WO2020107122A1 - Procédé de récupération de métaux de valeur à partir de minerais, de concentrats, d'intermédiaires et de déchets contenant du zinc - Google Patents

Procédé de récupération de métaux de valeur à partir de minerais, de concentrats, d'intermédiaires et de déchets contenant du zinc Download PDF

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WO2020107122A1
WO2020107122A1 PCT/CA2019/051710 CA2019051710W WO2020107122A1 WO 2020107122 A1 WO2020107122 A1 WO 2020107122A1 CA 2019051710 W CA2019051710 W CA 2019051710W WO 2020107122 A1 WO2020107122 A1 WO 2020107122A1
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Prior art keywords
zinc
iron
metals
leaching
lead
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PCT/CA2019/051710
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English (en)
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Bryn Harris
Carl White
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9203-5468 Quebec Inc. Dba Nmr360
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Publication of WO2020107122A1 publication Critical patent/WO2020107122A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • 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
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B19/28—Obtaining zinc or zinc oxide from muffle furnace residues
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0004—Crystallisation cooling by heat exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates generally to processes for the recovery of zinc and associated value metals, such as lead, silver, copper, manganese, iron and cadmium in a marketable form from various zinc-bearing feedstocks.
  • Primary zinc is generally recovered from ores and concentrates either pyrometallurgically by smelting, hydrometallurgically by pressure leaching combined with electrowinning, or a combination thereof by roasting and atmospheric leaching together with electrowinning (the so-called RLE process). All of these processes have significant issues with sulphur in one way or another, resulting in the requirement for either a sulphuric acid plant, or a method of disposing of the excess sulphate. Disposal practices focus on the formation of jarosite, an iron-sulphate compound, or gypsum, both of which result in the need for dedicated large tailings ponds. Other valuable metals, such as silver, lead, copper and cadmium in zinc concentrates are generally not recovered, or are recovered as impure by-products, or disposed of.
  • a number of pyrometallurgical and hydrometallurgical techniques have been developed for recovering zinc and associated metals such as lead, silver, cadmium, copper and iron from various intermediate zinc-bearing sources, especially from steel plant EAFD (Electric Arc Furnace Dust).
  • W.P.C. Duyvesteyn and M.C. Jha in U.S. Patent 4,572,771 issued to Amax Inc. on February 25, 1986 entitled“ Zinc Recovery from Steel Plant Dusts and Zinciferous Materials”, describe a process wherein a zinc-bearing residue, and especially EAF dust, is leached with hydrochloric acid to provide a pregnant liquor containing zinc, iron, and lead.
  • the iron and other impurities such as lead are selectively removed from the pregnant liquor by precipitation with lime, and the zinc extracted from the purified liquor by solvent extraction.
  • the zinc is subsequently stripped from the organic solvent using water or hydrochloric acid to provide a zinc chloride solution which is then fed to an electrowinning cell for the production of marketable electrolytic zinc.
  • Chlorine gas from zinc electrowinning is burned with hydrogen to reconstitute the hydrochloric acid for recycle to the leaching stage.
  • Zinc chloride is very soluble (1800 g/L or 27M at 20°C), such that 18% acid ( ⁇ 6M) is very dilute in comparison, and does not take advantage of the high zinc solubility, therefore leading to appreciable water balance issues.
  • Spent zinc pickle liquor is the waste product containing zinc and ferrous chlorides from steel plant galvanizing pickling lines. At the present time, there is no method for treating this, and it is commonly disposed of by deep well injection.
  • Steel plant spent pickle liquor is a waste material containing predominantly ferrous chloride.
  • Current methodology for treating this is via spray or fluid bed roasting, which is costly and is only able recover acid at a strength of 18%, rather than concentrated acid at 33- 35% strength.
  • the invention is directed to a process for recovering zinc and associated value metals from zinc-bearing feed material, the process comprising:
  • the process may further comprise oxidising the solution containing iron to convert ferrous iron to ferric iron, the iron in the solution being predominantly in its ferric state or brought to ferric state.
  • the oxidation of ferrous iron is carried out electrolytically, including by adding HC1 if necessary.
