RU1785536C - Method for winning precious metals from ores and from products of their processing - Google Patents

Abstract

The use relates to the extraction of noble: metals from ores by autoclave, vat and heap leaching. Essence: in the process of processing ores with a manganese-containing metal aqueous acid composition in the presence of chloride ions, under the condition of chemical reduction and complete production of manganese, acidity and redox potential are measured ( ORP) of the original acid composition. Only a part is introduced into the ore. The invention relates to metallurgy, and in particular to wet processes for the recovery of precious metals from ores and products of their processing, including chlorination, and can be used in autoclave, vat and heap leaching of precious metals. A known method for the extraction of precious metals metals from refractory sulfide ores, a fully developed manganese-containing material, and the other part is treated with the initial acid composition. The resulting solution is diluted with water containing α-chloride ions, and the ore is treated with the diluted solution. The ORP of the obtained production solution is measured. The manganese-containing material and ores are processed at the acidity of the initial acid composition and dilution, ensuring that the ORP of the production solution is higher than the ORP of one composition These operations allow leaching under milder conditions: the minimum required excess of acid and manganese-containing material, providing; more complete recovery of noble metals with a smaller paradise code of the reagents Into the composition of the aqueous acid composition are introduced acids that do not contain the potential of the constituent components, which ensures that the ORP of the production solution exceeds the ORP of the initial acid composition, while maintaining a minimum excess of noble metal oxidants in the leach solution 1 z..p, f-crystals, 2 tab. including treatment with an aqueous acidic composition in the presence of Fe3f ions and a material containing manganese capable of chemical to reduction The method involves de-stadine processing of ores. At the first stage, sulfides are dissolved under the action of oxidizing agents, Fe ions and pyrolusite. As a result, noble metals are bitter. XI 00 ate.

Description

R sulfides discharged. The second stage stage leaching agent is leached out; their own noble metals are globin and by the treasured method, for example cyanirovane. The value of the redox potential (ORP) of an aqueous acidic humicity and production solution are not regulated here. Acidification of the composition recommends maintaining sulfuric acid at a level of pI from O. B to 5.0 Manganese-containing material is introduced t ore either by agglomeration, or on the composition of the aqueous whisper of koi position

The two-stage processing of the horn, according to this method, is associated with an additional consumption of reagents and an increase in the process time. The degree to which metal metals are extracted depends on the degree and association with sulfides, which is not known before and requires almost complete production of sulfides in stage I for the efficient extraction of metapps in stage II And this leads to unproductive reagent consumption

There is also known a one-stage method for the extraction of noble metals, for example gold, from powdered materials and a low-frequency treatment in the presence of pyrolusite, where a significantly higher acidity of the scrubbing solution is used - at a level of 5 M. The method involves the oxidation of β-poride pony by the action of pyrolusite in free: pore and dissolving stomp. AFP measurement and control are not regulated.

Using this method to recover noble metapps or ores can result in high acid consumption.

The most important aspect of the invention is the one-step method of extracting the noble - meta-ore from ores, which also involves the treatment of an aqueous whisper of humic acid containing either hydrochloric acid or sulfuric acid in the presence of sodium porphyry and pyrolusite. hydrochloric acid with a concentration of 3 M when loading pyrolusite 8 kg / t of ore, and in another embodiment, a solution of sulfuric whisper and porous 1da sodium with concentrations of 3 M when loading pyrolyuzite 8 pulp, I1 ontropic ORP is not provided here otren and pyrolusite ore and the acid solution are treated otsnoere- Menno

The application of this method with the process parameters tagged leads to a high consumption of acid and pyrolyusite. On the other hand, the absence of a trophic ORP of a production solution may reduce the degree of extraction of precious metals from ores.

