Hydrometallurgical process for recovering a plurality of metals from complex rare and precious material

Abstract

A hydrometallurgical process for recovering a plurality of metals from a complex rare and precious material, comprising the following steps: step 1: adding a complex rare and precious material to a hydrochloric acid solution, adding an oxidant for reaction, and then performing filtration to obtain a chlorination liquid and a chlorination residue; step 2: using two-stage counter-current gold loading to obtain a gold-loaded liquid and a post-loading liquid, reducing the gold-loaded liquid, performing clarification to obtain an organic phase, and filtering a precipitate to separate a post-reduction liquid and sponge gold; performing evaporation and concentration on the post-reduction liquid to produce a concentrate 1 and a condensate; and cooling and crystallizing the concentrate, performing filtration to obtain residual oxalic acid, and returning the residual oxalic acid to the reduction process and a post-crystallization liquid to gold loading; step 3: performing low-temperature distillation on the post-loading liquid to obtain a concentrate 2; step 4: performing high-temperature distillation on the concentrate 2 to obtain a concentrate 3; step 5: performing directional crystallization and centrifugal filtration on the concentrate 3 to obtain a crystallization residue and selenous acid; and step 6: washing the crystallization residue by using cold water or a low-acid-level condensate produced in step 3, and performing filtration to obtain a tellurium residue and a palladium-platinum-rhodium-rich liquid.

Description

Process for recovering multiple metals from complex rare and precious materials by full wet method

[0001] Cross-reference to Related Applications

[0002] The present application claims priority to the Chinese patent application No. 202411128723.X filed on August 16, 2024 in the China Patent Office and entitled "Process for recovering multiple metals from complex rare and precious materials by full wet method", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0003] The present application belongs to the field of comprehensive recovery of rare and precious metals, and specifically relates to a process for recovering multiple metals from complex rare and precious materials by full wet method. BACKGROUND

[0004] In the non-ferrous metal smelting process, non-ferrous metals are enriched in anode slime along with gold, platinum, palladium, rhodium, selenium and tellurium. After wet treatment of the anode slime, a product co-enriched with gold, platinum, palladium, rhodium, selenium and tellurium is often produced, such as crude gold powder and platinum-palladium concentrate. These products are intermediate products containing rare and precious metals obtained by reduction of the solution after chlorination of the anode slime.

[0005] The complex rare and precious material containing gold, platinum, palladium, rhodium, selenium and tellurium is treated by the following conventional wet process: complex precious metal material-water solution chlorination dissolution-purification-reduction-gold powder (gold grade ≤ 99.9%), and the platinum, palladium and part of the rhodium in the reduced solution is precipitated by ammonium chloropalladate, and the tellurium and selenium are recovered separately from the reduced solution. The conventional process can well separate tellurium and bismuth from precious metals, but there are problems:

[0006] First, the low dissolution rate of platinum, palladium and rhodium in the chlorination gold separation process leads to dispersion and difficulty in enrichment, and the subsequent recovery rate is low;

[0007] Second, the chlorination slag is difficult to filter, and gold, platinum, palladium and rhodium are easily wrapped and entrained, resulting in loss;

[0008] Third, the gold recovery wastewater is difficult to treat, a large amount of neutralizing agent needs to be added, and neutralization slag containing gold, platinum and palladium is produced, and the high-chlorine and salt-containing wastewater after neutralization cannot be recycled. SUMMARY

[0009] One or more embodiments of the present application provide a process for recovering multiple metals from complex rare and precious materials by full wet method, comprising the following steps:

[0010] Step 1: chlorination dissolution, in a reaction kettle, adding hydrochloric acid aqueous solution, complex rare and precious materials for stirring reaction, heating to 60-70℃, slowly adding oxidant, after the reaction is completed, adding a small amount of complex rare and precious materials for stirring to remove chlorine, stopping stirring to clarify, then extracting the upper chlorination liquid to gold loading, the precipitated chlorination slag is used as raw material for recovering silver; the technical conditions are controlled as follows: the concentration of hydrochloric acid aqueous solution is 5-7 mol / L, the liquid-solid ratio is 3-6:1, and the oxidation process temperature is 80-95℃.

