Method for producing metal zinc

Abstract

A method for producing metal zinc by liquid/liquid extraction, comprising leaching of a zinc-bearing solid raw material containing antimony with a slightly acid aqueous solution, at a pH value maintained above 3 and less than or equal to 5, with formation of a suspension, drawing-off from the suspension of an aqueous phase containing zinc in solution to be subject to the extraction, additional leaching of the remaining suspension with an acid aqueous solution, at a pH value maintained below 3.5 and greater than or equal to 1, with formation of a pulp, introduction of a neutralizing agent in this pulp with coprecipitation of antimony and other impurities and separation from this neutralized pulp of a zinc-bearing aqueous solution which is recycled to the step for leaching the zinc-bearing solid raw material.

Claims

1. A method for producing metal zinc, comprising the steps of: a step for neutral leaching wherein a zinc-bearing solid raw material consisting of electric arc oven dusts, of impure zinc oxide obtained by a thermal method for volatilizing galvanization ashes, oxidized zinc ores or mixtures thereof undergoes neutral leaching with an aqueous solution, at a pH value maintained greater than 3.8 and less than or equal to 5, with formation of a suspension in which an aqueous phase contains a main fraction of the zinc of the raw material, which has passed into solution, and a solid phase contains a residual fraction of this zinc as well as antimony and other impurities, the step for neutral leaching comprising an addition of iron, as a soluble iron compound, into the suspension for contributing to coprecipitation of iron, antimony, and other impurities as well as maintaining oxidizing conditions in the suspension for causing oxidation of the iron and of antimony and said other impurities, a drawing-off step wherein said aqueous phase containing zinc in solution is drawn off from said suspension and exposing the zinc in solution to an extraction step, wherein the zinc in solution is extracted from the aqueous phase with an acid organic solvent, with formation of a zinc-loaded organic liquid phase and of an acid aqueous raffinate, an additional leaching step wherein the remaining suspension is leached after said drawing-off with an acid aqueous solution, at a pH value maintained below 3.5 and greater than or equal to 1, with formation of an aqueous pulp in which a liquid phase contains, solubilized, said residual fraction of the zinc of the raw material, iron, antimony, and other impurities, a step for introducing a neutralizing agent wherein a neutralizing agent is introduced into the liquid phase of this aqueous pulp with the obtaining of coprecipitation of iron, antimony, and other impurities, a solid/liquid separation in this neutralized pulp, with the obtaining of a zinc-bearing aqueous solution which is recycled to the step for neutral leaching the zinc-bearing solid raw material, re-extraction of the zinc from the zinc-loaded organic liquid phase, by means of an acid aqueous solution, and recovery of the re-extracted zinc from the acid aqueous solution by electrolysis.

2. The method according to claim 1, comprising before the step for neutral leaching, a prewashing step wherein the zinc-bearing solid raw material is prewashed with an aqueous solution of an alkaline basic reagent, with solubilization of chlorides and fluorides, and removal of the solubilized chlorides and fluorides, with formation of a prewashed zinc-bearing solid raw material to be subject to said step for neutral leaching.

3. The method according to claim 2, wherein the alkaline basic reagent of the prewashing step is selected from the group formed by sodium and potassium oxides, hydroxides and carbonates, and mixtures thereof.

4. The method according to claim 2, wherein the neutralizing agent is formed with a portion of the prewashed zinc-bearing raw material.

5. The method according to claim 2, wherein a portion of the acid aqueous raffinate is recycled to the prewashing step.

6. The method according to claim 1, wherein the aqueous solution of the neutral leaching step at least partly consists of the acid aqueous raffinate from the extraction step.

7. The method according to claim 1, wherein the iron is added in an amount at least equal to 250 times the amount of antimony contained in the zinc-bearing raw material.

8. The method according to claim 1, wherein the drawing-off step comprises the steps of: decantation of the suspension with formation of a clarified supernatant, and filtration of this clarified supernatant with the obtaining of a filtrate forming said aqueous phase containing zinc in solution to be subject to the extraction step.

9. The method according to claim 1, wherein the acid aqueous solution of the additional leaching at least partly consists of the acid aqueous raffinate of the extraction step.

10. The method according to claim 1, comprising, before said step for introducing a neutralizing agent, a solid/liquid separation in the pulp from the additional leaching, with the obtaining of a solid residue containing lead and of said liquid phase containing, solubilized, zinc, iron, antimony, and other impurities, and introduction of the neutralizing agent into this liquid phase before this separation.