The chain of the invention is to increase the degree of extraction of precious metals and to reduce the consumption of slot and mergenetic material,

Post-foaming, the goal is achieved by introducing into the ore only a part of the manganese-containing paterpap is treated with water

0 the other part with the acid composition and dilute the resulting solution with water, treat the ore with a dilute solution, and treat the margai-containing material and ores with the initial acidity

5 compositions and subsequent dilution, which ensure the AFP product.cipnox rostolra is higher than the potential of the I-ACID COMPOSITION

SUMMARY OF THE INVENTION The processes of extraction are noble: the metals from ores to alloys, the corporide medium in the presence of pyrolusite is presented, for example, by dissolving gold in the form of sporadic reactions. 5HCI-H + CI- (1} MnO: + 4H4 - -Mn; | H K2HMJ (2) 2СГ-МпС12 +

0

MnCh: + - 4 dn2f + ci j Mn H f Mn: + - 2 Mrv 4 Mn H-Cr-MnCI-11

(3) 141

(5)

(6)

2MnCI: + -2Mrrf + Cbr (7) 2Au + 3MnlHH-8Cr-2AuCU to ЗМп2 + (В) 2Au + 3d + 2СГ- 2АиС1,1 (9 | / ml 3MnJI к4СГ-АиЦЦ + 3MnJ + (10)

5

A. H + -HAuCU

(111

3l flnCn + 14HCI + 2Au-

-: i-IA.uCh + ЗМпСЬ to 6НлО (12)

f1 ai- will spontaneously react, - ,, the majority of whispers of the race will be put on dissolving the mer merc dioxide by cutting | 2), for which reason the concentration of yelates in the openings is rather high Presence

non-first-party non-first. for avoiding hgcppn, the pyrolysite raster is due to four initial ions; - and of manganese with c, an ionapi leader according to reactions | 3 and 6), secondly

days of free pore formation according to reanalyses 14 and 7) and, thirdly, for dissolving gold at reanalysis (8 9, 10) In the oxidation of zoopot, as: we see not only the sorbic “pore” can directly participate

reactions | 9), but also ions and Mn l + no peai-- cp m (V, 10 V. As a source of Mn + ions and Mn4f noffiHO, use any other material containing manganese with higher oxidation states i- along with pyrolusite З, к4, 47) or. in other words

chemical reducible manganese in the described process conditions

To dissolve a solid crystalline substance, such as pyrolusite, a higher acidity of the solution is always needed than to prevent the formation of a precipitate of this substance as a result of hydrolysis. This phenomenon occurs because solids have a strong crystal lattice, the destruction of which requires an additional concentration of ions N Therefore, if pyrolyusite is dissolved at high acidity, and then the solution is diluted with water several times, then the diluted solution will have a greater e a high concentration of ions Mn + and Mn S1g than that which can be obtained initially Mpolo solid solution with diluted solution acidity Consequently dilution moi- but prepare a solution with the required concentration of oxidizing agents are noble; metals at significantly lower acidity of the leach solution. For the greater stability of Mn + and Mn ± + ions in a dilute solution, it is better if the water also contains primer ions, forming complex compounds with them. The resulting dilute solution with lower acidity when contacted with ore material will be less reactive. the stronger the solution, as a result of which the incidental acid consumption during the interaction with the ore of the dilute solution will be lower. Thus, if the ore and manganese-containing material are treated with an acid solution at the same time, it is necessary to maintain a high acidity of the solution in order to extract noble metals, thereby increasing races od od. If HIe is first treated with a strong acid solution of only a manganese-containing material, and then diluted with a solution and treated with ore, then the total acid will decrease

Usually, in the composition of ruts and materials containing noble metals, and reducing agents that by-use the oxidizing agent used. Such reducing agents may be ferrous iron minerals sulfides, organic matter, etc. Some of them, passing into the solution, can react directly with solid MnOa, others are more resistant only with the products of dissolution of MpCs with Mn1 ions. CI; However, the latter, as stronger oxidizing agents, react with both those and other reducing agents, cause an increased side consumption In the case of input of the entire load of girganz-containing material B ore and complete production of manganese, i.e. when treated with a strong solution of acid and ore and Mn02, most of the manganese is transferred to the solution in the form of Mn f, Mn + and Cli. But a high concentration of strong oxidizing agents causes both increased and. ” If, however, only part of the fully developed manganese-containing material is introduced into the ore and the other part is used to generate Mn3, Mn4 + and Cb, then under the conditions of low acidity of the diluted solution, solid MnOz to ore E will mainly react directly with reducing agents, without transformation into a form of strong oxidizing agents and in a flail oxidation process in the ore mass will