[0011] Step 2: gold loading, using two-stage countercurrent gold loading, after the chlorination liquid is loaded, gold-loaded liquid and post-loading liquid are obtained, the gold-loaded liquid is reduced to the end point and then is separated statically, the organic phase is clarified, and the precipitate is filtered to separate the post-reduction liquid and sponge gold; the post-reduction liquid is evaporated and concentrated to produce concentrated liquid 1 and condensate;

[0012] Step 3: cooling the concentrated liquid 1 in step 2 to <30℃, stirring to crystallize, and then filtering to obtain crystallized liquid and residual oxalic acid, wherein the crystallized liquid returns to the gold loading process in step 2, and the residual oxalic acid returns to the reduction process of the gold-loaded liquid in step 2;

[0013] Step 4: low-temperature distillation, the post-loading liquid in step 2 is subjected to low-temperature distillation to distill low-acid condensate and high-acid condensate, the high-acid condensate returns to step 1 as hydrochloric acid, the low-acid condensate enters step 6 for washing, and the post-distillation residue is concentrated liquid 2;

[0014] Step 5: high-temperature distillation, the concentrated liquid 2 in step 4 is subjected to high-temperature distillation to remove residual water to obtain concentrated liquid 3;

[0015] Step 6: directional crystallization and centrifugal filtration, the concentrated liquid 3 is subjected to directional crystallization and centrifugal filtration to obtain crystallization residue and selenous acid;

[0016] Step 7: washing, the crystallization residue is washed by cold water or the low-acid condensate produced in step 4, and then is filtered to obtain tellurium residue and palladium-platinum-rhodium rich liquid.

[0017] In one or more embodiments, in step 1, the complex rare and precious material composition includes, in mass percentage, selenium 3-20%, tellurium 3-40%, gold ≥1%, platinum ≥0.1%, palladium ≥0.1%, rhodium ≥0.005%, and other impurities <30%.

[0018] In one or more embodiments, selenium, tellurium, gold, platinum, palladium and rhodium all exist in the form of elemental phase.

[0019] In one or more embodiments, in step 1, the oxidant is perchloric acid.

[0020] In one or more embodiments, in step 1, the concentration of the oxidant is 26-30%.

[0021] In one or more embodiments, in step 1, the oxidizing agent is added in an amount of 2.5-4 times the total amount of gold, selenium and tellurium in the input material.

[0022] In one or more embodiments, in step 2, the gold loading is specifically performed by controlling the flow ratio of the loading agent:chlorinated liquid to be 1:0.8-8, using the loading counter-tower 1 and the loading tower 2, and adopting a two-stage loading reaction kettle to countercurrently load the gold, to obtain the gold-loaded liquid and the post-loading liquid after loading, and sending the gold-loaded liquid into a reduction reaction kettle for reduction, and performing static separation when the reduction reaches the end point, and standing for more than 10 minutes, and separating the clarified organic phase, and filtering the precipitate to separate the post-reduction liquid and sponge gold; evaporating and concentrating the post-reduction liquid to produce concentrated liquid 1 and condensate; and returning the concentrated liquid 1 to the reduction process, and returning the condensate to step 1 to supplement the hydrochloric acid aqueous solution.

[0023] In one or more embodiments, the loading agent is a mixture of methyl isobutyl ketone (MIBK) and TBP.

[0024] In one or more embodiments, the diluent is a mixture of one or both of n-dodecane and sulfonated kerosene and chloroform.

[0025] In one or more embodiments, in step 2, the two-stage loading reaction kettle includes a first-stage loading reaction kettle and a second-stage loading reaction kettle.

[0026] In one or more embodiments, a potentiometer is installed at the water phase outlet of the first-stage loading reaction kettle to monitor the potential value of the water phase.

[0027] In one or more embodiments, when the potential value decreases to <520 mV, the chlorinated liquid is stopped, at which time the first-stage gold-loaded liquid is pumped to the reduction reaction kettle for reduction, and the second-stage loading reaction kettle is switched to the first-stage loading reaction kettle.

[0028] In one or more embodiments, in step 2, the gold-loaded liquid is sent into the reactor for reduction.

[0029] In one or more embodiments, in step 2, the reduction temperature is 90-95°C.

[0030] In one or more embodiments, in step 2, the reduction end point of the gold-loaded liquid after reduction contains <0.1 g / L of gold; and the reducing agent is oxalic acid.

[0031] In one or more embodiments, in step 4, when low-temperature distillation is performed, the liquid temperature in the low-temperature distillation tower is controlled to be 60-75°C.

[0032] In one or more embodiments, in step 4, when low-temperature distillation is performed, the pressure in the low-temperature distillation tower is controlled to be 55-65 kPa.