  • the feed material may comprise other metals selected from the group consisting of copper, silver, lead, cadmium, manganese and magnesium, the process further comprising leaching the resulting solids in dilute hydrochloric acid to effect re-dissolution of at least one of copper, silver, lead, cadmium, manganese and magnesium, if present.
  • the amount of hydrochloric acid as used is at least stoichiometric for the other metals present.
  • the process may further comprise treating the fdtrate from zinc precipitation using pyrohydrolysis to recover HC1.
  • a part of HC1 recovered by pyrohydrolysis is recycled within the process.
  • the feed material is electric arc furnace dust (EAFD), or a complex lead-zinc-copper-silver ore or concentrate.
  • EAFD electric arc furnace dust
  • the spent zinc pickle liquor may be added to the electric arc furnace dust to provide additional iron and a portion of the HC1 leaching medium.
  • the leaching step is performed at a temperature of 25-110°C, preferably 80-100°C, more preferably 90-95°C.
  • the leachate is cooled to crystallise out lead chloride.
  • step (d) the ferric solution is heated to a temperature of about 170-200°C, preferably about 180-190°C, in order to effect the hydrolysis of ferric iron and precipitation of hematite.
  • the reaction in step (d) may be allowed to proceed until no more HC1 is evolved. More preferably, water or steam may be added at the end of the reaction in step (d) to ensure complete hydrolysis of all metals present except zinc, calcium and the alkali metals which do not hydrolyse.
  • the amount of water used in the quenching step (e) is controlled to produce a magnesium chloride solution of 30 wt.% to 50 wt.%, when magnesium is present in the feed material.
  • a process for treating zinc bearing ores, concentrates, intermediates or residues, and in particular from steel plant toxic wastes such as electric arc furnace dust (EAFD) and spent pickle liquors is disclosed.
  • EAFD electric arc furnace dust
  • Such materials may contain lead, silver, cadmium, calcium, magnesium, manganese, aluminium and copper in addition to iron and zinc, all of which can be recovered in a marketable form, thereby maximising the value of the feed material.
  • EAFD electric arc furnace dust
  • the process applies to electric arc furnace dust (EAFD) and complex zinc- bearing ores and concentrates, and combined with SPL/ZPL (steel plant spent pickle and zinc pickle liquors).
  • EAFD electric arc furnace dust
  • SPL/ZPL steel plant spent pickle and zinc pickle liquors
  • the process combines EAFD and ZPL more efficiently than treating either on their own.
  • feed materials may be advantageously combined with other steel plant wastes where appropriate, in particular spent zinc pickle liquor (ZPL) and/or spent pickle liquor (SPL). It is a further aspect of the invention that addition of ZPL or ZPL/SPL significantly improves the water balance of the process.
  • ZPL spent zinc pickle liquor
  • SPL spent pickle liquor
  • Figure 1 is a flowchart illustrating the process according to a preferred embodiment
  • Figure 2 is a flowchart illustrating the process according to another preferred embodiment.
  • Figure 3 is a flowchart illustrating the process according to yet another preferred embodiment.
  • % or wt.% means weight % unless otherwise indicated. When used herein % refers to weight % as compared to the total weight percent of the phase or composition that is being discussed.
  • weight % wt.%
  • time, pH, volume or temperature can vary within a certain range depending on the margin of error of the method or device used to evaluate such weight %, time, pH, volume or temperature.
  • a margin of error of 10% is generally accepted.
  • concentrate used herein is a generic term used in mineral processing. Mined ore is crushed and ground, and then this undergoes some form of physical separation to separate the valuable minerals (concentrate) from the gangue (tailings).
  • the method of separation may be for instance by flotation, gravity separation or dense medium, sieving, or magnetic separation, or any other known methods.
  • the feed has been taken to be electric arc furnace dust (EAFD) containing recoverable amounts of iron, zinc, cadmium, copper, silver, lead, manganese, magnesium and, optionally, calcium.
  • EAFD electric arc furnace dust
  • a process for treating a feed comprising zinc and/or iron, and optionally other metals selected from copper, silver, lead, cadmium, manganese and magnesium comprising the following steps:
  • oxidising the ferric solution to convert any ferrous iron to ferric iron; iv. raising the temperature of the ferric solution to cause precipitation of the metals, except zinc, or calcium and any alkali metals if present, to generate a heated slurry and to recover hydrochloric acid in a concentrated form;
  • the oxidation if needed, has to occur before the hydrolysis step, and the hydrolysis step preferably occur after solid/liquid separation of the leach.
