CN109402410B - Method for enriching precious metals through iron matte acid slag pretreatment - Google Patents
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Abstract
The invention discloses a method for enriching precious metals by pretreating iron matte acid-soluble slag, and belongs to the technical field of precious metal hydrometallurgy. The invention comprises the following steps: carrying out water leaching treatment on the iron matte acid leaching slag, and carrying out solid-liquid separation to obtain a water leaching solution and water leaching slag; separating impurity elements such as copper, arsenic, antimony, nickel and the like from the water leaching residue by a potential-controlled leaching process to obtain impurity-removed liquid and impurity-removed residue; desulfurizing the impurity-removed slag by adopting a sulfating roasting process to obtain high-grade precious metal gold mud, and then recovering gold, silver and other precious metals in the gold mud by adopting a conventional method; separating valuable metal antimony from the mixed leaching solution by adopting a hydrolysis process to obtain an antimony oxychloride intermediate product and an antimony separating solution; recovering copper from the antimony separating liquid, and oxidizing the copper separating liquid to fix arsenic; and carrying out rotary evaporation treatment on the arsenic removal liquid to obtain a nickel salt crude product. The method can effectively separate and recover various metals in the iron matte acid slag, has higher recovery rate of valuable metals, and can effectively treat harmful arsenic element in the iron matte acid slag.
Description
Technical Field
The invention belongs to the technical field of precious metal wet smelting, and particularly relates to a method for separating impurity elements such as copper, arsenic, antimony, nickel, iron and the like from iron matte acid-soluble slag through a wet process so as to achieve the purpose of enriching precious metal gold and silver, comprehensively recovering valuable elements obtained through separation, and harmlessly treating harmful element arsenic.
Background
The fine particle dip-dyed gold concentrate and gold concentrate containing harmful elements such as arsenic, antimony, carbon and the like are controlled to have lower oxygen potential in the pyrometallurgical smelting process, so that low-melting volatile elements such as arsenic, antimony, lead, zinc and the like are mainly formed into oxide forms and are escaped in a smoke form, silicon dioxide, a small amount of iron elements and smelting additives mainly form a slag phase, the smelting slag is lighter than sulfonium in specific gravity and floats on the upper layer of a molten pool, and pyrite mainly forms iron sulfonium with good trapping effect on precious metals under low oxygen potential. Meanwhile, a small amount of accompanying elements such as copper, nickel and the like in the concentrate mainly form copper matte and low nickel matte to be symbiotic, and a small amount of non-oxidized antimony forms antimony matte to be symbiotic with iron matte. The noble metal is enriched in a sulfonium system mainly comprising iron sulfonium, and is separated from impurities of arsenic, antimony and carbon to obtain good enrichment.
Because iron is an active metal, smelting to form iron matte requires a strong reducing atmosphere to further blow to obtain elementary iron, precious metals such as gold and silver can be enriched in the elementary iron, the obtained elementary iron can be used for obtaining anode mud through an electrolysis mode, the precious metals are mainly enriched in iron electrolysis anode mud, and the process has high cost and basically no industrial application value due to the low value of iron. The iron matte can be leached by sulfuric acid, the iron matte is decomposed into ferrous sulfate and hydrogen sulfide, the precious metals of gold and silver, copper, antimony, arsenic and nickel and part of iron compounds are enriched in acid-soluble slag, the gold and silver are efficiently enriched, and various valuable metals are further recovered by taking the acid-soluble slag as a raw material. Because the contents of heavy metal elements such as copper, antimony, arsenic, nickel and the like in the iron-sulfonium acid-soluble slag are high, and the phase composition is complex, the heavy metal elements need to be separated and valuable metals need to be comprehensively recovered before the gold and the silver are recovered, harmful arsenic elements are properly treated, and the precious metals are further enriched, so that the separation and enrichment of the next working procedure are facilitated.