[0033] In one or more embodiments, in step 5, the temperature of the high-temperature distillation is 90-100°C.

[0034] In one or more embodiments, in step 5, the pressure in the evaporator of the high-temperature distillation is 60-80 kPa.

[0035] In one or more embodiments, in step 6, the temperature of the directional crystallization is 75-80°C. BRIEF DESCRIPTION OF DRAWINGS

[0036] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort on the basis of the provided drawings.

[0037] FIG. 1 is a process flow diagram of a complex rare and precious material full-wet recovery of multiple metals disclosed by the present application. DETAILED DESCRIPTION

[0038] The embodiments of the present application are described below, examples of which are shown in the drawings, and the embodiments described with reference to the drawings are exemplary and are intended to explain the present application, but are not understood as limiting the present application.

[0039] The present application discloses a process for complex rare and precious material full-wet recovery of multiple metals, i.e. no sodium salt, no cyanide, no nitrogen oxide, no sulfide in the water phase system, which creates conditions for the cooperation of ion exchange technology and distillation concentration, realizes the regeneration and recycling of hydrochloric acid and water, and produces gold powder with gold content greater than 99.99%, so that noble metals, especially platinum, palladium and rhodium with relatively high content, are treated to obtain high enrichment ratio (liquid phase enrichment ratio of noble metals after dissolution is greater than 30) of these metals, no wastewater is generated in the whole process, the process is short, and the recovery rate of noble metals is high.

[0040] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0041] Step 1: chlorination dissolution, adding hydrochloric acid aqueous solution and complex rare and precious material in a reaction kettle for stirring reaction, heating to 60-70°C, slowly adding oxidizing agent, after the reaction is completed, adding a small amount of complex rare and precious material for stirring and chlorine removal, stopping stirring and clarifying, then extracting the upper chlorination liquid clarification liquid into gold upper loading, and the chlorination slag precipitated as a raw material for recovering silver; the technical conditions are controlled as follows: the concentration of hydrochloric acid aqueous solution is 5-7 mol / L, the liquid-solid ratio is 3-6:1, and the temperature of the oxidation process is 80-95°C;

[0042] Step 2: gold loading, gold is loaded by two-stage countercurrent loading, a gold loading solution and a post-loading solution are obtained after the chlorination solution is loaded, the gold loading solution is reduced, static separation is performed until the end point, the organic phase is clarified, and the precipitate is filtered to separate a post-reduction solution and sponge gold; the post-reduction solution is concentrated by evaporation to produce a concentrated solution 1 and a condensate;

[0043] Step 3: the concentrated solution 1 in step 2 is cooled to <30℃, and stirring crystallization is performed, and a post-crystallization solution and residual oxalic acid are obtained by filtration, wherein the post-crystallization solution is returned to the gold loading process in step 2, and the residual oxalic acid is returned to the reduction process of the gold loading solution in step 2;

[0044] Step 4: low-temperature distillation, the post-loading solution in step 2 is subjected to low-temperature distillation, and a low-acid condensate and a high-acid condensate are distilled out, the high-acid condensate is returned to step 1 as hydrochloric acid, the low-acid condensate is used for washing in step 6, and a post-distillation residual solution is concentrated solution 2;

[0045] Step 5: high-temperature distillation, the concentrated solution 2 in step 4 is subjected to high-temperature distillation to remove residual water to obtain concentrated solution 3;

[0046] Step 6: directional crystallization and centrifugal filtration, the concentrated solution 3 is subjected to directional crystallization and centrifugal filtration to obtain crystalline residue and selenous acid;

[0047] Step 7: washing, the crystalline residue is washed by cold water or the low-acid condensate produced in step 4, and filtration is performed to obtain tellurium residue and a palladium-platinum-rhodium rich solution.

[0048] The chemical equation of step 1 reaction is as follows: 7Au + 3HClO4 + 25Cl - + 21H - = 7[AuCl4] -1 + 12H2O.

[0049] Beneficial effects are: the problems of long reaction time and poor on-site environment caused by the chlorine chasing operation in the chlorination dissolution process of other technologies can be avoided; the gold leaching effect in the chlorination dissolution process is improved by re-chlorination of the chlorination residue, the filtration frequency of the chlorination residue is reduced, and gold loss in the filtration process is avoided.