  • the feed material is electric arc furnace dust.
  • the feed material is a complex lead-zinc-copper- silver ore or concentrate.
  • the hydrochloric acid is recycled within the flowsheet.
  • an oxidant optionally may also be used in the leaching step.
  • electric arc dust and spent zinc pickle liquor are beneficially combined.
  • spent steel plant pickle liquors are used to provide additional iron and to provide a portion of the chloride leaching medium.
  • the spent pickle liquors are used to replace fresh water and to improve the water balance.
  • the temperature of the leaching reaction is 25- 110°C, preferably 80-100°C, more preferably 90-95°C.
  • temperatures mentioned herein refer to temperatures measured under atmospheric pressure. It has to be understood that that the process temperatures can be shifted by changing (increasing/decreasing) the pressure of reaction.
  • the leach filtrate is optionally cooled to crystallise out lead chloride.
  • the oxidation for ferrous iron is carried out electrolytically.
  • sufficient HC1 is added to convert ferrous chloride to ferric.
  • any temperature from ambient to 100°C may be used.
  • the temperature is raised in step (iv) to 170- 200°C, preferably 180-190°C, in order to effect the hydrolysis of ferric iron and precipitation of hematite.
  • the reaction in step (iv) is allowed to proceed until no more HC1 is evolved.
  • water, or more preferably steam, is added at the end of the reaction to ensure complete hydrolysis of all metals present except zinc, calcium and the alkali metals, which do not hydrolyse.
  • the amount of acid added in step (vi) is at least stoichiometric for the base metals, silver and magnesium present.
  • the temperature in step (vi) is from ambient to 100°C, preferably ambient.
  • the silver content is such as to produce a solubility of silver >100 mg/L, then sufficient recycled magnesium chloride is added to raise the chloride concentration to 2-5M, preferably 2-3M.
  • the silver is recovered by cementation with copper metal, and after silver is recovered, cadmium may be recovered by ion exchange with a strong sulphonic acid cationic resin or by ion exchange with a weak base quaternary amine resin. After silver and cadmium are recovered, copper is recovered by ion exchange with an iminodiacetate cationic resin or is recovered by ion exchange with a basic complex amine resin.
  • the chloride content of the solution may be adjusted to 6-12M, preferably 8-10M, with recycled magnesium chloride, and manganese is recovered by ion exchange with a bis-picolylamine resin.
  • Lead may be recovered by cementation with zinc dust, preferably with a temperature being from ambient to 100°C, preferably from 40-50°C.
  • air is excluded from the reactor.
  • the residence time is limited from 2-10 minutes, preferably 5 minutes.
  • the spent solution may be magnesium chloride with minor amounts of other metals including zinc, and may be recycled to the acid recovery stage of step (iv).
  • the quenching step (v), the amount of water is controlled to produce a magnesium chloride solution of 30 wt.% to 50 wt.%, in step (vii). It is understood that some magnesium could be present where there is magnesium present in the feed.
  • FIG 1 there is shown a schematic representation of a process for the recovery of zinc in accordance with one embodiment of the invention.
  • Figure 1 depicts the process as it applies to electric arc furnace dust (EAFD), but it is understood that it equally applies to other zinc-rich feed materials.
  • EAFD electric arc furnace dust
  • the process as shown in Figure 1 and Figure 2 combined involves the recovery of iron material, zinc material, a copper material, a silver material, a manganese material, a magnesium material, a cadmium material and a lead material, and where ZPL and SPL are included, of concentrated hydrochloric acid.
  • the feed material 10 is leached 13 with recycled hydrochloric acid 11 to dissolve all of the iron and zinc. Additionally, lead, copper, silver, cadmium, manganese and some flux/slag material within the dust containing magnesium and calcium also dissolve. Any aluminium present will also partially dissolve, the degree of dissolution being highly dependent on the source of the material.
