JPS602371B2 - Wet metallurgy method for treating lead-containing sulfide compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a green metallurgical process for treating lead-containing sulphide compounds.

More particularly, the present invention relates to a method for selectively dissolving lead relative to iron and other non-ferrous metals contained in such sulfide compounds. It is known that in its natural state lead sulfide is interspersed in pyrite, blends, sulfided steels and other sulfides commonly referred to as non-ferrous metal sulfides.

According to conventional metallurgical methods, the various sulfides forming part of the ore are separated by differential flotation and then processed by conventional thermometallurgical methods.

However, complete separation is not always achieved by differential flotation. The resulting concentrate is sometimes a concentrate on its own, sometimes a mixed concentrate, and sometimes containing less than 40 or 50% lead compared to the usual 60-80% lead content. It is a highly impure lead concentrate. All such concentrates are extremely difficult to process using techniques developed in conventional metallurgy.

By the applicant May 15, 1973 and Hand 4, 1973
French Patent Application No. 74-1 filed on the 21st of May, respectively.
The method described in No. 6773 and No. 75-12373 is
Significant advances have been made in the field of composite ores and flotation concentrates.

The former application discloses a method for dissolving the entire non-ferrous metal contained in a sulfide compound using cupric chloride which is regenerated with air and a regenerant consisting of hydrochloric acid or ferrous chloride. If the solution obtained as above contains zinc, a method for treating the solution is described in the latter application.

The application states that lead can be separated from other non-ferrous metals by lowering the temperature to precipitate lead chloride.
The lead chloride obtained from this process is extremely pure. especially,
The lead chloride contains only small amounts of bismuth, which is extremely difficult to separate from the lead. Lead chloride is precipitated by metals that are more reducing than lead, such as zinc or iron. Although this technology has many advantages, it is sometimes expensive and
Also, it is not always suitable for the processing conditions of lead sulfide deposits. In particular, this method requires a lead chloride precipitation device and its thermal balance is not always favorable. Accordingly, one object of the present invention is to provide a method by which a chlorinated steel can be applied to a lead-containing sulfide compound to produce a copper-free lead chloride solution.

Another object of the invention is to provide a process of the above type that is as selective as possible towards other non-ferrous metals.

Another object of the invention is to provide a method for treating the solution resulting from this selective action.

Finally, another object of the invention is to provide a method for purifying lead chloride solutions.

According to the present invention, these objects and further objects which will become clear from the description below are to provide a method for treating sulfide compounds containing at least lead as non-ferrous metals using a hydrometallurgical method having the following characteristics: achieved.

The method of the present invention is characterized in that the sulfide compound is brought into contact with an aqueous solution containing at least one chloride selected from the group consisting of steel chloride, bismuth chloride, antimony chloride, chloride, and silver chloride. and the amount of said chloride used in the treatment is less than or equal to the stoichiometric amount required to completely dissolve the lead contained in the sulfide compounds. One of the main applications of the invention is the selective leaching of lead contained in sulfide compounds.

In this case, preference is given to choosing cuprous chloride and cupric chloride. Since copper is present in limited amounts during this leaching,
The dissolution of lead is caused not only by the action of cupric chloride on lead sulfide, but also by the exchange between the copper cations of the solution and the lead sulfide compounds. Furthermore, if leaching is carried out using only chlorinated steel, the stoichiometry is 2
determined with respect to individual reactions.

Xu++ solution + Pb ore...> Pb 10 solution + next u+ solution and Shio u 10 solution + Pb ore...
...>P is ten solution ten Xu ore.

Therefore, the conditions applicable to the amount of chlorinated steel used during processing are given by the inequality below. [Cu++] 12
[Cu+] [Pb++] [where [CuH] indicates the molar amount of cupric initially used during the process;
u+] indicates the molar amount of cuprous initially used during the treatment, and [Pb10] is the amount of lead initially present in the sulfide compound, i.e. the amount of lead that can be dissolved in the solution. Indicate quantity.

] The second section of chloride may be regenerated in part “in situ”;
Alternatively, it may be regenerated by dissolution according to the method described in French Patent Application No. 74-16,773 of May 15, 197 by the present applicant.

Such regeneration, which may be carried out "in situ" or in a separate reactor, oxidizes the steel ions in the presence of hydrochloric acid and/or ferrous chloride.