[0050] In one or more embodiments, in step 1, the complex rare and precious material components include, in mass percentage: selenium 3-20%, tellurium 3-40%, gold ≥1%, platinum ≥0.1%, palladium ≥0.1%, rhodium ≥0.005%, and other impurities <30%.

[0051] In one or more embodiments, selenium, tellurium, gold, platinum, palladium, and rhodium are in the form of elemental phase.

[0052] In one or more embodiments, in step 1, the oxidizing agent is perchloric acid.

[0053] In one or more embodiments, the concentration of the oxidizing agent in step 1 is 26-30%.

[0054] In one or more embodiments, the oxidizing agent in step 1 is added in an amount of 2.5-4 times the total amount of gold, selenium, and tellurium in the input material.

[0055] In one or more embodiments, in step 2, the gold loading process is as follows: the flow ratio of the loading agent (chlorinated liquid) is controlled to be 1:0.8-8, and the gold is loaded in two stages using countercurrent loading in loading reactor 1 and loading reactor 2. After loading, a gold-loaded liquid and a post-loading liquid are obtained. The gold-loaded liquid is sent to a reduction reactor for reduction. After reduction to the end point, static separation is performed, and the system is allowed to stand for more than 10 minutes. The clarified organic phase is separated, and the precipitate is filtered to separate the post-reduction liquid and sponge gold. The post-reduction liquid is evaporated and concentrated to produce concentrated liquid 1 and a condensate. The concentrated liquid 1 is returned to the reduction process, and the condensate is returned to step 1 to supplement the hydrochloric acid aqueous solution.

[0056] In one or more embodiments, the loading agent is a mixture of methyl isobutyl ketone (MIBK) and TBP.

[0057] In one or more embodiments, the diluent is a mixture of one or both of n-dodecane and sulfonated kerosene and chloroform.

[0058] In one or more embodiments, in step 2, the two-stage loading reactor includes a first-stage loading reactor and a second-stage loading reactor.

[0059] In one or more embodiments, a potentiometer is installed at the water phase outlet of the first-stage loading reactor to monitor the potential value of the water phase.

[0060] In one or more embodiments, when the potential value decreases to <520 mV, the flow of chlorinated liquid is stopped. At this time, the first-stage gold-loaded liquid is pumped to the reduction reactor for reduction, and the second-stage loading reactor is switched to the first-stage loading reactor.

[0061] The loading reaction is as follows: R + HAuCl4= [RH + ][AuCl4 - ].

[0062] In one or more embodiments, in step 2, the reduction temperature is 90-95°C.

[0063] In one or more embodiments, in step 2, the reduction end point of the gold-loaded liquid contains <0.1 g / L of gold, and the reducing agent is oxalic acid.

[0064] The reduction reaction is as follows: 3H2C2O4+ 2[RH + ][AuCl4-] = 2Au + 6CO2+ 8H ++8Cl - +2R。

[0065] In one or more embodiments, in step 4, the temperature of the liquid in the low-temperature distillation column is controlled to be 60-75℃ during the low-temperature distillation.

[0066] In one or more embodiments, in step 4, the pressure in the low-temperature distillation column is controlled to be 55-65kPa during the low-temperature distillation.

[0067] In one or more embodiments, in step 5, the temperature of the high-temperature distillation is 90-100℃.

[0068] In one or more embodiments, in step 5, the pressure in the evaporator during the high-temperature distillation is 60-80kPa.

[0069] In one or more embodiments, in step 6, the temperature of the directional crystallization is 75-80℃.

[0070] The principle of the directional crystallization is that, after the high-temperature distillation, the free water and hydrochloric acid in the loaded liquid are distilled dry, and the remaining part is platinum chloride, palladium chloride, rhodium chloride, tellurium chloride and selenious acid. When the temperature is reduced to 75-80℃, all except selenious acid are precipitated in solid form, and the directional crystallization separates the noble metals and tellurium from selenium.

[0071] The crystallization residue is washed with cold water to dissolve the soluble noble metal salts into the palladium-platinum-rhodium rich liquid, and the tellurium is separated. The obtained palladium-platinum-rhodium rich liquid has high noble metal concentration and impurity tellurium, and can be used as a liquid raw material for the separation and purification of palladium, platinum and rhodium. The palladium, platinum and rhodium can be separated and purified by the processes of palladium extraction, platinum extraction and reduction precipitation of rhodium to obtain corresponding products or high-grade concentrates.