However, the existing technology for processing the iron matte acid-soluble slag is only reported, and the iron matte acid-soluble slag has great difference from the existing precious metal-containing materials in the aspects of element types, grade compositions and chemical substances. The existing mature precious metal material treatment process is not suitable for iron matte acid soluble slag. If the existing mature sulfating roasting process is adopted to treat the iron matte acid-soluble slag, a large amount of acid smoke is inevitably generated, and more harmful arsenic is taken away, so that the arsenic is dispersed in the roasted slag and the smoke, more importantly Guo scholar et al (Chinese non-ferrous metals bulletin, 2010,20(5): 990-; the oxygen pressure leaching process can be used for separating impurity elements in the precious metal materials, but for the iron sulfonium acid soluble slag, the leaching valence state of antimony is difficult to control in the oxygen pressure leaching process, the subsequent antimony recovery process flow is increased, and meanwhile, the recovery difficulty is increased. If the iron matte acid slag can not be efficiently and comprehensively treated to recover various valuable metals and precious metals, the normal operation of the complex gold concentrate pyrometallurgical smelting process is influenced, and meanwhile, valuable elements cannot be effectively recovered, so that the enterprise benefit and the normal operation are influenced. Therefore, the proper disposal of the iron matte acid slag is an important link and a basic guarantee for the normal operation of the complex gold concentrate pyrometallurgical smelting process.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect that the existing method is difficult to effectively separate and recover various impurities in the iron matte acid slag, and provides a method for enriching precious metals by pretreating the iron matte acid slag. By adopting the technical scheme of the invention, various metal elements in the iron matte acid slag can be effectively separated, the enrichment of noble metals is realized, and the recovery rate of the multi-metal is higher.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention discloses a method for enriching noble metals by pretreating iron matte acid soluble slag, which comprises the following steps:
step one, performing water leaching desalination on iron matte acid-soluble slag
Carrying out water leaching treatment on the iron sulfonium acid leaching slag, separating soluble metal salts, and carrying out solid-liquid separation after leaching to obtain a water leaching solution and water leaching slag;
step two, potential-controlled leaching of water leaching slag to pre-enrich precious metals
Separating impurity elements such as copper, arsenic, antimony and nickel from the water leaching residue by a potential-controlled leaching process to obtain impurity-removed liquid and impurity-removed residue, and mixing the impurity-removed liquid and the water leaching solution to obtain mixed leaching solution;
step three, removing impurity slag, roasting, desulfurizing and further enriching precious metals
Desulfurizing the impurity-removed slag by adopting a sulfating roasting process to obtain high-grade precious metal gold mud, and recovering gold, silver and other precious metals in the gold mud by adopting a conventional process;
step four, mixing the leaching solution to recover antimony
Separating valuable metal antimony from the mixed leaching solution by adopting a hydrolysis process to obtain an antimony oxychloride intermediate product and an antimony separating solution;
step five, recovering copper from the antimony separating liquid and oxidizing and fixing arsenic from the copper separating liquid
Separating high-value metal copper in the antimony separating liquid by adopting an iron powder replacement process to obtain sponge copper and copper separating liquid; carrying out arsenic fixation treatment on the copper separation solution by adopting a ferric salt oxidation arsenic removal process to convert arsenic into stable ferric arsenate, and carrying out solid-liquid separation to obtain arsenic removal solution and ferric arsenate;
sixthly, evaporating the crude nickel product from the arsenic removal liquid
And carrying out rotary evaporation treatment on the arsenic removal liquid to obtain a nickel crude product.
Furthermore, the liquid-solid mass ratio of the water leaching treatment in the step one is 2-10:1, the temperature of ore pulp is controlled to be 30-95 ℃, and leaching is carried out for 0.5-5 h; and simultaneously, the leaching water used in the step one is condensed water or demineralized water of decalcification and magnesium in an arsenic removal liquid evaporation process, and electromagnetic stirring is carried out during leaching treatment.
Furthermore, the treatment process for removing impurities in the control potential in the second step comprises the following steps: adding the water leaching slag into the chloride ion acidic leaching solution according to the liquid-solid mass ratio of 4-8:1, heating to 70-95 ℃ under the stirring condition, detecting the leaching potential of ore pulp by using a double-electrode system, adjusting the ore pulp potential by adding an oxidant to dissolve out copper, arsenic, antimony and nickel elements, reacting for 2-6 hours after the ore pulp potential reaches a preset value, allowing antimony to enter the solution as low-valence ions, and performing solid-liquid separation after the reaction is finished to obtain impurity removing liquid and impurity removing slag.
Furthermore, the chloride ion acid leaching solution uses HCl or HCl and H2SO4Wherein the molar amount of HCl is 3 times or more the molar amount of antimony.
Furthermore, in the second step, the working electrode in the double-electrode system is one of a gold electrode, a platinum electrode, a palladium electrode and a silver electrode, and the counter electrode is one of a copper sulfate reference electrode, a silver-silver chloride electrode, a mercury-mercurous sulfate electrode and a calomel electrode; the oxidant is one or more of chlorine, potassium chlorate, sodium chlorate and sodium hypochlorite.
Furthermore, in the third step, the impurity-removing slag is spread in a roasting plate and placed in a roasting furnace, the spreading thickness is not more than 4mm, the roasting temperature is controlled to be 620-680 ℃, more preferably 650 ℃, sulfating roasting is carried out under the condition of continuous stirring, the roasting is prolonged for 0.5-1h until no spark exists, the roasted sand obtained after the roasting is finished is the high-grade gold mud, and the gold mud is obtained by recovering gold and silver precious metals by adopting the traditional process.
Further, adding quantitative water into an acid-resistant reactor with a stirrer, heating to a preset temperature under the stirring condition, adding the mixed leachate into the reactor according to the concentration of antimony of 1-5g/L, and maintaining the temperature for reaction for 0.5-3h to prepare antimony oxychloride seed crystals; then slowly and quantitatively adding the mixed solution according to the ratio of the total amount of the mixed solution to the total volume of the seed crystal of 1:1-5, and continuously growing fine-particle antimony oxychloride to obtain large-particle antimony oxychloride so as to realize the separation of antimony and other elements; more preferably, the mixed leaching solution is added into a reactor according to the concentration of antimony of 2.5g/L, the reaction temperature is controlled to be 60 ℃, and the reaction time is 2 hours; the ratio of the total amount of the mixed liquid to the total volume of the seed crystals is preferably 1: 1-5.