11. The method according to claim 1, comprising, during the introduction of a neutralizing agent, an addition of iron, as a soluble iron compound, in order to contribute to coprecipitation of iron, of antimony and of other impurities as well as maintaining oxidizing conditions in the liquid phase of the aqueous pulp from the additional leaching, in order to cause oxidation of the iron and of said other impurities.

12. The method according to claim 1, further comprising the steps of: washing with water the zinc-loaded organic liquid phase from the extraction step, the water from this washing containing residual chlorides and fluorides, and acid washing this zinc-loaded organic liquid phase, washed with water, with an acid aqueous solution containing zinc in solution, the acid aqueous solution from this washing containing metal impurities.

13. The method according to claim 12, wherein, during said washing with water, a ratio between organic flow and aqueous flow of less than 20 is maintained.

14. The method according to claim 12, wherein, during said acid washing with an acid aqueous solution containing zinc in solution, a ratio between organic flow and aqueous flow of more than 20 is maintained.

15. The method according to claim 12, wherein the washing water containing residual chlorides and fluorides is at least partly recycled to the prewashing step.

16. The method according to claim 12, further comprising neutralization of the acid aqueous solution containing metal impurities from the acid washing step, filtration with the obtaining of a filtrate and of a cake, purification of the filtrate with zinc dust, with formation of a cement containing metal impurities, the purified filtrate being recycled to the zinc recovery step and the filtration cake to the additional leaching step.

17. The method according to claim 1, further comprising regeneration of the organic liquid phase having been subject to said re-extraction and recycling of this organic liquid phase regenerated in the extraction step.

18. The method according to claim 1, wherein the acid aqueous raffinate consists of a majority weight of sulfuric acid.

Description

(1) Other details of the invention will become apparent from the exemplary embodiments given hereafter as non-limiting.

(2) FIG. 1 illustrates a flow diagram of an installation for producing zinc applying a method according to Example 1 of the invention.

EXAMPLE 1

Prewashing

(3) 1,000 g of a zinc-bearing raw material in the form of dry dusts and containing as impurities i.a. antimony, are fed in 1 to a prewashing installation 2. This material has the following specifications:

(4) TABLE-US-00001 TABLE 1 Zn 57.48% by weight Fe  0.29% by weight Sb 40 ppm Cu 580 ppm Cl 11.15% by weight F 1,300 ppm

(5) In this installation, the raw material is mixed with 4,000 of water injected at 3. 100 g of a basic reagent, such as sodium carbonate for example, are introduced at 4 in the formed slurry, which gives rise to the formation of sodium chloride and fluoride which are soluble in water. In the exemplary embodiment, this prewashing installation 2 comprises at least two stirred reactors positioned in a cascade and a solid/liquid separation device, in particular a filter. It is further possible to envision a step for washing with water the filtration cake, into which 2,000 of water may be introduced. The main parameters observed in this prewashing installation are indicated in Table 2 below.

(6) The liquids obtained in the solid/liquid separator and the step for washing with water, are then transferred through conduit 5 to a routine installation for treating effluents 6 in which a separation is carried out between liquid effluents 7 and solid materials 8.

(7) In this way, more than 90% by weight of sodium and potassium chlorides present in the raw material and more than 80% of the fluorides are removed, while less than 1% of the zinc is lost with this operation.

(8) TABLE-US-00002 TABLE 2 pH 7-10 Temperature 20-95° C. Density of the slurry 10-40% by weight of solid mateiral Dwelling time .sup. 0.5-3 h

The Leaching Circuit

(9) The prewashed zinc-bearing raw material now has the following specifications:

(10) TABLE-US-00003 TABLE 3 Mass 870 g Humidity level 41.9% Zn 69.10% by weight  Fe 0.30% by weight Sb 49 ppm Cu 650 ppm Cl 0.25% by weight F 170 ppm

(11) It is transferred through conduit 9 to a leaching installation 10, called neutral leaching. This installation comprises, in this exemplary embodiment, at least two stirred reactors positioned in a cascade. In the illustrated example, 21.5 of a slightly acid aqueous solution which consists of one portion of the aqueous acid raffinate from the extraction step, are introduced at 11 and form a suspension with the prewashed zinc-bearing raw material. This raffinate is mainly formed with sulfuric acid and has the following specifications:

(12) TABLE-US-00004 TABLE 4 H.sub.2SO.sub.4 38 g/l Zn 12.5 g/l Fe 3.8 mg/l Sb 0.080 mg/l Cu 474 mg/l Cl 15.65 g/l F 84 mg/l

(13) The main parameters maintained in this leaching installation are indicated in Table 5 below.