  • spent pickle liquor and/or spent zinc pickle liquor may be added along with the recycled hydrochloric acid as an additional source of zinc, iron and/or hydrochloric acid, and in particular, in place of any fresh water that might be needed, to the solids concentration in the leach.
  • sulphuric acid 12 is also added to the leach to precipitate any calcium as calcium sulphate, which may be in the form of gypsum, hemi-hydrate or anhydrite, with the former phase preferred. Adding sulphuric acid at this stage allows for maximum dissolution of the other metals, since the hydrochloric acid associated with the calcium is liberated. An added advantage of doing so is that the calcium phase markedly improves the subsequent solid/liquid separation step 15.
  • Alternative embodiments especially if gypsum is a desired product in its own right, is to add the sulphuric acid in a separate step after the leach, or prior to magnesium chloride hydrolysis 35 at the end of the circuit.
  • the hydrochloric acid concentration may be of any value that causes leaching to take place, but ideally will be such to give metal ion concentration in the range of 70-100% of its solubility, and preferably 80-90% of its solubility. Since zinc, and to a lesser extent ferric iron, is highly soluble (>2000 g/L Zn in chloride media at leaching temperatures), realistically, the maximum acid concentration possible is used. This is a significant advantage over those processes employing pyrohydrolysis, where the acid concentration is limited to 6M. The addition of ZPL, in particular, allows for a very high zinc concentration, and a more efficient process.
  • the leaching stage 13 is carried out at atmospheric pressure.
  • the leaching temperature is maintained above 70°C, and preferably above 90°C.
  • Solid-liquid separation 15 of the leach slurry 14 may be effected by any convenient means, such as, but not limited to, flocculation and thickening, fdter press or vacuum belt fdter.
  • the solids 16 will be predominantly silicate flux and calcium sulphate, and as such are environmentally benign. They are suitable for return to the steel plant or may be disposed of as landfill.
  • the solution from the leach may be treated with sulphuric acid of concentration 50-98%, but preferably of 70-93%, and most preferably 93% in order to precipitate the majority of the calcium as a pure form of gypsum, CaS04*2H20 or hemihydrate, CaSO-r'rifhO.
  • the slurry so-generated may be fdtered by any convenient means, such as, but not limited to, flocculation and thickening, fdter press or vacuum belt fdter.
  • the calcium sulphate produced is pure and may be sold.
  • leaching will be carried out under oxidising conditions, with the addition of an appropriate oxidant such as, but not limited to, oxygen gas, chlorine, hydrogen peroxide or nitric acid.
  • an appropriate oxidant such as, but not limited to, oxygen gas, chlorine, hydrogen peroxide or nitric acid.
  • oxygen gas such as, but not limited to, oxygen gas, chlorine, hydrogen peroxide or nitric acid.
  • the majority of the sulphur in the feed is converted to its elemental form rather than fully oxidised to sulphate, which is a distinct advantage of chloride leaching.
  • the solution 17 from the leaching circuit irrespective of its original feed, will contain iron in its predominantly ferric state. Thus, an oxidation step for iron is not needed, which is a significant advantage of this process.
  • This solution may be thermally decomposed 18 at a temperature of 160-200°C, and preferably in the range 170-190°C, resulting in the hydrolysis of ferric and any other trivalent ions present, such as aluminium, to form their respective oxides and evolve hydrogen chloride vapour 20.
  • This HC1 vapour may be used as-is in the leach circuit, or condensed to concentrate (30-35% HC1) hydrochloric acid 11.
  • the quench slurry 24 proceeds to solid-liquid separation 25, which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the solids 26 will be predominantly hematite (Fe 2 0 3 ), together with some alumina and basic metal chlorides, which may be further treated (Figure 2) to separate and recover the various metals.
  • the solution 27 is predominantly pure zinc chloride, which is then treated with recycled slaked 37 magnesia 29 to effect precipitation 28 of zinc hydroxide 31.
  • This may be carried out in any suitable reactor, preferably a stirred tank reactor.
  • the temperature may be from ambient to 100°C, preferably from 60-65°C.
  • the pH is from 6.0-8.5, preferably from 6.5-7.0.
  • the precipitation may be carried out in one, two or three stages, with a single stage being shown for convenience.