Further, in the fifth step, the antimony separating liquid is heated to 60-95 ℃, quantitative iron powder is added under the stirring condition, after reaction is carried out for 0.5-2h, nickel powder is added until bubbles are generated, and solid-liquid separation is carried out after reaction is carried out for 0.5-2h, so that a sponge copper intermediate product and a copper separating liquid are obtained; heating the obtained copper separating liquid to 55-95 ℃, then adding quantitative hydrogen peroxide to oxidize low-valence arsenic and iron, keeping the temperature under the stirring condition to react for 2-4h, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removal liquid.
Furthermore, in the fifth step, the antimony separating solution is heated to 75 ℃ to carry out iron powder replacement reaction, the particle size of the iron powder is less than 200 meshes, and the molar weight of the iron powder is the difference between the molar weights of arsenic and iron in the solution; the copper separating liquid is preferably heated to 85 ℃, and the addition amount of hydrogen peroxide is equal to the Fe in the copper separating liquid2+And As3+The content is less than 10-6The mol/L is standard.
Further, in the sixth step, the arsenic removal liquid is fixed on a rotary evaporator through a round-bottom flask, an evaporator vacuum system and cooling water are opened, the vacuum degree is controlled to be less than-0.06 MPa, the round-bottom flask is heated to be higher than 95 ℃, vacuum rotary evaporation is carried out until crystals are generated, the flask is taken down to be cooled to grow crystals, the temperature is reduced to room temperature, then filtration is carried out to obtain a crude nickel product, a crystallization mother liquid is returned to the arsenic removal liquid to carry out secondary evaporation, and evaporation condensate water is returned to the water leaching process; more preferably, the crystal growth temperature is 45 ℃. 3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention relates to a method for enriching precious metals by pretreating iron matte acid-soluble slag, which is characterized in that the inventor adopts the process optimization and adopts the combination of processes of water leaching and desalting of iron matte acid-soluble slag, potential control leaching of water leaching slag to pre-enrich precious metals, roasting and desulfurizing of impurity-removed slag to further enrich precious metals, antimony recovery of mixed leaching solution, copper recovery of antimony separation solution, oxidation and arsenic fixation of copper separation solution, evaporation and crude nickel product evaporation of arsenic removal solution and the like.
(2) The method for pre-treating the iron matte acid soluble slag to enrich the precious metals has high comprehensive recovery rate, can recover various valuable elements such as copper, antimony, nickel and the like from the water leaching solution and the impurity removing solution, simultaneously converts harmful element arsenic into ferric arsenate which has low toxicity and can stably exist by utilizing iron in the leaching solution, realizes the proper treatment of the harmful element arsenic, and has obvious environmental protection benefit.
(3) The method for pre-treating the iron matte acid-soluble slag to enrich the precious metals mainly adopts a wet process flow, the generation of harmful dust is less, the arsenic removal liquid adopts an evaporation process to recover valuable element nickel, and the obtained evaporation condensation is recycled for a front-end leaching process, so that the closed cycle of water is realized, the discharge of waste water is basically avoided, and the method is green and environment-friendly.
Drawings
FIG. 1 is a process flow diagram of a method for pre-treating iron matte acid slag to enrich precious metals.
Detailed Description
With reference to fig. 1, the method for pre-treating iron matte acid slag to enrich precious metals comprises the following steps:
step one, performing water leaching desalination on iron matte acid-soluble slag
Adding a certain volume of water into an acid-resistant reactor, starting electromagnetic stirring, quantitatively adding iron sulfonium acid dissolving slag according to the liquid-solid mass ratio of 2-10:1, controlling the temperature of ore pulp to be 30-95 ℃, stirring and leaching for 0.5-5h, and performing solid-liquid separation after leaching to obtain water leaching liquid and water leaching slag; the leaching water is condensed water or demineralized water of decalcification and magnesium in an arsenic removal liquid evaporation process so as to reduce the influence of calcium and magnesium ions on subsequent evaporation crystallization.
The higher solid mass of the leaching solution can increase the leaching rate of various soluble salts in the water leaching process, but the generated water leaching solution has overlarge volume and can increase the subsequent treatment cost, so the principle of controlling the solid mass ratio of the leaching solution in the water leaching process at a fixed temperature is favorable for ensuring that various salts in the water leaching solution are not saturated, and the higher leaching temperature and the leaching time are favorable for improving the leaching rate of various metal salts.
