) * | 1930-12-30 | 1934-01-16 | Lafayette M Hughes | Method of chloridizing ores by means of ferric chloride |
| US3839013A (en) * | 1973-06-18 | 1974-10-01 | Steel Corp | Copper recovery from lean sulfide ores |
| US4144056A (en) * | 1978-05-04 | 1979-03-13 | Cato Research Corp. | Process for recovering nickel, cobalt and manganese from their oxide and silicate ores |
| WO1999063121A1 (en) * | 1998-06-04 | 1999-12-09 | Jussi Rastas | Melt and melt coating sulphation process |
| US20110142736A1 (en) * | 2009-07-14 | 2011-06-16 | Vale S.A. | Process of recovery of base metals from oxide ores |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015527492A (en) | 2015-09-17 |
| US9169534B2 (en) | 2015-10-27 |
| EP2875160A1 (en) | 2015-05-27 |
| CU20150008A7 (en) | 2015-08-27 |
| CU24204B1 (en) | 2016-10-28 |
| TW201408786A (en) | 2014-03-01 |
| JP6169692B2 (en) | 2017-07-26 |
| IN2015DN00973A (en) | 2015-06-12 |
| AU2013296080A1 (en) | 2015-02-12 |
| KR20150036720A (en) | 2015-04-07 |
| RU2015105799A (en) | 2016-09-10 |
| CA2879877A1 (en) | 2014-01-30 |
| AU2013296080B2 (en) | 2017-02-02 |
| AR091869A1 (en) | 2015-03-04 |
| CN105392907A (en) | 2016-03-09 |
| US20140020510A1 (en) | 2014-01-23 |
| TWI573879B (en) | 2017-03-11 |
| RU2628183C2 (en) | 2017-08-15 |
| DOP2015000017A (en) | 2017-08-31 |
| BR112015001602A2 (en) | 2017-08-22 |
| CL2015000180A1 (en) | 2015-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Study of extraction and purification of Ni, Co and Mn from spent battery material | |
| Wang et al. | Recovery of soluble manganese from electrolyte manganese residue using a combination of ammonia and CO2 | |
| JP4880909B2 (en) | Purification method for removing sulfur from nickel compounds or cobalt compounds, and ferronickel production method | |
| Van Schalkwyk et al. | Leaching of Ni–Cu–Fe–S converter matte at varying iron endpoints; mineralogical changes and behaviour of Ir, Rh and Ru | |
| Zhang et al. | Recovery of valuable metals from copper slag | |
| KR102460982B1 (en) | metal recovery from pyrite | |
| Dreisinger | Keynote address: Hydrometallurgical process development for complex ores and concentrates | |
| WO2020107122A1 (en) | Process for the recovery of value metals from zinc-bearing ores, concentrates, intermediates and wastes | |
| Kumar et al. | Recovery of cadmium from hydrometallurgical zinc smelter by selective leaching | |
| Lin et al. | One-step extraction of bismuth from bismuthinite in sodium carbonate–sodium chloride molten salt using ferric oxide as sulfur-fixing agent | |
| CN104203830B (en) | The manufacture method of ferrum bloodstone processed | |
| AU2013296080B2 (en) | Recovery of base metals from sulphide ores and concentrates | |
| Li et al. | A near-zero waste process for the full-component utilization of deep-sea polymetallic nodules based on reductive leaching with SO2 followed by separation and recovery | |
| JP6683910B2 (en) | Purification method of nickel chloride aqueous solution | |
| Mu et al. | Eco-friendly and selective separation of nickel and copper from low-grade nickel sulfide ore via sulfur fixation roasting with MgCO3 followed by sulfuric acid leaching | |
| WO2020075288A1 (en) | Method and device for processing nickel oxide ore | |
| Lucas et al. | Conditioning of bauxite residue with bottom ash in view of recovery of valuable metals: A sustainable approach | |
| Agapova et al. | Electrochemical processing of metal wastes of rhenium-containing heat-resistant nickel alloys | |
| D Turan et al. | An alternative approach for the metal production from copper slag | |
| Mayhew et al. | Nickel and cobalt recovery from Mesaba concentrate | |
| Lakshmanan et al. | Application of mixed chloride technology for the recovery of TiO2 and base metals | |
| RU2484154C1 (en) | Processing wastes containing nonferrous and platinum metals | |
| WO2023119017A1 (en) | Hydrogen-based valorisation of metal-containing feed materials to extract metals | |
| Sepulveda et al. | Leaching of white metal in a NaCl-H2SO4 system under environmental conditions | |
| Kaya | Impurity Purification Before Electrowinning |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 201380039461.3 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13747955 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2879877 Country of ref document: CA Ref document number: 2015523350 Country of ref document: JP Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: IDP00201500367 Country of ref document: ID |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2015000180 Country of ref document: CL |
|
| ENP | Entry into the national phase |
Ref document number: 2013296080 Country of ref document: AU Date of ref document: 20130722 Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 20157004351 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2013747955 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2015105799 Country of ref document: RU Kind code of ref document: A |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015001602 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 112015001602 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150123 |