  • Solid-liquid separation of the precipitation slurry 30 may be effected by any convenient means, such as, but not limited to, flocculation and thickening, fdter press or vacuum belt fdter.
  • the solids 31 are pure zinc hydroxide, which are calcined 32 to generate pure zinc oxide 33.
  • the temperature of calcination is low, from 150-300°C, preferably from 200-250°C.
  • the solution 34 is pure magnesium chloride, which may be treated by conventional pyrohydrolysis 35 to recover hydrochloric acid 38 for recycle to the leaching stage, or to the thermal decomposition stage to increase its concentration, and pure magnesia (MgO) 36. Part of the magnesia 42 is recycled to the impurity and zinc precipitation stages, and the balance 56, equivalent to fresh input from the feed, is suitable for sale.
  • MgO magnesia
  • the metal oxides/basic chlorides solids 26 are treated with dilute HC1 39 in a re-dissolution reactor to selectively dissolve the basic chlorides.
  • Such acid may be that from the magnesium chloride pyrohydrolysis stage 35.
  • This is a novel and unique aspect of the current invention, separating valuable base and precious metals from more common metals such as iron and aluminium in this manner.
  • the basic metal chlorides are readily soluble in very dilute acid, whereas the higher-valent metal oxides such as hematite and alumina are not. Any magnesium present will also dissolve.
  • the re-dissolution slurry 41 undergoes solid-liquid separation 42, which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, fdter press or vacuum belt fdter.
  • the solids 43 will be predominantly hematite, but may contain some alumina if there was any aluminium present in the feed which dissolved. If desired, this alumina may be conveniently separated by a simple caustic dissolution (not shown).
  • the solution 44 now comprises a mixture of magnesium, base metal and silver chlorides.
  • Silver chloride although nominally insoluble, does in fact have a small solubility, which is usually not exceeded, especially for feeds such as EAFD. However, if there is a large amount of silver present, its solubility can be enhanced by increasing the chloride content during re-dissolution so as to make it more soluble. This is conveniently achieved by adding recycled magnesium chloride 34.
  • Silver and the various base metal chlorides are separated by the following series of steps.
  • Silver is recovered via a cementation 46 reaction with scrap or recycled copper 45.
  • the cementation slurry 47 undergoes solid-liquid separation 48, which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, fdter press or vacuum belt fdter. In practice, a small vacuum pan fdter is preferred.
  • the solids 43 will be pure silver metal, which may be washed, melted and cast into bars.
  • the solution 50 then undergoes a series of ion exchange separations. Cadmium 51 is recovered first. If the silver content is low, then the chloride content of the solution will be low, close to stoichiometric for the metal ions present, and the pH of the solution will be around 2.0. In this case, cadmium will be present as a cation, and may be selectively recovered using a strong sulphonic acid cation ion exchange resin in its hydrogen form. Such resins are extremely effective for cadmium, and have a very high loading capacity (>100 g/L Cd per litre of wet settled resin).
  • the resin may be stripped with either sulphuric or hydrochloric acid, the strength of the stripping solution being dependent on the amount of cadmium on the resin, but calculated to be stoichiometric for 100% stripping in two bed volumes, to give a cadmium salt solution 52.
  • Copper is recovered next, and a similar logic as for cadmium applies. If the chloride content is low (not shown), then copper will be present as a cation, and may be conveniently recovered with an iminodiacetic acid resin 55. In this case, loading up 30 g/L Cu per liter of wet settled resin can be achieved. After washing, the resin may be stripped with either sulphuric or hydrochloric acid, the strength of the stripping solution being dependent on the amount of copper on the resin, but calculated to be stoichiometric for 100% stripping in two bed volumes, to give a copper salt solution 56.
  • the chloride concentration may be adjusted with recycled magnesium chloride 54, wherein copper can be selectively loaded 55 onto a weak base complex amine resin, with similar loading to those achieved with the iminodiacetate resin.
  • the copper chloro complex is not as strong as that of cadmium, and hence requires a strong base quaternary amine resin, and also is not efficiently stripped with water. In this case, copper is stripped with 5% HC1 to generate a copper chloride salt solution 56.
  • Manganese is recovered next. It forms a very weak chloro complex, and is generally difficult to load onto resins. However, it has been found that in chloride media, a bis picolylamine resin 59 is effective for recovering manganese.