Step two, potential-controlled leaching of water leaching slag to pre-enrich precious metals
Adding chloride ion acidic leaching solution with a certain concentration into an acid-resistant reactor, adding water leaching residues according to a liquid-solid mass ratio of 4-8:1, heating to 70-95 ℃ under stirring, detecting the leaching potential of ore pulp by using a double-electrode system, adjusting the ore pulp potential by adding an oxidant to dissolve out elements such as copper, arsenic and antimony, reacting for 2-6 hours after the ore pulp potential reaches a preset value, allowing antimony to enter the solution in a low valence state, performing solid-liquid separation after the reaction is finished to obtain impurity-removing liquid and impurity-removing residues, and mixing the impurity-removing liquid and the water leaching solution to obtain mixed liquid.
The acidic chloride ion leaching solution is HCl or HCl and H2SO4The molar amount of HCl is more than 3 times of the molar amount of antimony, and it should be noted that the higher liquid-solid mass ratio and the higher temperature are particularly beneficial to improving the leaching rate of metals, and the liquid-solid mass ratio is controlled by unsaturated precipitation of polymetallic salts in the leachate. The working electrode in the double-electrode system is one of an inert electrode such as a gold electrode, a platinum electrode, a palladium electrode or a silver electrode, and the counter electrode is one of reference electrodes such as a copper sulfate reference electrode, a silver-silver chloride electrode, a mercury-mercurous sulfate electrode or a calomel electrode. The control of the pulp potential is directly related to the selection of the working electrode and the reference electrode, the potentials controlled by different double-electrode systems are different, and the pulp potential value is controlled to be smaller than the dissolution potential of gold after the pulp potential is converted into the standard electrode potential, so that the dissolution of impurities such as copper, arsenic, antimony and the like is ensured, and the oxidation of antimony into Sb is avoided5+. The oxidant is one or any combination of more than one of chlorine, potassium chlorate, sodium chlorate and sodium hypochlorite, and particularly, the chlorine is used as the oxidant, and metal ions are not introduced, so that the subsequent arsenic removal liquid is utilized to recover nickel.
Step three, removing impurity slag, roasting, desulfurizing and further enriching precious metals
The impurity-removed slag is desulfurized by adopting a static oxygen-enriched roasting process to improve the grade of noble metal, quantitative impurity-removed slag is weighed and is flatly paved into a roasting plate, the paving thickness is not more than 4mm, the thinner impurity-removed slag paving thickness is beneficial to shortening the roasting time, and the roasting treatment amount of unit time and unit area is reduced. And (3) placing the roasting disc into a roasting furnace, controlling the roasting temperature at 620-680 ℃, carrying out sulfating roasting under the condition of continuous stirring, prolonging for 0.5-1h after roasting until no spark exists, wherein the roasted product obtained after roasting is high-grade gold mud, and the gold mud is prepared by recovering gold, silver and other precious metals by adopting the traditional process.
Step four, mixed liquor is used for recovering antimony
Adding quantitative water into an acid-resistant reactor with a stirrer, heating to a preset temperature under the stirring condition, adding the mixed solution into the reactor according to the concentration of antimony of 1-5g/L, and maintaining the temperature for reaction for 0.5-3h to prepare the antimony oxychloride seed crystal. Slowly and quantitatively adding the mixed solution according to the ratio of the total amount of the mixed solution to the total volume of the seed crystal of 1:1-5, and continuously growing fine-particle antimony oxychloride to obtain large-particle antimony oxychloride, thereby realizing the separation of antimony and other elements.
The method is characterized in that the amount of the seed crystal is small due to excessively low antimony concentration, the seed crystal particles are large, other ions are easy to wrap, the content of antimony oxychloride impurities is increased, subsequent antimony recovery is not utilized, the amount of the seed crystal is excessive due to excessively high antimony concentration, the seed crystal particles are too small, subsequent antimony recovery is not utilized, 2.5g/L is preferably the proper seed crystal antimony concentration, the preferable reaction temperature is 60 ℃, and the reaction time is 2 hours. It should be noted that, the smaller volume ratio makes the separation of antimony incomplete, the larger volume ratio makes the volume of antimony-separating liquid larger, which increases the cost of subsequent treatment, and the invention preferably has the ratio of the total volume of the mixed liquid to the total volume of the seed crystal of 1: 3.
Step five, recovering copper from the antimony separating liquid and oxidizing and fixing arsenic from the copper separating liquid
Heating the antimony separating liquid to 60-95 ℃, adding quantitative iron powder under the stirring condition, reacting for 0.5-2h, then adding nickel powder until bubbles are generated, and reacting for 0.5-2h, and then carrying out solid-liquid separation to obtain a copper sponge intermediate product and a copper separating liquid; wherein the preferred temperature is 75 ℃, which is the starting temperature of the replacement copper, the reaction can be rapidly carried out after reaching 75 ℃, and the reaction is an exothermic process, and the reaction temperature can be maintained by the reaction heat subsequently. The amount of the used iron powder is the difference between the molar weight of arsenic and the molar weight of iron in the solution, high-quality raw materials with the granularity of iron powder smaller than 200 meshes are preferred, and the smaller granularity of the iron powder is beneficial to accelerating the reaction process.