[0072] Compared with the prior art, the present application has the following beneficial effects:

[0073] (1) The present application proposes a wastewater zero discharge technology, i.e. there is no sodium salt, no cyanide, no nitrogen oxide, no sulfide in the aqueous phase system, which creates conditions for the cooperation of ion exchange technology and distillation concentration, and realizes the regeneration and circulation of hydrochloric acid and water.

[0074] (2) The present application has strong adaptability to complex materials containing gold, platinum, palladium, rhodium, selenium and tellurium, and is particularly suitable for materials with high selenium and tellurium and low noble metals. Higher direct recovery rate and recovery can be obtained, selenium and tellurium are separated from the solution, and higher concentration of platinum, palladium, rhodium and rhodium noble liquid is obtained, which facilitates the further extraction of these metals.

[0075] For better understanding of the present application, the following examples are further illustrated in detail, but can not be understood as limiting the present application, some non-essential improvements and adjustments made by those skilled in the art according to the above content are also regarded as falling within the scope of the present application.

[0076] Example 1

[0077] The precious and rare materials of selenium 3.0%, tellurium 37.3%, gold 1.16%, platinum 0.107%, palladium 0.31%, rhodium 0.0052% are put in 100 kg, and the operation steps of example 1 are as follows:

[0078] Step 1: chlorination dissolution, 36% hydrochloric acid 355 kg is added in the reaction kettle according to the liquid-solid ratio of 5:1, and water is supplemented to prepare 500 ml of 7 mol / L hydrochloric acid solution, then the stirrer is started, the complex precious and rare materials are slowly added and stirred, the temperature is raised to 60℃, 28% perchloric acid 47 kg is slowly added, the oxidation temperature is controlled at 82℃, after the reaction is completed, 3 kg of complex precious and rare materials are added for stirring and chlorine removal, after stopping stirring and clarifying, the upper chlorination liquid clarification liquid is extracted into gold upper loading, the chlorination slag precipitated is left in the kettle and continues to chlorinate and dissolve with the next batch of materials, and the process is repeated for 2 times, then the chlorination slag 3.2 kg is filtered as the raw material for recovering silver. The weight composition of the chlorination slag is: gold 0.188%, platinum 0.066%, palladium 0.0165%, rhodium 0.0012%, tellurium 11.73%, selenium 1.65%, silver 28.67%, lead 7.35%, and the chlorination liquid clarification liquid 461 L is produced (containing gold 2.59 g / L, platinum 0.234 g / L, palladium 0.693 g / L, rhodium 0.0112 g / L, tellurium 82.7 g / L, selenium 6.61 g / L).

[0079] Step 2: Gold recovery: The loading agent is prepared by MIBK: TBP: sulfonated kerosene: chloroform = 30%: 10%: 50%: 10%. The chlorination solution of step 1 is loaded with gold by countercurrent loading in two stages (stage 1 and stage 2) at a flow ratio of loading agent to chlorination solution of 1:8. A potential meter is installed at the water phase outlet of the loading reactor in stage 1 to monitor the potential value of the water phase. When the potential value decreases to 508 mV, the chlorination solution is stopped. At this time, the gold-loaded solution in stage 1 is pumped into the reduction reactor for reduction, and stage 2 is switched to stage 1. After loading, 58 L of gold-loaded solution and 460.6 L of post-loading solution are obtained, with gold content of 20.58 g / L, platinum, palladium, and rhodium content all less than 0.001 g / L. The gold-loaded solution is sent to the reducer for reduction. The reducer is oxalic acid, prepared as an 80 g / L oxalic acid solution of 20 L. The reduction temperature is 90°C. The gold content of the post-reduction solution is 0.01 g / L at the end of reduction. After reduction to the end point, static separation is performed for more than 10 minutes. The organic phase and the post-reduction solution mixed with the coarse gold powder are separated by filtration to obtain 19.5 L of post-reduction solution and 1.192 kg of sponge gold with a gold grade of 99.996%. The post-reduction solution is evaporated in an evaporator to obtain concentrated solution 1 (3 L) and condensate (16 L). The concentrated solution 1 is returned to the reduction process, and the condensate is returned to step 1.

[0080] Step 3: The concentrated solution 1 is cooled to 26°C and stirred to crystallize. After filtration, the crystallized solution and residual oxalic acid are obtained. The crystallized solution is returned to the gold loading process of step 2, and the residual oxalic acid is returned to the reduction process of the gold-loaded solution of step 2.