The reactions involved in this regeneration are shown below. The next plate ten is CI+
Ticket 2--------> 120 days 2 for the book. In the case of fox cl+ = 6 cl2 2 other o...>4 skin l2 sides, nada side regeneration, the conditions applicable to the amount of chloride used during treatment are expressed as follows. That is, originally chlorinated steel,
The amount of chlorine ions in the form of bismuth chloride, antimony chloride, phosphoric chloride, chloride, ferrous chloride and/or hydrogen chloride is calculated by taking all lead present in the sulfide compound as leadous chloride. , must be less than or equal to the amount of chloride ions present in the form of lead chloride. Two types of technical effects can be achieved by the selective leaching of the present invention.

That is, to obtain a sulfide compound that is practically lead-free, or to directly obtain a lead chloride solution that is as pure as possible. In the first case, it is preferable to leach with as much chlorinated steel as possible. It should be pointed out that the expression "equal to a stoichiometric quantity" herein should not be interpreted as equivalent in the strict sense of the term.

That is, in the method of the present invention, it is also possible to carry out leaching using an excess amount of steel chloride, bismuth chloride, antimony chloride and/or silver chloride, and this excess amount may be 10% or even 20%. This means that it can even reach %. However, this value of 20% represents the maximum allowable value. In the second case, it is preferred to leach with less than stoichiometric amounts of chloride.

The chloride selected is advantageously a chlorinated steel. If possible, leaching is carried out above ambient temperature, preferably between 60° and the boiling point of the reaction mixture.

Depending on the solubility of the leachate phase, the lead chloride is obtained in the form of a solution or bound in the form of a lead chloride pulp. In the first case, in order to ensure that the lead goes into solution, the concentration of chloride ions in the aqueous phase is advantageously at least equal to 2 g/eq. / is preferably larger than that.

These chloride ions can be supplied to the aqueous phase in the form of ammonium chloride or alkali metal or alkali metal chlorides.

In short, any metal chloride form that dissociates in the aqueous phase may be conjugated. In the second case, lead chloride is recovered in the form of pulp.

For this purpose, the amount of lead to be leached per unit volume need only be greater than the dissolving capacity of the leaching solution. What is thus obtained after leaching is on the one hand a saturated lead chloride solution and may contain small amounts of zinc chloride, and on the other hand two solid phases.

One solid phase consists of lead chloride, another solid phase consists of sulfided steel, consisting primarily of cupric sulfide, the sulfide of the metal whose chloride was used to act on the lead sulfide, and the sulfide of the metal in the attack solution. It consists of metal sulfides that did not react with the metal sulfide.

According to the applicant's surprising findings, the appearance of a third phase, crystalline lead chloride, does not interfere with the attack reaction at all.

Although the crystals of leadous chloride are highly dispersed and tend to mix very homogeneously with the sulfide and coat the ore or concentrate particles, the attack reaction is not hindered. One of the main advantages of this second embodiment is that the copper concentration is at least 30%/so 0chi0.
．． Concentrated steel chloride solutions such as 8M' or more can be used.

In order to prevent an increase in the solubility of lead chloride, the concentration of free chloride ions is advantageously equal to at most 2 gram equivalents/sod, regardless of the chloride causing leaching, and 0.5
~1.5 gram equivalent/so is preferred.

The chloride ions may be supplied in the form of wholly or partially dissociated chloride. In the latter case, the portion of chloride that is not dissociated and therefore not liberated has to be taken into account when determining the amount of chloride to be added. The solid mixture obtained after the action is then subjected to a treatment to separate the lead chloride from the remaining sulfides.

For this, one has to resort to physical treatments commonly used in metallurgy to produce concentrates from ores.

Examples of this include flotation, separation in thick soot, and elutriation. Another possible method is to precipitate the solid mixture in the pulp using a metal more electropositive than lead, such as iron or zinc, to obtain metallic lead.

Such metallic lead will be easily separated from the sulfide phase by any of the physical separation techniques described above. The pulp may be the reaction mixture after it has been attacked, or it may be the pulped cake obtained after filtration of the reaction mixture and, if necessary, washing. In a third possible method, the lead chloride and sulfide cake obtained after filtration of the reaction mixture and, if necessary, washing, is dissolved in a solution of dissociated metal chloride to dissolve the lead chloride; Separate this from other solids. It is advantageous in each case to maintain the pH value between 0 and 3.