(14) TABLE-US-00005 TABLE 5 pH in the first reactor  >3-5 pH in the last reactor 3.8-5 Temperature 20-95° C. Density of the suspension 2-30% by weight of solid material Dwelling time .sup. 0.5-4 h

(15) In the illustrated example, during this neutral leaching, iron, for example 75 g of ferrous sulfate, and an oxidizing agent, such as potassium permanganate, are introduced at 12.

(16) At a pH from 3 to 5, the zinc passes into solution with a high yield of more than 80%, in the illustrated case of the order of 86.8%, by weight of the zinc in the raw material and the iron as well as the antimony, the arsenic, the bismuth, etc., are oxidized and coprecipitated. The residual chlorides and fluorides are on the other hand carried away in the aqueous phase.

(17) In the exemplary embodiment, the suspension formed is then transferred at 13 to a decantation device 14 including a decanter in which the pH increases up to values from 5 to 5.4. Indeed, the not yet solubilized zinc oxide continues to consume sulfuric acid. A flocculant may advantageously be added, for example an anionic polyacrylamide such as KRF 1210 (Kroff Inc.), in an amount of an addition of 50 g per metric ton of dry solid materials, in order to clarify the suspension. The supernatant portion is then drawn off and passes through a sand filter in order to exclude any passage of solid material into the extraction. 22.3 of filtrate is then obtained, which contains zinc in solution and residual chlorides and fluorides and which is then discharged from the filter through the conduit 15 where it may be optionally separated into two streams. One of these streams passes through the supply conduit 16 of the extraction installation 17 and the other one through an optional purging conduit 18 which then sends back a portion of the filtrate to the prewashing installation 2, so as to maintain, in the aqueous phase containing zinc in solution passing through the supply conduit 16, a chloride content always below 20 g/L.

(18) The remaining non-clarified suspension and therefore not drawn off from the decanter has the following specifications:

(19) TABLE-US-00006 TABLE 6 Mass 301 g Humidity level 38.9% Zn 26.38% by weight  Fe 6.37% by weight Sb 140 ppm Cu 500 ppm Cl 0.44% by weight F 350 ppm

(20) It is transferred through the conduit 19 to an additional leaching installation 20, called slightly acid leaching. This installation comprises, in this exemplary embodiment, at least two reactors positioned in a cascade. 4.15 of an acid aqueous solution, which consists of a portion of the aqueous acid raffinate from the extraction step, are introduced at 21 and form a pulp with said remaining, non-clarified suspension. This raffinate therefore has the specifications given in Table 4. In 22, it is possible to envision a supply of fresh sulfuric acid in order to compensate for the acid losses in the process. The conditions observed in this additional leaching installation are indicated in Table 7 below.

(21) TABLE-US-00007 TABLE 7 pH in the first reactor 1.5 pH in the second reactor 2.4 Temperature 20-95° C. Density of the pulp 22-30% by weight of solid material Dwelling time .sup. 0.5-3 h

(22) At a pH from 1 to 3, the residual zinc is totally leached and a few impurities (iron, antimony, arsenic, bismuth etc.) are also dissolved. The lead is found in the form of insoluble lead sulfate. In this exemplary embodiment, the additional leaching installation further includes a solid/liquid separation device, for example a filter, which allows recovery of a cake containing lead sulfate. The latter is discharged from the circuit at 23, while the filtrate formed with a zinc-bearing aqueous solution is, in the illustrated example, brought by the conduit 24 into a purification installation 25. This filtrate has the following specifications:

(23) TABLE-US-00008 TABLE 8 H.sub.2SO.sub.4 0.2 g/l Zn 38.6 g/l Fe 1327 mg/l Sb 2.4 mg/l Cu 494 mg/l Cl 17.85 g/l F 91 mg/l

(24) It should be noted that according to the invention it is possible to abandon filtration of the aqueous pulp obtained in the leaching installation 20, in particular when the raw material contains very little or no lead.

(25) The purification installation 25 comprises, in the exemplary embodiment, at least two stirred reactors positioned in a cascade. A neutralizing agent is introduced at 26 in a sufficient amount so as to obtain precipitation of impurities, in the present case, 12.7 g, of the prewashed zinc-bearing raw material. At 27, it is optionally possible to further introduce iron, for example as ferrous sulfate, and an oxidizing agent, such as potassium permanganate. Optionally, air or oxygen may be bubbled in the solution to be purified. All these conditions contribute to oxidation and coprecipitation of the iron and of the other impurities and to reaching a high purification yield. The conditions of the purification emerge from Table 9 below.