  • the copper barren solution 57 is adjusted with recycled magnesium chloride 58 to raise the chloride content to 6-10M, the actual level depending on the amount of manganese present.
  • Manganese can load up to similar levels as copper does for its resins, and may be stripped with 100 g/L H2SO4 or HC1 to yield a manganese salt 60.
  • Lead can be recovered from the manganese barren solution 61 by cementation 63 with zinc metal 62. Although this particular process is well-known in sulphate circuits, it is more difficult in chloride. There should be ⁇ 5 g/L free HC1 present and preferably ⁇ 1 g/L, since the acid will not only consume the zinc powder added, but will also tend to re-dissolve the cemented lead. Recycled magnesia can be used to adjust the acidity if required (not shown). Additionally, it should also be carried out in the absence of air, and with a very short residence time of 5-10 minutes, preferably 5 minutes.
  • the cementation slurry 64 undergoes solid/liquid separation 65 in a manner analogous to that of the silver cement.
  • the solids are pure lead 66, which may be washed, melted and cast to give lead bullion.
  • the solution 67 is predominantly magnesium chloride, with a small amount of zinc, which is recycled to acid recovery 18.
  • the feed material with a HC1 leaching medium to generate a leachate and a solid residue, the leachate comprising at least zinc and iron (1200);
  • a complex lead-silver ore, also containing copper, with a chemical analysis of 0.13% Ag, 0.11% Cu, 19.2% Fe, 5.5% Pb and 25.7% S was leached with the addition of 350 kg/tonne of hydrochloric acid and 200 kg/tonne of hydrogen peroxide at 90°C and 15% solids loading for a period of four hours.
  • Metal extractions obtained were 85% for silver, 95% for lead and 90% for copper.
  • This example demonstrates the viability of oxidative hydrochloric acid leaching for complex lead-silver ores, with the data being directly applicable to EAF dusts as above.
  • a three-day miniplant leaching campaign was carried out using a large sample of dust from the same source as sample 1 in Example 1 as feed. Leaching was carried out at 20% solids loading with 750 kg/tonne acid addition (100% HC1 basis), a temperature of 90- 100°C, and a nominal residence time of 60 minutes in each of five cascading reactors.
  • the column was drained, and then stripped with a first pass of 5BV of DI water (de-ionised water), followed by 5BV of 5% HC1.
  • the HC1 was used, because it was clear that water had not fully stripped the resin.
  • the water strip showed a concentration of 22 g/L Cu in the first BV, a concentration factor of 1.5 times.
  • the 5% HC1 strip showed 20 g/L Cu in the first bed volume.
  • Magnesium chloride brine containing 61.9 g/L Mg, 34.0 mg/L Ni and 4.36 mg/L Mn, was passed through an ion exchange column containing a bis-picolylamine resin, at a flowrate of 10 BV/h for 1000BV (bed volumes).
  • the objective of the test was to demonstrate the removal of nickel and manganese from chloride solutions, not specifically to recover manganese. Analysis of the solution exiting the column was ⁇ 0.5 mg/L Ni and Mn for the first 60 BV, and the resin was not fully loaded even after the passage of 1000 BV of feed solution.
  • Stripping of the partially loaded resin was effected by 5BV of 10% HC1, generating a solution analyzing 6.0 g/L Ni and 0.77 g/L Mn. This shows that manganese can be effectively recovered from chloride solutions, such as that obtained from the leaching of the hematite residue, or any remaining in the magnesium chloride solution after zinc precipitation.
  • Example 6 A sample of leach solution after removal of all impurities was precipitated using lime slurry. The zinc hydroxide produced was fdtered off and well-washed, dried and analysed. The sample showed only calcium as an impurity at a concentration of 0.07%, showing that a purity for zinc oxide of >99.9% could be achieved.
  • Iron is invariably present in all feedstocks, and is generally regarded as being a significant problem, one that has to be removed before the value metals can be recovered. It is also usually present in significant quantities, far more so than the value metals. Most processes regard iron in this light and the iron solids are first removed and then disposed of, usually by a neutralisation/precipitation process. This new process not only provides a novel and efficient method of separating iron from the value metals, but it also recovers the iron in a useful and valuable form of itself. It also allows for the recycle of hydrochloric acid in a concentrated form, which no other process is able to accomplish.