Leaching may be carried out in a moving bed or in several successive reactors.

The sulfide compounds move countercurrently with the attacking solution. If the sulfide compound is brought into contact with ferric chloride or ferric chloride in advance, the ore will be activated.

That is, the selectivity and rate of leaching are significantly increased. This contact causes a change in the surface condition in the first stage and a change in the sulfur concentration of the sulfide compound in the second stage due to dissolution of a portion of the lead. It is obvious that this preferred modification is likewise obtained if the remaining mixture contains sulfur. Ferric chloride is preferred over ferric chloride because it is included in the group of chlorides that tend to selectively leach lead. Note that leaching using cupric chloride simultaneously activates the ore and allows for selective leaching as is.

The selectivity obtained by applying the present invention is exhibited for metals that are less reducing than lead such as bismuth, metals that are more reducing than lead such as zinc, and non-metals such as phosphorus. Therefore, it deserves even more attention.

Bismuth, phosphorus, and even copper and silver are among the most troublesome impurities of lead and must be removed from the lead solution when direct cementation is desired. Therefore,
According to the method of the present application, impurities in the sulfide compound itself can be used to selectively leach out lead contained in the sulfide compound.
New applications of the method of the invention can be deduced from these findings. Thus, the method of the invention can also be used to remove special impurities such as silver, bismuth, phosphorus, and copper from lead chloride solutions. It is pertinent to point out that the ease with which these impurities are absorbed by the ore varies with the steel ion concentration of the solution to be purified. The purity obtained is truly excellent. It is pertinent to point out that in this application the amount of lead contained in the ore must be greater than the stoichiometric requirement to precipitate these impurities in the form of sulphate. Will. This purification technique is well suited for lead chloride solutions obtained as a result of ferric chloride attack. Lead contained in the form of chloride in the solution obtained in this way can be used, for example, in French patent application no.
It may be recovered by any known method, such as the method disclosed in No. 373.

However, preferred are methods which can directly or indirectly produce the chlorinated second section regenerant, i.e. hydrochloric acid and/or ferrous chloride.

0 Examples of methods by which regenerants may be provided include cementation with iron to produce ferrous chloride, or zinc chloride which is thermally hydrolyzed at least in part to form zinc oxide and hydrochloric acid. Cementation with zinc, which produces
Another example is the reduction of lead chloride with hydrogen.

It is to be understood that the term "cementation" in this application does not mean only proper cementation, but also techniques equivalent to cementation.
An example of a technology equivalent to cementation is soluble zero anodic electrolysis. The metal that forms the anode is a different type of metal than the metal that is desired to be recovered. Similarly, one can mention cells of the Daniel-Se'zo type; the latter can actually be interpreted as a cementation of copper with zinc. In these two cases, the electrolyte contains chloride ions. It may be separated by a permeable partition.The preferred metal for carrying out lead cementation is iron, especially in the form of pre-reduced iron.

Reduction with hydrogen can be carried out using the conventional method for reducing metal chlorides with hydrogen, known as the "Vuin Arker method". Also, new methods such as those described below may be used. That is, the lead chloride obtained after the attack is recovered in crystalline form, for example by cooling a solution saturated with lead chloride. The lead chloride is then melted and reduced using hydrogen. Reduction of molten lead chloride takes place at a temperature of approximately 700°C.
Advantageously, the temperature is raised between 950°C and 85°C.
The temperature is preferably 950°C. Reactions can occur at various pressures.

However, from a practical standpoint, it is preferable to carry out the reduction at ambient pressure. Hydrogen may be used pure or diluted with an inert gas such as nitrogen or a noble gas.

In one preferred embodiment of this reduction, the lead chloride is melted and hydrogen is piped into the tank.

Preferably, the hourly flow rate of hydrogen is greater than about twice the stoichiometric amount required to reduce all of the lead chloride. Stoichiometry corresponds to the reduction below. POC12 10 days 2...
...>Pb.

The gas generated by the reduction therefore contains, on the one hand, the unreacted hydrogen fraction and, on the other hand, the hydrochloric acid formed during the reaction. Hydrogen may be combusted to heat the lead chloride. Hydrochloric acid mixed with hydrogen may be separated before combustion or recovered after combustion. Alternatively, hydrogen separated from the hydrochloric acid by conventional methods such as gas diffusion or cooling followed by absorption in water may be reused for the reduction of lead chloride. The use of hydrogen on such an industrial scale to reduce molten lead chloride is both a wonder to those skilled in the art and a particularly important inspiration to the industry.