Then heating the copper separating liquid to 55-95 ℃, adding a certain amount of hydrogen peroxide to oxidize low-valence arsenic and iron, keeping the temperature under stirring for reaction for 2-4h, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removing liquid, wherein the adding amount of the hydrogen peroxide is equal to the Fe in the copper separating liquid2+And As3+The content is less than 10-6The mol/L is standard.
Sixthly, evaporating the crude nickel product by the arsenic removal liquid
Transferring a quantitative arsenic removal solution into a round-bottom flask, fixing the round-bottom flask on a rotary evaporator, opening an evaporator vacuum system and cooling water, wherein the lower vacuum degree is favorable for reducing the boiling point of the solution and improving the evaporation efficiency, preferably the vacuum degree is less than-0.06 MPa, then heating the round-bottom flask to more than 95 ℃, performing vacuum rotary evaporation until a small amount of crystals are generated in the flask, taking down the round-bottom flask for slow cooling and crystal growing, cooling the temperature to room temperature, filtering to obtain a crude nickel product, returning a crystallization mother solution to the arsenic removal solution for secondary evaporation, and returning evaporation condensate water to the water leaching process. Wherein, higher crystal growing temperature can obtain higher purity nickel salt product, lower crystal growing temperature can obtain more evaporation product, and the crystal growing temperature is preferably 45 ℃.
For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention.
Example 1
The method for enriching the precious metals by pretreating the iron matte acid slag comprises the following steps:
1. iron matte acid soluble slag water leaching desalination
2000ml of distilled water is measured and added into a 3L beaker, the beaker is placed on a universal electric furnace and is electromagnetically stirred, 1000.0g of iron matte acid-soluble slag is added according to the liquid-solid mass ratio of 2:1, the leaching temperature is controlled to be 85 ℃, the stirring leaching is carried out for 2h, the solid-liquid separation is carried out after the leaching is finished, the leaching slag rate is 51.20 percent, the precious metal is enriched by about 2 times, and the detection result of the water leaching slag is shown in Table 1.
2. Potential-controlled impurity removal and pre-enrichment of precious metals from water leaching slag
2000ml of hydrochloric acid solution with the concentration of 4mol/L is measured and added into a 3L beaker, 400.0g of water is added for leaching residues under the condition of electromagnetic stirring, the temperature of the solution is controlled to be 95 ℃ by a universal electric furnace, a gold electrode is used as a working electrode, a calomel electrode is used as a reference electrode to form a double-electrode system, the potential of ore pulp is detected, the leaching potential is controlled to be not more than 380mV by introducing ore pulp chlorine, the reaction is carried out for 4 hours after the potential is stabilized, solid-liquid separation is carried out after the reaction is finished, impurity removing liquid and impurity removing residues are obtained, the leaching residue rate is 29.55%, the leaching rate of copper is 94.53%, the leaching rate of arsenic is 95.23%, the leaching rate of antimony is 98.68%, noble metals are further enriched by about 3 times.
3. Roasting and desulfurizing impurity-removed slag to further enrich precious metals
Weighing 100.0g of impurity-removed slag, paving the impurity-removed slag in a roasting tray, putting the roasting tray into a roasting furnace, controlling the roasting temperature to be 650 ℃, roasting in an oxygen-enriched mode until no spark exists, then preserving heat for 0.5h, wherein the roasting rate is 66.47%, the precious metals gold and silver are further enriched by about 1.5 times, the roasted sand is high-grade gold mud, and the precious metals such as gold, silver and the like can be recovered by adopting the traditional process.
4. Recovery of antimony from mixed liquor
Weighing 1L of distilled water, pouring the distilled water into a 2L beaker, heating the distilled water to 60 ℃ under the condition of stirring, slowly adding the mixed solution to ensure that the concentration of antimony in the solution is 2.5g/L, and stirring and reacting for 2 hours to prepare antimony oxychloride seed crystals; maintaining the reaction temperature, adding a mixed solution with the total volume of the seed crystal of 1/3, and carrying out solid-liquid separation after reacting for 2 hours to obtain an antimony oxychloride primary product and an antimony separating solution;
5. recovery of copper from antimony separating liquid and oxidation of copper separating liquid to fix arsenic
Weighing 1L of antimony separating liquid, pouring the antimony separating liquid into a 2L beaker, heating to 85 ℃, adding a certain amount of 200-mesh iron powder under a stirring condition, reacting for 1h, then adding 200-mesh nickel powder until bubbles are generated, reacting for 1h, and then carrying out solid-liquid separation to obtain a sponge copper intermediate product and a copper separating liquid; heating the copper separating solution to 90 ℃, adding hydrogen peroxide until more bubbles are generated, keeping the temperature for reaction for 3 hours under the stirring condition, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removing solution;
6. evaporating crude nickel product from arsenic removing liquid
Transferring 100ml of arsenic removal liquid, adding into a 300ml round-bottom flask, fixing the round-bottom flask on a rotary evaporator, opening an evaporator vacuum system to maintain the vacuum degree of-0.06 MPa, opening cooling water, heating the round-bottom flask to above 95 ℃, performing vacuum rotary evaporation for 30min, generating a small amount of crystals, taking down the round-bottom flask, slowly cooling to 45 ℃, maintaining the temperature for crystal growth for 2h, filtering to obtain a crude nickel product, and returning a crystallization mother liquid to the arsenic removal liquid for secondary evaporation.