[0081] Step 4: Low-temperature distillation: The post-loading solution of step 2 is pumped into a low-temperature vacuum evaporator. The liquid temperature in the low-temperature distillation column is controlled at 65°C, and the pressure in the distillation column is controlled at 55 kPa. The low-acid condensate 143.2 L (containing gold 0.0001 g / L, platinum 0.0001 g / L, palladium 0.0001 g / L, rhodium 0.0001 g / L, tellurium 2.2 g / L, selenium 0.12 g / L) and high-acid condensate 113 L (containing gold <0.0001 g / L, palladium <0.0001 g / L, rhodium <0.0001 g / L, tellurium 2.21 g / L, selenium 0.1 g / L, H + 2.6 g / L) are distilled. The high-acid condensate is returned to step 1 as hydrochloric acid, and the low-acid condensate is used for washing in step 6. The concentrated solution 2 (204.4 L) is obtained, containing gold 0.0026 g / L, platinum 0.527 g / L, palladium 1.56 g / L, rhodium 0.0251 g / L, tellurium 184.86 g / L, and selenium 14.77 g / L.

[0082] Step 5: High-temperature distillation: The concentrated solution 2 of step 4 is transferred to a high-temperature evaporator, and the temperature is further increased to 96°C. The pressure in the evaporator is controlled at 68 kPa to remove residual water until crystals are produced, and concentrated solution 3 is obtained.

[0083] Step 6: directional crystallization and centrifugal filtration: the concentrated solution 3 (63 L) discharged in step 5 contains gold 0.0017 g / L, platinum 1.705 g / L, palladium 4.93 g / L, rhodium 0.079 g / L, tellurium 585.93 g / L, selenium 45.0 g / L, and the discharge is cooled to 76°C to perform directional crystallization to obtain crystalline residue 58.45 kg (containing gold 0.0002%, platinum 0.184%, palladium 0.53%, rhodium 0.0084%, tellurium 62.78%, selenium 0.39%) and selenous acid 4.3 L (containing gold 0.0004 g / L, platinum 0.04 g / L, palladium 0.159 g / L, rhodium 0.0067 g / L, tellurium 50.64 g / L, selenium 606.25 g / L) by centrifugal filtration;

[0084] Step 7: washing the crystalline residue in step 6 with cold water or low-acid condensate produced in step 4, controlling the pH during the washing process to be 2-3, and filtering after washing to obtain tellurium residue 63.4 kg (containing gold <0.0001%, platinum <0.0001, palladium 0.001%, rhodium <0.0001%, tellurium 56.55%, selenium 0.19%) and palladium-platinum-rhodium rich liquid (containing gold 0.004 g / L, platinum 4.52 g / L, palladium 13.11 g / L, rhodium 0.209 g / L, tellurium 35.76 g / L, selenium 4.491 g / L).

[0085] Comparative Example 1: implementation method:

[0086] For the composition of the waste acid treated in Example 1, the aqueous solution chlorination method is used to dissolve to obtain a chlorinated solution containing noble metals - neutralize and adjust the pH - reduce and precipitate gold - precipitate platinum palladium with ammonium chloropalladate, and the specific operation steps are as follows:

[0087] (1) According to the liquid-solid ratio of 5:1, 60 g / L hydrochloric acid, sodium chlorate 15 kg, control the temperature to 95°C, stir for 4 hours after dissolution, obtain chlorinated solution 452 L (containing gold 2.46 g / L, containing palladium 0.65 g / L, platinum 0.33 g / L, rhodium 0.01 g / L, selenium 5.37 g / L, tellurium 79.72 g / L), chlorinated residue 18.6 kg (gold 0.477%, palladium 0.14%, rhodium 0.0037%, platinum 0.033%, tellurium 13.24%, selenium 3.51%).

[0088] (2) The chlorinated solution obtained in step (1) is neutralized to pH=3 by adding sodium hydroxide, and filtered to obtain a neutralized solution 449 L (containing gold 2.2 g / L, platinum 0.22 g / L, palladium 0.63 g / L, rhodium 0.01 g / L, tellurium 75.84 g / L, selenium 5.38 g / L), neutralized residue 3.4 kg, containing gold 2.05%, platinum 0.153%, palladium 0.322%, rhodium 0.0009%, tellurium 58.3%, selenium 0.34%.

[0089] (3) The neutralized solution from step (2) is heated to 86-90°C and 0.3 kg of oxalic acid is added to reduce the gold content to 99.9% to obtain about 0.988 kg of gold powder, and 445 L of reduced solution is produced.