0 to carry out milder conditions. The consequence of this will be a smaller overall range of manganese-containing material. On the other hand, the ore may contain some components and when processing it

5 with a strong solution of hyaluron in the presence of MnO3, the residual acidity in the production solution may decrease by so much that the generation of ions, Mn 4, will cease. As a result, this will lead to

0 to decay + degree of extraction of the black city. metappe The incidence of dilution of the dilution solution does not affect the concentration of Mn Mn nCbTt solution and contains + it

5 Redox potential (GENERAL aqueous solutions is determined by the ratio of the concentrations of the oxidized and reduced forms of the potential-determining components and the value and

0 standard potential Potential determining components are ions or molecules of substances that form thermodynamically reversible electrode redox pairs in an aqueous solution and change

5 is the measured ORP value with a change in concentration. However, irreversible electrode processes of oxidation or reduction are present. In this case, changes in the concentrations of only reduced

0 or only the oxidized form of the products of such a process does not affect the ORP value of solution 11, finally, in the presence of several substances in the solution, forming “somewhat redox, sp, mixed potential” will be determined by the resulting value for which the greatest substances with the highest concentration values and standard potentials in terms of algebraic magnitude influence, for example, acids that do not contain

The composition of the potential of the master components is sulfuric, hydrochloric, phosphoric, acetic, hydrofluoric and others, since sulfates, chlorides, etc. are oxidized 1type reduced products of the corresponding irreversible electrode processes and do not affect the measured ORP their solutions. On the contrary, the potential-containing components contain acids such as sulfur dioxide, nitric acid, hypochlorite, lornet and others,

In an aqueous solution of qspog that does not contain a potential. Prescriptive. ": Of components, in contact with the atmosphere, the ORP is determined by the standard oxygen potential and the pH value. According to the well-known transformed Nernst formula Eli 1.228-0.059, the pH value of the ORP in such a solution is measured: - depends pH only, i.e. from acidity, and tends to a value of + 1.228 V for so that such a solution with pyrolusite according to reactions 1-7) the solution will be enriched with ions Mn, C1t, the standard potentials of converting them into their reduced forms are +1.82 , 41.51 +1 ZBv, respectively. As you can see, these values exceed the standard potential of the oxygen electrode, and therefore the real potentials of these: substances will exceed it with the process of dissolution of MpCi. When the solution containing Mpl + Mn4 + Cb is in contact with ore reducing agents material these oxidizing agents will irreversibly transform into its reduced form — ions and SH, which are not potential cascading. Therefore, the potential of the production solution will decrease at best to the value of a non-fashionable acid composition and, taking into account the decrease in acidity, it should become even less Reducers from ore (Fed, Pe52ydr), transition to the solution in the separated form, the swamp will lower the potential even more, since this is an indispensable condition for the progress of the redox process. Thus, provided that the full production of strong oxidizing agents in the production solution, its ORP will always be lower than the ORP of the original acid composition. However, this condition implies an under-production of the noble .: metals., T, such processes occur before the youngster only if oxidants are killed in the production solution 11, on the contrary, if even an arbitrarily small excess is contained in the production solution, it is oxidative of the noble metapps, then the degree of their extraction will be higher, but the ORP of the production solution in this case should be higher than in the initial acid composition

From the above reasoning

it follows that if :: introduce a part of the fully developed manganese-containing material into the ore, measure the acidity and