TABLE 1 iron matte acid slag pretreatment results
Example 2
The method for enriching the precious metals by pretreating the iron matte acid slag comprises the following steps:
1. iron matte acid soluble slag water leaching desalination
Weighing 2500ml of distilled water, adding the distilled water into a 3L beaker, placing the beaker on a universal electric furnace, starting electromagnetic stirring, adding iron sulfonium acid dissolving slag according to the liquid-solid mass ratio of 6:1, controlling the leaching temperature to be 30 ℃, stirring and leaching for 5 hours, and after leaching, carrying out solid-liquid separation to obtain water leaching liquid and water leaching slag.
2. Potential-controlled impurity removal and pre-enrichment of precious metals from water leaching slag
Measuring 2000ml of hydrochloric acid solution with the concentration of 4.5mol/L, adding the hydrochloric acid solution into a 3L beaker, adding water-soaked slag under the condition of electromagnetic stirring according to the liquid-solid mass ratio of 4:1, controlling the temperature of the solution to 83 ℃ through a universal electric furnace, adopting a gold electrode as a working electrode and a calomel electrode as a reference electrode to form a double-electrode system, detecting the potential of ore pulp, controlling the leaching potential to be not more than 380mV through introducing ore pulp chlorine, reacting for 6 hours after the potential is stabilized, allowing antimony to enter the solution in a low valence state, performing solid-liquid separation after the reaction is finished to obtain impurity-removed liquid and impurity-removed liquid, and mixing the impurity-removed liquid and the.
3. Roasting and desulfurizing impurity-removed slag to further enrich precious metals
Weighing 100.0g of impurity-removed slag, paving the impurity-removed slag in a roasting tray, putting the roasting tray into a roasting furnace, controlling the roasting temperature to be 620 ℃, roasting in an oxygen-enriched mode until no spark exists, then preserving heat for 1 hour, further enriching the precious metals of gold and silver by about 1.5 times, and recovering the precious metals of gold, silver and the like by adopting a traditional process.
4. Recovery of antimony from mixed liquor
Weighing 1L of distilled water, pouring the distilled water into a 2L beaker, heating the distilled water to 65 ℃ under the stirring condition, slowly adding the mixed solution to ensure that the concentration of antimony in the solution is 1g/L, and stirring and reacting for 3 hours to prepare antimony oxychloride seed crystals; maintaining the reaction temperature, adding a mixed liquid with the same volume of seed crystals, reacting for 2 hours, and then carrying out solid-liquid separation to obtain an antimony oxychloride primary product and an antimony separation liquid;
5. recovery of copper from antimony separating liquid and oxidation of copper separating liquid to fix arsenic
Weighing 1L of antimony separating liquid, pouring the antimony separating liquid into a 2L beaker, heating to 95 ℃, adding a certain amount of 200-mesh iron powder under a stirring condition, reacting for 0.5h, then adding 200-mesh nickel powder until bubbles are generated, reacting for 0.5h, and then carrying out solid-liquid separation to obtain a sponge copper intermediate product and a copper separating liquid; heating the copper separating solution to 95 ℃, adding hydrogen peroxide until more bubbles are generated, keeping the temperature for reaction for 2 hours under the stirring condition, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removing solution;
6. evaporating crude nickel product from arsenic removing liquid
Transferring 100ml of arsenic removal liquid, adding into a 300ml round-bottom flask, fixing the round-bottom flask on a rotary evaporator, opening an evaporator vacuum system to maintain the vacuum degree of-0.06 MPa, opening cooling water, heating the round-bottom flask to above 95 ℃, performing vacuum rotary evaporation for 30min, generating a small amount of crystals, taking down the round-bottom flask, slowly cooling to 45 ℃, maintaining the temperature for crystal growth for 2h, filtering to obtain a crude nickel product, and returning a crystallization mother liquid to the arsenic removal liquid for secondary evaporation.
Example 3
The method for enriching the precious metals by pretreating the iron matte acid slag comprises the following steps:
1. iron matte acid soluble slag water leaching desalination
Measuring 2000ml of distilled water, adding the distilled water into a 3L beaker, placing the beaker on a universal electric furnace, starting electromagnetic stirring, adding iron sulfonium acid dissolving slag according to the liquid-solid mass ratio of 10:1, controlling the leaching temperature to 95 ℃, stirring and leaching for 0.5h, and after leaching, carrying out solid-liquid separation to obtain water leaching liquid and water leaching slag.