[0090] (4) The reduced solution from step (3) is controlled at 57°C and 8 kg of sodium chlorate is slowly added to produce 1.0 kg of ammonium chloropalladate, containing 0.28% gold, 7.78% platinum, 24.72% palladium, 0.169% rhodium, 3.4% tellurium, and 1.1% selenium. The palladium-containing solution is 445 L, containing 0.519 g / L of gold, 0.061 g / L of platinum, 0.08 g / L of palladium, 0.0063 g / L of rhodium, 76.45 g / L of tellurium, and 5.1 g / L of selenium.

[0091] Example 1 Effect Comparison:

[0092] Example 1 recovers gold powder with a purity of 99.99% from rare and valuable materials containing 3.0% selenium, 37.3% tellurium, 1.16% gold, 0.107% platinum, 0.31% palladium, and 0.0052% rhodium. The metal direct yield is shown in Table 1. The direct yield and recovery rate of each metal in Example 1 are superior to those in Comparative Example 1. In addition, the method of Example 1 does not use nitric acid, cyanide, sulfur dioxide, alkali, and other reagents, truly achieving acid regeneration and use, and achieving zero emission. The specific implementation technical and economic indicators are shown in Table 1.

[0093] Table 1 Effect Comparison of Example 1 and Comparative Example 1

[0094] Example 2

[0095] For 100 kg of rare and valuable materials containing 11.9% selenium, 17.8% tellurium, 15.0% gold, 0.146% platinum, 11.93% palladium, and 0.0064% rhodium, the operation steps of Example 2 are as follows:

[0096] Step 1: Chlorination dissolution: according to the liquid-solid ratio 3:1, 36% hydrochloric acid 182.5 kg is added, water is added in the reaction kettle to prepare 300 L of hydrochloric acid solution containing 6 mol / L hydrochloric acid, the stirring is started, the complex rare and precious materials are slowly added and stirred, the temperature is raised to 65°C, 26% perchloric acid 43 kg is slowly added, the temperature of the oxidation process is controlled at 88°C, after the reaction is completed, 3 kg of complex rare and precious materials are added for stirring and chlorine removal, after the stirring is stopped and clarification, the upper chlorination liquid clarification liquid is extracted into the gold loading, the chlorination residue left in the kettle is continuously chlorinated with the next batch of materials, and the process is repeated for three times, 2.7 kg of chlorination residue is obtained by filtration, and the chlorination residue is used as the raw material for recovering silver. The composition of the chlorination residue obtained by filtration is: gold content 0.41%, platinum 0.0011%, palladium 0.0957%, rhodium 0.0041%, tellurium 11.65%, selenium 1.82%, silver 29.2%, lead 3.51%, and 296 L of chlorination liquid clarification liquid is produced (containing gold 41.52 g / L, platinum 0.51 g / L, palladium 4.147 g / L, rhodium 0.0065 g / L, tellurium 60.76 g / L, selenium 41.39 g / L).

[0097] Step 2: Gold recovery: the loading agent is prepared according to MIBK:TBP:sulfonated kerosene:chloroform=35%:5%:55%:5%. The chlorination liquid of step 1 is loaded according to the flow ratio of the loading agent:chlorination liquid:1:6, and the gold is loaded in two stages (first stage and second stage) countercurrently. A potential meter is installed at the water phase outlet of the first stage loading reactor to monitor the potential value of the water phase. When the potential value decreases to 512 mV, the chlorination liquid is stopped. At this time, the first stage loaded gold liquid is pumped into the reduction reactor for reduction, and the second stage loading is switched to the first stage loading. After loading, 164 L of loaded gold liquid and 295 L of loaded liquid are obtained, the loaded gold liquid contains gold 74.87 g / L, platinum, palladium and rhodium all <0.001 g / L, which is sent to the reducer for reduction. The reducing agent is oxalic acid, which is prepared into 85 g / L oxalic acid solution 50 L. The reduction temperature is 92°C. The reduction endpoint of the loaded gold liquid contains gold 0.007 g / L. The reduction is stopped at the endpoint and static separation is carried out. After 10 minutes of static separation, the organic phase and the mixed crude gold powder after reduction of the reduction liquid are separated by filtration to obtain 49.6 L of reduction liquid and 12.28 kg of sponge gold with gold grade 99.996%. The reduction liquid is evaporated in an evaporator to obtain concentrated liquid 1 (8 L) and condensate (41 L). The concentrated liquid 1 is returned to the reduction process, and the condensate is returned to step 1.