In fact, according to thermodynamic calculations, the reaction is extremely difficult. As shown in the following table, the standard free enthalpy change (ΔG) is greater than or equal to 0 at various temperatures. △G Temperature Kilocalories/mole 900q0 0 8270 14 5270 111 Enthalpy change calculations can be found in “The Thermochemical Properties of Oxides, Fluorides and Chlorides 25000 K” by Alvin Glassner. -Report ANL (Arnnhi NatioMI
This was carried out based on the tables and graphs published in Laborato 15107-1.

The sulfurized liquid obtained by purification or leaching may be treated to recover the non-ferrous metals it contains.

Particularly suitable methods are those described in French Patent Application No. 74-16772, No. 74-16773, No. 74-
No. 16774 and No. 75-12373. The first three applications were filed on May 15th, 1975, and the last one was filed on April 11th, 1975.
By applying the method of the present application, it is possible to improve and/or extend the scope of the method described in the above-mentioned patents. In fact, these methods are also capable of using the ferrous chloride produced during lead cementation to regenerate cupric chloride, and to provide the chloride solution necessary for leaching. is also possible. The following description is not intended to be limiting in any way.

The following description is intended to explain how to carry out the subject matter of the present application and should be read in conjunction with the accompanying drawings.
The drawing is a very schematic illustration of the method of the present application applied for treating lead-containing sulphide compounds. In the figure, the corporate circuit is shown as a double line, and the liquid circuit is shown as a single line.

According to the figure, lead-containing sulfide compounds are present in selective action reactor 1
supplied to

In the reactor the compound is contacted with a chlorinated steel solution. The source of chlorinated steel will be discussed later. The lead chloride solution obtained as described above is conveyed to a cementation device 2, and the sulfurized residue is conveyed to a separate attack reactor 4.

In the reactor, the retentate is contacted with a cupric chloride solution, and all non-ferrous metals in the retentate are dissolved. In the cementation device 2, the lead chloride solution comes into contact with metallic lead or a metal that is more reducing than lead.

This causes residual impurities of metals more precious than lead to precipitate in the form of metals. The lead chloride solution produced in the device 2 is conveyed to the cementation device 3, where it comes into contact with a metal more reducing than lead, preferably iron.

This causes the lead to precipitate in metallic form and the iron to dissolve to form ferrous chloride.

The ferrous chloride solution produced in the counterfeit 3 is mixed with the nonferrous metal chloride solution produced in the reactor 4 and conveyed to the device 5.

The device regenerates cupric chloride by bubbling air or oxygen-containing gas. Ferrous chloride is precipitated in the form of goethite by the following reaction. 4 Cu++ is eC12 10 days 20 10 pots 2......->stop u++ 12 Fe.

(14 animals) Additionally, a supplementary amount of ferrous chloride and, if necessary, hydrochloric acid may be supplied into the apparatus. The ferric chloride solution recovered as described above is divided into two parts by means of a valve system 6.

The first part is sent to reactor 1 in such an amount as to selectively dissolve the lead. The second part is sent to reactor 4 to dissolve all the non-ferrous metals. It is pertinent to point out that part of the phosphorus as well as the bismuth and antimony that is optionally dissolved in the solution is removed in the goethite precipitation step.

The ferric acid is removed in the form of ferric phosphate, the latter in the form of oxychloride. Processing systems such as those described above are disclosed in French patent applications Nos. 74-06765 and 74-167.
72, 74-16773, 74-16774 and 75-12373, and that these methods are thereby greatly improved. A person skilled in the art would recognize this.

Therefore, when referring to the drawings of the several applications mentioned above,
Devices 4 and 5 of this application are respectively France *Patent Application No. 74
The diamond pupils 2 and 6 of FIG. 1 of No. 116,774 would correspond to devices A and B of French Patent Application No. 75-12,373.

The purpose of the following non-limiting examples is to facilitate the determination of the appropriate processing conditions to be used in each particular case.