2. Potential-controlled impurity removal and pre-enrichment of precious metals from water leaching slag
Measuring 2000ml of hydrochloric acid solution with the concentration of 5mol/L, adding the hydrochloric acid solution into a 3L beaker, adding water-soaked slag under the condition of electromagnetic stirring according to the liquid-solid mass ratio of 8:1, controlling the temperature of the solution to be 70 ℃ through a universal electric furnace, adopting a gold electrode as a working electrode and a calomel electrode as a reference electrode to form a double-electrode system, detecting the potential of ore pulp, controlling the leaching potential to be not more than 380mV through introducing ore pulp chlorine, reacting for 2 hours after the potential is stable, allowing antimony to enter the solution in a low valence state, performing solid-liquid separation after the reaction is finished to obtain impurity-removed liquid and impurity-removed liquid, and mixing the impurity-removed liquid and.
3. Roasting and desulfurizing impurity-removed slag to further enrich precious metals
Weighing 100.0g of impurity-removed slag, paving the impurity-removed slag in a roasting tray, putting the roasting tray into a roasting furnace, controlling the roasting temperature to be 680 ℃, roasting in an oxygen-enriched mode until no spark exists, then preserving heat for 0.7h, further enriching the precious metals of gold and silver by about 1.5 times, and recovering the precious metals of gold, silver and the like by adopting a traditional process.
4. Recovery of antimony from mixed liquor
Weighing 1L of distilled water, pouring the distilled water into a 2L beaker, heating the distilled water to 50 ℃ under the stirring condition, slowly adding the mixed solution to ensure that the concentration of antimony in the solution is 5g/L, and stirring and reacting for 2 hours to prepare antimony oxychloride seed crystals; maintaining the reaction temperature, adding a mixed solution with the total volume of the seed crystal of 1/5, reacting for 2.5 hours, and then carrying out solid-liquid separation to obtain an antimony oxychloride primary product and an antimony separation solution;
5. recovery of copper from antimony separating liquid and oxidation of copper separating liquid to fix arsenic
Weighing 1L of antimony separating liquid, pouring the antimony separating liquid into a 2L beaker, heating to 60 ℃, adding a certain amount of 200-mesh iron powder under a stirring condition, reacting for 2 hours, then adding 200-mesh nickel powder until bubbles are generated, reacting for 2 hours, and then carrying out solid-liquid separation to obtain a sponge copper intermediate product and a copper separating liquid; heating the copper separating solution to 55 ℃, adding hydrogen peroxide until more bubbles are generated, keeping the temperature for reaction for 4 hours under the stirring condition, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removing solution;
6. evaporating crude nickel product from arsenic removing liquid
Transferring 100ml of arsenic removal liquid, adding into a 300ml round-bottom flask, fixing the round-bottom flask on a rotary evaporator, opening an evaporator vacuum system to maintain the vacuum degree of-0.06 MPa, opening cooling water, heating the round-bottom flask to above 95 ℃, performing vacuum rotary evaporation for 30min, generating a small amount of crystals, taking down the round-bottom flask, slowly cooling to 45 ℃, maintaining the temperature for crystal growth for 2h, filtering to obtain a crude nickel product, and returning a crystallization mother liquid to the arsenic removal liquid for secondary evaporation.
Claims (10)
1. The method for enriching the precious metals by pretreating the iron matte acid slag is characterized by comprising the following steps of:
step one, performing water leaching desalination on iron matte acid-soluble slag
Carrying out water leaching treatment on the iron sulfonium acid leaching slag, separating soluble metal salts, and carrying out solid-liquid separation after leaching to obtain a water leaching solution and water leaching slag;
step two, controlling potential of water leaching slag to remove impurities and pre-enriching precious metals
Separating impurity elements such as copper, arsenic, antimony, nickel and the like from the water leaching residue by a potential-controlled leaching process to obtain impurity-removed liquid and impurity-removed residue, and mixing the impurity-removed liquid and the water leaching solution to obtain mixed leaching solution; the processing technology of potential control leaching comprises the following steps: adding the water leaching slag into the chloride ion acidic leaching solution according to the liquid-solid mass ratio of 4-8:1, heating to 70-95 ℃ under the stirring condition, detecting the leaching potential of ore pulp by using a double-electrode system, adjusting the potential of the ore pulp by adding an oxidant to dissolve out copper, arsenic, antimony and nickel elements, reacting for 2-6 hours after the potential of the ore pulp reaches a preset value, allowing antimony to enter the solution in a low-valence state ion form, and performing solid-liquid separation after the reaction is finished to obtain impurity removal liquid and impurity removal slag;
step three, removing impurity slag, roasting, desulfurizing and further enriching precious metals
Desulfurizing the impurity-removed slag by adopting a sulfating roasting process to obtain high-grade precious metal gold mud, and then recovering gold, silver and other precious metals in the gold mud by adopting a conventional process;
step four, mixing the leaching solution to recover antimony
Separating valuable metal antimony from the mixed leaching solution by adopting a hydrolysis process to obtain an antimony oxychloride intermediate product and an antimony separating solution; specifically, adding quantitative water into an acid-resistant reactor with a stirrer, heating to a preset temperature under the stirring condition, adding the mixed leachate into the reactor according to the concentration of antimony of 1-5g/L, and reacting for 0.5-3h at the reaction temperature of 60 ℃ to prepare antimony oxychloride seed crystals; then slowly and quantitatively adding the mixed solution according to the ratio of the total amount of the mixed solution to the total volume of the seed crystal of 1:1-5, and continuously growing fine-particle antimony oxychloride to obtain large-particle antimony oxychloride so as to realize the separation of antimony and other elements;
step five, recovering copper from the antimony separating liquid and oxidizing and fixing arsenic from the copper separating liquid
Separating high-value metal copper in the antimony separating liquid by adopting an iron powder replacement process to obtain sponge copper and copper separating liquid; carrying out arsenic fixation treatment on the copper separation solution by adopting a ferric salt oxidation arsenic removal process to convert arsenic into stable ferric arsenate, and carrying out solid-liquid separation to obtain arsenic removal solution and ferric arsenate;
sixthly, evaporating the crude nickel salt product from the arsenic removal liquid
And carrying out rotary evaporation treatment on the arsenic removal liquid to obtain a nickel salt crude product.
2. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 1, characterized in that: the liquid-solid mass ratio of the water leaching treatment in the step one is 2-10:1, the temperature of ore pulp is controlled to be 30-95 ℃, and leaching is carried out for 0.5-5 h; and simultaneously, the leaching water used in the step one is condensed water or demineralized water of decalcification and magnesium in an arsenic removal liquid evaporation process, and electromagnetic stirring is carried out during leaching treatment.
3. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 1, characterized in that: the chloride ion acid leaching solution uses HCl or HCl and H2SO4Wherein the molar amount of HCl is 3 times or more the molar amount of antimony.
4. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 1, characterized in that: in the second step, the working electrode in the double-electrode system is one of a gold electrode, a platinum electrode, a palladium electrode and a silver electrode, and the counter electrode is one of a copper sulfate reference electrode, a silver-silver chloride electrode, a mercury-mercurous sulfate electrode and a calomel electrode; the oxidant is one or more of chlorine, potassium chlorate, sodium chlorate and sodium hypochlorite.
5. The method for pre-treating iron matte acid slag to enrich precious metals according to any one of claims 1-4, wherein: and step three, paving the impurity-removing slag in a roasting plate and placing the roasting plate in a roasting furnace, paving the impurity-removing slag to a thickness not more than 4mm, controlling the roasting temperature to be 620-680 ℃, performing sulfating roasting under the condition of continuous stirring, prolonging the roasting time by 0.5-1h after no spark exists, and recovering gold and silver precious metals from the obtained gold mud by adopting a traditional process.
6. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 5, characterized in that: in the third step, the roasting temperature is controlled to be 650 ℃.
7. The method for pre-treating iron matte acid slag to enrich precious metals according to any one of claims 1-4, wherein: and in the fourth step, the mixed leaching solution is added into a reactor according to the concentration of antimony of 2.5g/L, and the reaction time is 2 hours.
8. The method for pre-treating iron matte acid slag to enrich precious metals according to any one of claims 1-4, wherein: heating the antimony separating liquid to 60-95 ℃, adding quantitative iron powder under the stirring condition, reacting for 0.5-2h, then adding nickel powder until bubbles are generated, and carrying out solid-liquid separation after reacting for 0.5-2h to obtain a sponge copper intermediate product and a copper separating liquid; heating the obtained copper separating liquid to 55-95 ℃, then adding quantitative hydrogen peroxide to oxidize low-valence arsenic and iron, keeping the temperature under the stirring condition to react for 2-4h, and carrying out solid-liquid separation to obtain ferric arsenate and arsenic removal liquid.
9. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 8, wherein the method comprises the following steps: in the fifth step, the antimony separating liquid is heated to 75 ℃ for iron powder replacement reaction, the particle size of the iron powder is less than 200 meshes, and the molar weight of the iron powder is solubleThe difference between the molar amounts of arsenic and iron in the liquor; the copper separating liquid is heated to 85 ℃, and the addition amount of the hydrogen peroxide is equal to the Fe in the copper separating liquid2+And As3+The content is less than 10-6The mol/L is standard.
10. The method for pre-treating iron matte acid slag to enrich precious metals according to claim 8, wherein the method comprises the following steps: fixing the arsenic removal liquid on a rotary evaporator through a round-bottom flask, opening an evaporator vacuum system and cooling water, controlling the vacuum degree to be less than-0.06 MPa, heating the round-bottom flask to be more than 95 ℃, performing vacuum rotary evaporation until crystals are generated, taking down the flask, cooling and crystallizing, cooling to room temperature, filtering to obtain a crude nickel salt product, returning crystallization mother liquor to the arsenic removal liquid for secondary evaporation, and returning evaporation condensate water to the water leaching process; the crystal growth temperature is 45 ℃.
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