ORP of the initial acid composition, treat it with another part of the manganese-containing material, dilute the resulting solution with water containing chloride ions, treat with diluted

0 solutzrom ore, measure the ORP of the production solution, and treat the manganese-containing material and ore

ACIDITY OF THE ORIGINAL ACID COMPOSITION and dilution, which ensure that the ORP of the production solution is higher than the ORP of the initial acid composition, this will lead to an increase in the recovery of noble metals, lower consumption of acid and manganese-containing material, and the delivered chain will be reached

According to the known and proposed options in the laboratory. The gold-bearing ore sample was treated with a solution of НЗЗСМ and Had in the presence of pyrolusite. The ore sample contained 4.6 g / t bit, 4.2% carbonates (calcite) and 1.3% sulfides (pyrite). The treatment was carried out for 24 hours at a temperature

0 2 | 5 ° С, ratio Ж Т 2: 1 and stirring in a glass of sealed, sealed vessels Rudu and pyrolusite were crushed to a particle size of 90% of the class -0.1 mm. According to a well-known embodiment, an aqueous base composition containing 300 g / l 3M) H2SQ4 and 175 g / l (3M | MaCI. MnO2 loading was 16 kg / t ore (8 kg / m pulp at K: T 2 :: 1 ), ORE and pyrolusite were treated with the acid composition simultaneously.

To the proposed option, several experiments were conducted on the processing of an ore sample with an aqueous acid composition containing 175 g / l MaCI, the acidity of the initial composition was changed from 50 to 450 g / l

5 H2S04 and the redox potential was measured in it. A portion of the pyrolusite load was introduced into the ore sample in the amount of 4 kg / t of ore. The unfinished whisper composition was treated for 3 hours with another part of pyrolysite, the amount of which was taken in unlimited excess. The pulp was filtered and the ore leach was treated with the leaching solution. In the leaching solution, the acidity and the total concentration of Mn4, Clz, and Mn3 oxidants were also measured (in terms of active oxidants) ( chlorine). In both solutions, acidity, active chlorine, and redox were measured in the production solution.

potential. The cache was filtered, washed with water and analyzed for gold by the assay method. The degree of gold recovery and specific consumption of HiSO4 and MnOz were calculated. The consumption of MnOi according to the proposed option was determined by the z-quapent conversion of the specific consumption of active chlorine into MnOg plus 4 kg / t of pyrolyusite ore introduced previously in ore, the production of which was considered complete

The results are presented in Table 1. From Table 1 it follows that, according to the well-known option, a decrease in acidity in the production solution from 300 to 207 g / l HzSCM led I to a decrease in the redox potential to 580 mV, which became significantly lower than its value in the initial acid composition — 890 mV The decrease in potential, in our opinion, was a consequence of, on the one hand, the cessation of the generation of the active pore in the amount necessary for the reductants to be redeemed into the solution, on the other hand, the result of the transfer to the solution stanoviteley in its oxidized and reduced form. For example, iron in the form of ions and As a result, the degree of gold recovery is 56.7% at a flow rate of Нл50} and MnO: 1B6 and 16 kg / t of ore, respectively ..

According to the proposed option, with an increase in the acidity of the initial acid composition in experiments. 1-4 from 50 to 200 g / l of H2-S04, the concentration of active chlorine in the leach solution increased from 0 to 0.9 g / l. As a result, the degree of Li excretion increased from 0 to 31.2%. and the redox potential of the production solution: although it increased from 380 to 510 mV, but there was always the potential of the initial acid composition, where it amounted to 610-790 mV. This happened for the same reason as in the known version, namely, due to the lack of gold oxidizing agents: Mnf, Mn +, and Cb. Starting from experiment 5, the potential of the production solution begins to sharply exceed the potential of the initial acid composition, which is accompanied by an increase in the concentration of active chlorine in the leaching and production solutions, and the degree of recovery and gold, which in the experiment to 5-10 amounted to 87-89%. When comparing the known option and experiment 7 of the proposed option, where the same acidity of the initial composition of 300 g / l H2S04 was applied, it is clear that the preliminary introduction of a part of pyrolusite into the ore and the treatment with the composition is different its parts led along with an increase

the degree of extraction of Au from 56.7 to 87.4% to reduce the total consumption of Mn02 from 16 to 11.1 ct / t of ore. Thus, preliminary introduction of part of MnOl into the ore and processing of its other part with the initial acid composition with acidity, which ensures oxidation the recovery potential of the production solution above the potential from a single position leads to an increase in the degree of gold recovery and a reduction in consumption