Example 1 Second chloride steel with dissolution of lead and precipitation of copper (
In a spherical flask equipped with a leaching heating system for lead concentrate according to CI2) and equipped with a vertical condenser at the top, 250 g/h of sodium chloride and 9.76 g of copper in the form of cupric chloride were added. A solution containing 6.00 g/ml is maintained at a temperature of 80°C.

Next, 428.2% of a finely ground lead concentrate containing 45.1% of lead and 5.83% of zinc in the form of sulphides is introduced at once.

A collection of solids and liquids is violently raped for two hours. After 2 hours of testing, the contents of the flask are filtered and a comparison table of the various components is prepared.

It is clear from this example that almost all of the lead is dissolved and at the same time the copper is precipitated into the solid.

Example 2 Consumption of Attack Residue 1 and Recovery of Precipitated Steel Steel content 9.08/The cupric chloride solution 2Z is maintained at 80° C. in a glass reactor equipped with a vertical cooler.

27.2 hours of the final solid obtained in Example 1 are introduced at once. Stir the whole thing evenly for 2 hours. During this time, the copper ion concentration reached 6.35 m/re. After the experiment is finished,
The aqueous phase is separated from the solid by filtration, and quantitative analysis allows a comparison table of the following substances to be prepared. This experiment reveals that the second attack can recover the copper precipitated during the first attack and dissolve most of the zinc and lead that were not dissolved during the selective attack.

Comparing the chemical composition of the retentate obtained from the second attack to the initial composition of the ore reveals the total dissolution rate of metal for the two attacks. Zinc: 69% Lead: 99.7% Steel: 46% In this way, in addition to the complete redissolution of the copper precipitated during the selective attack, the copper originally present in the concentrate is Almost half of the amount is recovered.

Example 3 Purification of a lead chloride solution by precipitation of impurities This experiment is carried out using a portion of the solution obtained in the experiment of Example 1.

Powdered lead 4 is added to 500' of this solution, which is maintained at 80°C.
Add the yam all at once and stir vigorously.

Continue the rope worship for 70 minutes. After this, solid-liquid separation is performed using a furnace, and an analytical comparison table for the content of impurities is prepared. Weight (9) Zn Cu Po Asi
、 Bi Ag Sb
-Solution amount (flow) large amount *Omitted solution large amount
Tsutomu Aya Solution 500 0.72 1.
82 311 0.1180.01 0.045 0
01 Starting powder lead 4 100 Final solution 500 059 002632.0 00320
0050002 001 It will be appreciated that at the end of this process, the main impurities that are likely to be entrained in the next lead cementation step have been removed from the solution.

These impurities precipitate as precipitates. Precipitates are formed especially in the case of copper and bismuth, as well as some parts of boronate. Example 4 Cementation of lead with spongy iron from a salt aqueous solution of the first chloride vessel (P in 12)* The solution obtained as a result of the precementation of Example 3 above is used for the experiments of this example.

4.3 tons of spongy iron, previously ground to a particle size of 80 to 200 microns, is added to this solution. This spongy iron contains 72.4% metallic iron. 1 at a temperature of 80℃
Dispose of it by worshiping it intensely for 00 minutes. At the end of the treatment, solid-liquid separation is performed and an analytical comparison table of introduced substances and extracted substances is prepared.

Summary Weight (9) Zn Cu Pb
Fe As Bi Ag Sb capacity (required) *- Approximately 1 *- Many *- Son - Approximately 1 Approximately - Pre-precipitation solution 450 9nom 9nori 9
/'' 9 nori 9 no must 9 no must 9 no must 9/〆 Spongy iron 43 0.59 0.03 32.
0 0032 001 0.005 0.0
05 final solution 400 ・,
- 97u final precipitate 11.6 0.58 0
04 9.76 5.94 0-003 0.01
0.001 0.010014 011 79
．． 5 11.0 Side yard edict 0.02 0.002
5 0005 Example 5 Dissolution of lead in salt water of chlorinated steel (C-1) Steel ion amount: 16.5 y/g and total amount of copper: 22.1 y/g
Two volumes of the solution containing it are introduced into a cylindrical reactor.

This solution is maintained at 80° C. and a fraction of Suzu concentrate is continuously introduced. After supplying one fraction of the concentrate, the process is continued by waiting for the concentration of steel ions to stabilize before supplying the next fraction.