(26) TABLE-US-00009 TABLE 9 pH 3-4.5 Temperature 20-95° C. Drying time  1-6 h

(27) The iron mainly precipitates as goethite. In the illustrated case, by a solid/liquid separation and without addition of iron, 13.4 g are obtained of a precipitate notably containing iron and antimony, which is discharged from the leaching circuit in 28. The purified zinc-bearing aqueous solution is, through the conduit 53, recycled to the leaching installation 10. It then has the following specifications:

(28) TABLE-US-00010 TABLE 10 Zn 42.9 g/l Fe 162 mg/l Sb 0.16 mg/l Cu 481 mg/l Cl 17.60 g/l F 75 mg/l

(29) All these steps in succession during the leaching circuit give the possibility of obtaining in this example, 22.3 of an aqueous phase containing zinc in solution which is drawn off at 15 from the decantation device 14 and which has the specifications given in Table 11 below.

(30) TABLE-US-00011 TABLE 11 H.sub.2SO.sub.4 0.1 g/l Zn 36.1 g/l Fe 2.8 mg/l Sb 0.039 mg/l Cu 498 mg/l Cl 15.25 g/l F 82 mg/l

(31) The limits reached by the leaching circuit according to the invention for iron and antimony are extremely important since these impurities, if they have not been extensively removed in the leaching circuit, would be, like the zinc, loaded into the organic liquid phase during the extraction process. The antimony, which cannot be separated from zinc during the re-extraction, would then reach the electrolyte and would then irremediably pollute it. Iron and other metal impurities such as tin would themselves remain in the organic phase during the re-extraction and would accumulate in the latter, consequently degrading its extraction agent properties.

The Liquid-Liquid Extraction Circuit

(32) In the illustrated exemplary embodiment, the aqueous phase containing zinc in solution (22.3 L) reaches the extraction installation 17 which includes several stages, in which it is put into contact as a counter-current with 42.3 of an organic phase formed with D.sub.2 EHPA diluted in kerosene. Each stage customarily comprises a mixing area with stirring where the aqueous phase and the organic phase are intimately put into contact and a decantation area where they separate given their density difference. During the extraction, the ratio between the organic flow and the aqueous flow O/A is comprised between 1 and 4 in order to reach a high transfer of zinc to the organic phase. The temperature is maintained between 20 and 60° C.

(33) This extraction is, as this is known, selective towards many metals. Chloride and fluoride extraction is extremely low. By exchange, a stoichiometric amount of acid is released into the aqueous phase. The aqueous phase flowing out of the extraction stage is therefore acid and is called an acid aqueous raffinate, which is collected in a tank 29 (see Table 4). As this is already indicated, a portion of the raffinate is transferred as a leaching medium to the installation of 10 and 20. As this raffinate contains chlorides, a portion of the latter may also optionally be recycled to the prewashing installation for the raw material through the conduit 30.

(34) However the extraction is not sufficient for totally removing chlorine and fluorine and some trace amounts of metals such as Ca, Cu, Cd, Ni, i.e., and on the other hand, a complete raffinate-organic phase separation cannot be obtained and therefore a portion of the raffinate containing chlorides, fluorides and impurities is carried away by the organic phase.

(35) According to the invention, through a conduit 31, the zinc-loaded organic phase is transferred to a washing installation. It has the following specifications:

(36) TABLE-US-00012 TABLE 12 Volume 42.3 l Zn 13.6 g/l Fe 6.1 mg/l Sb 0.019 mg/l Cu 0.80 mg/l Cl 0.165 g/l F 3.0 mg/l

(37) This washing installation includes two sections.

(38) The first section, called a section for washing with water 32, comprises at least one stage where the organic phase is put into contact with 4.23 of water introduced at 33, i.e. in an O/A ratio of about 10. In the exemplary embodiment, a small amount of a basic agent, for example sodium carbonate may be added to the washing water, which increases the efficiency of the washing of the halides and reduces possible carrying-away of the zinc. The washing water containing the halides is discharged and transferred through the conduit 34 to the prewashing installation 2 for the raw material.

(39) The zinc-loaded organic phase, washed with water, has the following specifications:

(40) TABLE-US-00013 TABLE 13 Volume 42.3 l Zn 13.6 g/l Fe 5.9 mg/l Sb 0.010 mg/l Cu 0.60 mg/l Cl 0.014 g/l F 0.5 mg/l

(41) It is then transferred through the conduit 35 to the second section, called an acid washing section 36. This section comprises at least one stage where the organic phase is put into contact with 2.04 of an acid zinc-bearing solution, in the illustrated case, used electrolyte supplied at 37 and diluted with water introduced at 38 so as to avoid precipitation of gypsum when calcium is carried away. The O/A ratio is 35 for example. The acid aqueous solution from the acid washing section 36 and containing the metal impurities is discharged through the conduit 39 so as to be optionally brought to a subsequent treatment.