Mp02

From experiments 5-10 it also follows that the increase in acidity from 230 to 450 g / l

5 Nd504 no longer leads to an increase in the degree of extraction of Au, but causes a sharp increase in specific: costs and MnOl. Therefore, a series of experiments were subsequently carried out under similar conditions, but with

0 dilution of the leach solution obtained in the experiments. 5-10 with water from a shell of 175 g / p NaCI to a concentration of active chore in experiment 5, those to a concentration of 1.8 g / p. In one experiment, dilution to a concentration of active lore of 09 g / p was carried out5 The results are shown in table 2

As follows from table 2 with an increase in dilution of the leach solution with

0 0 to 8.4 times with the same concentration of active ENT 1.8 g / p, the acidity of the diluted solution decreased from 225 to 48 g / l. As a result, with an approximately equal degree of gold recovery, 87-89%

5, the specific consumption of sulfuric acid was reduced from 122 to 56 kg / t of ore. The consumption of proliferation was 8.4 kg / t. Compared with the known option (sn tab T), the proposed option made it possible to increase the degree of extraction of Au from 56.7 to 87- 89% with a reduction in the amount of NlBOa and MpOl from 186 and 16 kg / t to 56 and 84 kg / t, respectively. The condition for excess of the redox potential of the production solution over the potential of the initial acid composition remained here. In experiment 11, the leaching rye: the creature was diluted to 0.9 g / l of the active pore as a result of the ORP of the production solution

0 (550 mV) fell below the ORP of the acid composition and the degree of Ai recovery decreased to 33.4%,

Thus, the introduction of a part of a fully developed manganese-containing material into the ore, the processing of another part of it with an aqueous acid composition, the dilution of the resulting solution with water containing “loride ions, treatment with a dilute ore solution, with the acidity of the original acid composition

dilution, which ensures the maintenance of the redox potential of the production solution above the potential of the initial composition, can increase the degree of extraction of precious metals and reduce the consumption of acid and mzganese-containing material

The economic effect of the implementation will be more than 1 million .. rub

Claims (1)

SUMMARY OF THE INVENTION 1. A method for recovering precious metals from ores and products of processing moss, including treating the ores with a manganese-containing material and an aqueous acid composition in the presence of chloride ions, chemical reduction and complete production of manganese, extraction of noble metals in a production solution, about ten due to the fact that, in order to increase the degree of extraction of precious metals to reduce the consumption of whispers and manganese-containing material, a part is introduced into the ore of a fully developed manganese-containing material, the acidity and redox potential of the initial acid composition are measured and treating it with another part of the marpene-containing material, the resulting solution was diluted with an aqueous solution containing chloride ions, and treated with a dilute ore solution, measured the redox potential of the obtained production solution, and the processing of manganese-containing material and ores is carried out with the acidity of the initial acid composition and dilution, providing: maintaining the oxidation-reduction potential of the product solution higher than the potential of the initial acid composition 2 The method according to claim 1, about g l and h a y u and s in that acids or mixtures which do not contain potential are added to the composition of the aqueous acidic composition. components T s b p i a 1 Reeupypts obrbbotm-1: w potent ore ore-water-nigpoto composition containing MjCI in the presence of MpCb according to the known and proposed options T e B p and a r and / pattatas of OG ||: pVtg | 1 juptogpprr of a general home test of iodine shotsppi unpoemms with razvelsmt M