The process continues until the steel ions are completely eliminated. The results are summarized in the table below. Misaki S) ” Selection S Flea Punishment Misty Beard S S” Sumiyori S Zehotatsu/Iso Minoru Q Surprise K Kameza Antei Ayaboku Kaoru Towing Carp Tora Za Kuwa Hakude Example 6 Effect of Temperature: Attack of the ore by chlorinated steel (C core 1) at the boiling point* Before introducing the ore, the reducing solution is heated to the boiling point.

Maintain boiling for 5 hours. The following table shows the results of this process.

Example 7 Activation test of ore with cupric chloride (COC12) First, the ore is activated for 18 minutes at 80 pm using a solution of ferric chloride of about 18 pm.

The amount of chlorinated steel used in the treatment was equal to 31.7% of the stoichiometric requirement (QS) to dissolve the lead. *
Next, an amount of the carbon solution is introduced into the reactor such that the initially introduced lead is in excess of 1.1 QS over the total amount of Cr ions bonded to the introduced copper. The results obtained are summarized in the table below.

Weight (9) Capacity (base) (Zn) Total amount of Zn (Cu) Total amount of Cu (Pb) Total amount of Pb Activated solubility 90
18.5 1.67 Attack Solution 410 0.12 0.05 2
2.3 9.14 002 0 new concentrate
38 5.83 222 1.42 0
．． 54 45.10 17.12 Total amount introduced
227 1135
- 17.12 Final solution 480
0.82 039 86 4.13
18.9 907 remaining bay 302
5.85 1.77 16.4 4.
95 24.9 7.52 Total extraction amount
2.16-908
- 16.59 Yield (Tsutomu)
18.1-
It can be seen that the yield and selectivity for 54.7 zinc was improved.

Example 8 Attack in the pulp of lead concentrate bound from 11 collars (Spain) 1762 volumes of lead concentrate are introduced with 4Z' of a cupric chloride solution containing 54 volumes of copper per volume.

This corresponds to 85% of the stoichiometric requirement to convert all the lead present in the ore to leadous chloride. After 11/2 hours of reaction, the reaction mixture is filtered to obtain a filtrate and a cake. The analysis results of the furnace liquid and cake are shown in the following table along with the analysis results of the ore. elemental ore cake
Furnace Liquid lead 47% 33.4% 1
1.19/Shiozinc 4.94 3.98
1.389 Z steel 0.96% 9
．． 10 more 0029 Buddhist iron 134*
Unmeasurable 1.46 9th silver 768
9/t Unmeasurable Chloride Unmeasurable 1
12* Yield of unmeasurable lead chloride is approximately 80% based on ore and 95% based on copper chloride initially used in processing.
It can be pointed out that the zinc dissolution rate is less than 6%, and the selectivity of attack is extremely high.

This experiment shows that chlorination of lead concentrates can improve the solids yield with a short reaction time.

Example 9 Dissolution of lead chloride contained in a chlorinated concentrate
SoPb 4.5 evening/SoZn
o. The brine obtained in the previous experiment containing 0.24 Cu/Cu is maintained at 9.0% in the reactor.

Next, homogeneous solid concubine 2000 obtained in various chlorination experiments
Introducing evening all at once.

This product has the following composition. Pb
33.5% CI 8.73 Taha Zn 3.24% Fe
9.94% Cu 9.24% Day 20 10.0% The solubility of lead chloride as a function of time is shown in the following table.

Time (hours. minutes.) Zngnom Cu9ノ Must Pb9/
0.00 0.22 0.24
4.50.05 0.26
1.0 19.90.10 0
．． 26 1.0 23.10.20
0.30 1.0 26.3
0.40 0.28 1.0
26.61.30 0.30 0.
94 26.0 These experiments confirm the rapidity of lead chloride dissolution.

This is because equilibrium is reached after 2 minutes and 70% of this equilibrium is reached after 5 minutes.

The copper that had precipitated in the previous attack remains virtually insoluble. Example 10 Recovery of HCI+Air from the Chlorinated Remains Channel This experiment was carried out in a 20 cylindrical reactor equipped with a special entrainment system.

In fact, this enrichment system is usually a floating turbine light mill configured to effect ore enrichment. A feature of this type of turbine is that the gas is well dispersed and the gas above the level of the liquid is well recirculated, so that a homogeneous contact between the gas and the mixture is ensured. A solution having the following composition Pb <0.2 t/t Cu 16-6 t/t Zn 41-6 t/t/sFe ○-2 t/t was heated to 80 qo in the reactor.