Abstract

L'invention concerne un procédé de récupération de zinc et de métaux de valeur associés à partir de minerais, de concentrats et d'intermédiaires contenant du zinc, en particulier à partir de poussières de four à arc électrique (electric arc furnace dust - EAFD) et de liqueur usée de décapage à base de zinc (zinc pickle liquor - ZPL) provenant d'aciéries, comprenant la lixiviation du matériau d'alimentation dans de l'acide chlorhydrique concentré recyclé, la récupération du fer sous forme pure d'hématite, la précipitation d'hydroxyde de zinc pur et le séchage dudit produit pour former de l'oxyde de zinc pur et la récupération de magnésie par pyrohydrolyse. Des métaux de valeur tels que l'argent, le cuivre, le plomb et le cadmium sont également récupérés sous forme de produits purs. Un mode de réalisation particulier concerne la combinaison d'EAFD avec des liqueurs usées de décapage provenant d'usines sidérurgiques et en particulier avec des ZPL usées provenant d'usines sidérurgiques. La présente invention concerne un procédé unique qui permet la récupération de fer, de zinc et d'autres métaux sous une forme de valeur économique et la génération, au sein du procédé, de ses propres réactifs pour un recyclage interne.
PCT/CA2019/051710 2018-11-30 2019-11-29 Procédé de récupération de métaux de valeur à partir de minerais, de concentrats, d'intermédiaires et de déchets contenant du zinc WO2020107122A1 (fr)

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WO2021177843A1 (fr) * 2020-03-02 2021-09-10 Bonelli Arenas Julio Domingo Procédé hydrométallurgique pour l'extraction simultanée de métaux et de gypse des poudres de four à arc électrique d'aciéries
EP3978442A1 (fr) * 2020-09-30 2022-04-06 ThyssenKrupp Steel Europe AG Procédé de production d'oxyde de fer à haut degré de pureté
CN115430516A (zh) * 2022-08-31 2022-12-06 云南黄金矿业集团股份有限公司 一种含金银铜的硫铁矿焙烧渣水洗液处理方法

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WO2011100820A1 (fr) * 2010-02-18 2011-08-25 Neomet Technologies Inc. Procédé pour la récupération de métaux et d'acide chlorhydrique
CN105776140A (zh) * 2016-03-17 2016-07-20 芦秀琴 一种从金属氯化物溶液中回收盐酸和金属氧化物的方法
WO2019006545A1 (fr) * 2017-07-07 2019-01-10 9203-5468 Québec Inc. Dba Nmr360 Procédé d'oxydation et de dissociation hydrothermique de chlorures métalliques pour la séparation de métaux et d'acide chlorhydrique

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WO2011100820A1 (fr) * 2010-02-18 2011-08-25 Neomet Technologies Inc. Procédé pour la récupération de métaux et d'acide chlorhydrique
CN105776140A (zh) * 2016-03-17 2016-07-20 芦秀琴 一种从金属氯化物溶液中回收盐酸和金属氧化物的方法
WO2019006545A1 (fr) * 2017-07-07 2019-01-10 9203-5468 Québec Inc. Dba Nmr360 Procédé d'oxydation et de dissociation hydrothermique de chlorures métalliques pour la séparation de métaux et d'acide chlorhydrique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021177843A1 (fr) * 2020-03-02 2021-09-10 Bonelli Arenas Julio Domingo Procédé hydrométallurgique pour l'extraction simultanée de métaux et de gypse des poudres de four à arc électrique d'aciéries
EP3978442A1 (fr) * 2020-09-30 2022-04-06 ThyssenKrupp Steel Europe AG Procédé de production d'oxyde de fer à haut degré de pureté
CN115430516A (zh) * 2022-08-31 2022-12-06 云南黄金矿业集团股份有限公司 一种含金银铜的硫铁矿焙烧渣水洗液处理方法
CN115430516B (zh) * 2022-08-31 2023-06-16 云南黄金矿业集团股份有限公司 一种含金银铜的硫铁矿焙烧渣水洗液处理方法

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