(42) The zinc-loaded organic liquid phase after the acid washing has the following specifications:

(43) TABLE-US-00014 TABLE 14 Volume 42.3 l Zn 13.1 g/l Fe 5.9 mg/l Sb 0.010 mg/l Cu 0.20 mg/l Cl 0.009 g/l F 0.3 mg/l

(44) It is then transferred through the conduit 54 to the re-extraction installation 40 which includes at least one stage, in which it is put into contact in a known way with 13.6 of an acid aqueous solution, in this case the used electrolyte introduced at 41. The O/A ratio is comprised between 2 and 10 and ensures a high zinc transfer yield to the electrolyte, preferably of more than 90% by weight.

(45) The organic phase reloaded with protons may then be recycled through the circuit 42 to the extraction installation 17. Advantageously, in this circuit, provision may be made for customarily regenerating the organic phase.

The Electrolysis

(46) In a conventional way, the zinc-loaded aqueous solution leaving at 55 the re-extraction installation 40 is supplied to a customary cell for electrodeposition of metal zinc 43. It has the following specifications:

(47) TABLE-US-00015 TABLE 15 Solution feeding the electrolysis Electrolyte Volume 13.6 l 13.6 l H.sub.2SO.sub.4 115 g/l 175 g/l Zn 91.1 g/l 50.8 g/l Fe 1.1 mg/l 0.8 mg/l Sb 0.015 mg/l 0.005 mg/l Cu 0.35 mg/l 0.3 mg/l Cl 0.26 g/l 0.24 g/l F 23 mg/l 24 mg/l

(48) The acid aqueous solution from the acid washing section 36 may advantageously be subject in the device 44 to neutralization by the prewashed raw material introduced at 45 and to filtration. The filtration cake obtained at 46 may be recycled to the additional so-called acid leaching installation 20. The filtrate is transferred through the conduit 47 to a purification device 48 in which zinc dust is conventionally introduced at 49 into a stirred reactor in order to cause precipitation of the metal impurities by reduction to the metal state. The purified solution is filtered and transferred through the conduit 50 to the electrodeposition cell 43 while a cement is discharged at 51.

(49) The metal zinc obtained in the cell 43 is then transferred in a known way to the installation 52 where it is subject to melting and casting operations.

(50) When the different steps of the method according to the invention are reviewed, it is observed that the liquid-liquid extraction is highly selective towards copper and that the step for washing with water is very efficient for removing chlorine and fluorine residues. For antimony, none of the different steps of the liquid-liquid extraction circuit is selective, the distribution of antimony among both organic and aqueous phases being of the order of 50% in a series of steps and of 0% for the acid washing. This circuit is therefore not a barrier for antimony and it is necessary to control the latter beforehand, in the leaching circuit.

EXAMPLE 2

(51) The steps of the leaching circuit of Example 1 are reproduced but by applying a final pH of 1.5 in the last reactor of the additional so-called acid leaching.

(52) When the pH is thereby lowered, an increase in the zinc leaching yield and strong dissolution of iron and antimony are observed. As regards the latter, the leaching yield passes from 7.8% to 84.8%. A significant weight loss of the final cake occurs, and the lead content of the latter passes from 38% by weight for the leaching at a pH of 2.4 to 60% by weight at a pH of 1.5. Therefore from an economical point of view it is more interesting to operate at a lower pH, since more value will be obtained from the lead residue and the zinc recovery yield will be improved. However, the possibility of reprecipitating antimony is required for controlling its content in the neutral leaching solution, which may, according to the invention be obtained by purification during the step for introducing a neutralizing agent.

EXAMPLE 3

(53) In two tests, the steps of the leaching circuit of Example 1 are reproduced. The conditions applied in the purification step are the following:

(54) Test 1

(55) Addition of finely milled limestone up to a final pH of 4.2 Temperature: 60° C. Drying time: 4 h Bubbling of air as an oxidizer
Test 2 Addition of prewashed zinc-bearing raw material up to a final pH of 3.8 Temperature: 40° C. Drying time: 4 h Bubbling of air as an oxidizer

(56) While in both cases, practically complete precipitation of the iron is observed, the precipitation of antimony is only 60% with limestone as a neutralizing agent while it is practically total with the prewashed zinc-bearing raw material. This result per se is surprising, since it is impredictable.

(57) It should be understood that the present invention is by no means limited to the embodiment described above and that many modifications may be made thereto without departing from the scope of the appended claims.