Solids 11 formed by ores that have been subjected to a continuous two-step process of chlorination and redissolution of 12 in precipitated P.
Introduce 00 evenings at once. This solid has the following composition. Pb 2.61% Cu 18.7% Zn 6. Hammer % Fe I9.2% Day 20 10% Compressed air with a flow rate of 1240 so/h is introduced into the mixture.

101/Solid-liquid separation is carried out after the incubation period. After washing with distilled water, the weight of the remaining solid was 7.5 kg, and the chemical composition was as follows. Pbo. 4
5% Cu o. 99% Zn l. 75% Day 20 16.6% Based on this analysis, the solubility of the element originally present in the solid can be calculated.

Pb spots. 0% Cu 96.3% Zn
82.2% As a result, it will be understood that the copper precipitated in the chlorine-Q stage can be recovered with a sufficient yield, and that the recovery of the remaining Pb and Zn is ensured.

Example 11 Removal of lead-associated impurities by crystallization of lead chloride The purpose of this example is to demonstrate the purity that can be achieved with lead chloride obtained by crystallization.

The crude solution of lead chloride is passed through a furnace and left undisturbed for 4 additional hours.

The initial temperature of the solution is 85°C and the final temperature is 16°C. The obtained crystals are separated by filtration. ** The analysis results of the starting solution and the obtained crystals are shown in the table below. P
b Cu Fe Zh Bi A
g Sb As Sn Summary Starting solution of the edict 1 of the small M omitted from the edict 1 of the small breast that robbed the clouds 8501 2
32 202 0.22 1.32 002800
44 0034 002 0.003 crystal 13.
529 74.4 0015 0.07 0005
0.009 0002 002 0.01 0.01
2 The purity obtained would be approximately 99.9%.

Processing method for Examples 12, 13 and 14: 80 kg of slightly wet lead chloride, equivalent to 56 kg of metallic lead, is melted in a quartz tube.

Hydrogen is bubbled into the molten chloride bath through a quartz pipe.
Prior to reduction, the molten chloride height reaches approximately 5°C.

The processing parameters and results for each example are summarized in the following table.

Example 12 Temperature 800°C Time
1 hour hydrogen flow rate
30〆/hour Weight of residual slag (P ratio 12) Weight of 0ta reduced lead
56 evening yield rate
Similar results can be obtained by using a hydrogen-nitrogen mixture containing 50% hydrogen instead of 100% hydrogen.

The flow rate of Namiai gas is set to 30 pm/hour, and the reaction time is extended to 2 hours. Other conditions remain unchanged. Example 13 Temperature 800°C Time
1 hour hydrogen flow rate
15〆/hour Residual slag weight (12 to P) 31
Weight of reduced lead
M% Example 14 Temperature 700°C Time
1 hour hydrogen flow rate
30Z/hr Weight of residual slag (12 in P) 36
Weight of reduced lead 28 Yield rate
52% The purity of the lead obtained is greater than 99.99%.

The content of various impurities in the lead obtained is summarized in the following table. Impurity amount/T
Elementary (As) 60 antimony (
Sb) Section 30 (Cu)
2 Tin (Sn)
2 Silver (Ag) amount (outside detection limit)
Bismuth (Bi) 〃 〃Zinc (Zn) 〃
Example 15 Purification of Lead Chloride Solution A crude lead chloride solution and fresh lead concentrate are brought into continuous contact in two 20 mm reactors in mutual exchange.

The following processing conditions are used. Average grain height of single grain concentrate: 2
00 micrometer concentrate flow rate: 7 total #/hr - Lead chloride solution flow rate: 202/hr - PH: 1.7 Temperature: 9 pi 0 - Residence time: 2 hours.

The results of this purification are shown in the table below.

This example demonstrates that sufficient purification occurs when a crude lead chloride solution is contacted with a galena-containing ore or concentrate.

With such purity available, it is possible to directly electrolyze (using soluble or insoluble anodes) lead chloride solutions to recover lead in metallic form. It is also pertinent to point out that the purification by contacting fresh galena with lead chloride dissolved in a concentrated chloride solution (more than state) is not interfered with by ferrous chloride.

[Brief explanation of drawings]

The drawing is a schematic illustration of the method of the present application used in the treatment of lead-containing sulfide compounds. 1,. ．． ．．・．． selective action reactor, 2... cementation device, 4... attack reactor, 3... cementation device, 5... device, 6... valve system.

Claims (1)

[Scope of Claims] 1. In a hydrometallurgical method for treating sulfide compounds containing at least lead as a non-ferrous metal, said compounds are selected from the group consisting of bismuth chloride, antimony chloride, arsenic chloride and silver chloride. contact with an aqueous copper chloride solution which may contain at least one chloride selected from A hydrometallurgical process characterized in that it is less than or equal to the stoichiometric requirement of. 2. Process according to claim 1, characterized in that the temperature of the aqueous solution is between 60° C. and the boiling point of the reaction mixture. 3. Process according to claim 1, characterized in that the aqueous solution contains at least 4 gram equivalents of chloride ions per liter. 4. The chlorine ions are introduced into the aqueous solution by adding at least one chloride selected from the group consisting of ammonium chloride, alkali metal chlorides, and alkaline earth metal chlorides. A method according to claim 3. 5. The method according to claim 1, wherein the aqueous solution has a pH value of 0 to 3. 6. A method according to claim 1, characterized in that the sulfide compound is activated before contacting with a chloride selected from the group consisting of ferric chloride and cupric chloride. . 7. The method according to claim 1, characterized in that the lead chloride solution obtained as a result of the contact is purified by contacting with metallic lead. 8. The method according to claim 1, characterized in that lead in the lead chloride solution obtained as a result of the contact is recovered by cementation with a metal more reducing than lead. 9. A method according to claim 8, characterized in that the cementation is electrolysis using a soluble anode of a metal more reducing than lead as an anode. 10. The method according to claim 8 or 9, wherein the reducing metal is zinc. 11. The method according to claim 8, wherein the metal more reducing than lead is iron. 12. The method of claim 1, wherein the aqueous solution contains cupric chloride, and the cupric chloride is regenerated using a regenerant and air. 13. A method according to claim 11 or 12, characterized in that the regenerant is ferrous chloride produced from cementation of lead with iron. 14. The method according to claim 1, characterized in that the amount of lead to be leached per unit volume is greater than the dissolving capacity of the aqueous leaching solution. 15. Process according to claim 14, characterized in that the copper concentration of the aqueous solution is at least equal to 30 g/l. 16 Claim 1, characterized in that the concentration of free chloride ions is equal to at most 2 gram equivalents per liter
The method described in Section 4. 17. The solid mixture of lead chloride and sulfide obtained after filtration of the reaction mixture is treated by a physical separation technique to separate lead chloride from the sulfide. Method. 18. Process according to claim 14, characterized in that the bulb obtained after contacting with the aqueous leach solution is cemented with a metal selected from the group consisting of iron and zinc. 19. Claim 14, characterized in that the mixture of lead chloride and sulfide obtained after filtration of the reaction mixture is returned to the pulp state and precipitated with a metal selected from the group consisting of iron and zinc. The method described in. 20. The method according to claim 18 or 19, characterized in that the metallic lead obtained after cementation is separated from the sulfides by a physical separation technique. 21. Claim 14, characterized in that the solid mixture obtained after filtration of the reaction mixture is redissolved in a solution of dissociated metal chlorides to obtain a solution of lead chloride and a solid phase formed by sulfides. The method described in section. 22. A process according to claim 1, characterized in that the dissolved lead is recovered in the form of crystalline lead chloride, which is then melted and reduced with hydrogen. 23. Process according to claim 22, characterized in that the temperature at which the reduction is carried out is between 850°C and 950°C. 24. Process according to claim 22, characterized in that the hydrogen is diluted in an inert gas. 25. A method according to any of claims 22 to 24, characterized in that hydrogen is blown into the molten lead chloride. 26. Process according to claim 25, characterized in that the hydrogen flow rate per hour is at least equal to twice the stoichiometric requirement for complete reduction of lead chloride. 27 Claim 22, characterized in that hydrogen contained in the gas generated by reduction is separated from hydrochloric acid and reused for reducing lead chloride, and the hydrochloric acid is reused for dissolving lead.
The method described in section. 28. The method according to claim 1, characterized in that metallic lead is obtained by electrolytically treating a lead chloride solution obtained after contact with a sulfide compound containing at least lead as a non-ferrous metal.