[0098] Step 3: The concentrated liquid 1 is cooled to 25°C and crystallized by stirring. After filtration, the crystallized liquid and residual oxalic acid are obtained. The crystallized liquid is returned to the gold loading process of step 2, and the residual oxalic acid is returned to the reduction process of the loaded gold liquid of step 2.

[0099] Step 4: Low temperature distillation: The liquid from Step 2 was pumped into a low temperature vacuum evaporator, the temperature of the liquid in the distillation column was controlled at 70°C, the pressure in the distillation column was controlled at 61 kPa, low acid condensate 124 L (containing gold 0.0001 g / L, platinum 0.0001 g / L, palladium 0.0001 g / L, rhodium 0.0001 g / L, tellurium 0.876 g / L, selenium 0.877 g / L) and high acid condensate 104 L (containing gold <0.0001 g / L, palladium <0.0001 g / L, rhodium <0.0001 g / L, tellurium 1.34 g / L, selenium 1.41 g / L) were distilled out, the high acid condensate was returned to Step 1 as hydrochloric acid, the low acid condensate was used in Step 6 for washing, and concentrated liquid 2 (67 L) was produced, containing gold 0.0147 g / L, platinum 2.227 g / L, palladium 18.31 g / L, rhodium 0.096 g / L, tellurium 263.67 g / L, selenium 178.67 g / L. + 2.6 g / L), high acid condensate was returned to Step 1 as hydrochloric acid, low acid condensate was used in Step 6 for washing, and concentrated liquid 2 (67 L) was produced, containing gold 0.0147 g / L, platinum 2.227 g / L, palladium 18.31 g / L, rhodium 0.096 g / L, tellurium 263.67 g / L, selenium 178.67 g / L.

[0100] Step 5: High temperature distillation: The concentrated liquid 2 from Step 4 was transferred to a high temperature evaporator, the temperature was further increased to 96°C, the pressure in the evaporator was controlled at 68 kPa, and the residual water was removed until crystals were produced, and concentrated liquid 3 was produced.

[0101] Step 6: Directional crystallization and centrifugal filtration: The concentrated liquid 3 (32 L) from Step 5, containing gold 0.306 g / L, platinum 4.66 g / L, palladium 38.245 g / L, rhodium 0.200 g / L, tellurium 545.35 g / L, selenium 372.67 g / L, was cooled to 73°C, directional crystallization was carried out, and crystalline residue 27.36 kg (containing gold 0.035%, platinum 0.544%, palladium 4.467%, rhodium 0.023%, tellurium 63.407%, selenium 3.504%) and selenous acid 16.83 L (containing gold 0.0004 g / L, platinum 0.04 g / L, palladium 0.159 g / L, rhodium 0.0067 g / L, tellurium 50.64 g / L, selenium 606.25 g / L) were obtained by centrifugal filtration.

[0102] Step 7: The crystalline residue from Step 6 was washed with cold water or low acid condensate produced in Step 4, the pH during the washing process was controlled at 2-3, and after washing, tellurium residue 63.4 kg (containing gold <0.0001%, platinum <0.0001, palladium 0.001%, rhodium <0.0001%, tellurium 56.55%, selenium 0.19%) and palladium platinum rhodium rich liquid (containing gold 0.004 g / L, platinum 4.52 g / L, palladium 13.11 g / L, rhodium 0.209 g / L, tellurium 35.76 g / L, selenium 4.491 g / L) were obtained by filtration.

[0103] Comparative Example 2: Method for implementation:

[0104] For the composition of the waste acid treated in Example 2, the water solution chlorination method is used to dissolve to obtain a chlorination solution containing noble metals - neutralize and adjust pH - reduce and precipitate gold - precipitate platinum palladium by ammonium chloropalladate, and the specific operation steps are as follows:

[0105] (1) According to the liquid-solid ratio of 3:1, 80 g / L hydrochloric acid, sodium chlorate 15 kg, control the temperature at 95℃, and stir for 4 hours after dissolution, obtain 297L of chlorination solution (containing gold 48.9g / L, palladium 3.84g / L, platinum 0.463g / L, rhodium 0.0197g / L, selenium 32.14g / L, tellurium 56.87g / L), and 16.3kg of chlorination residue (gold 5.99%, palladium 0.551%, rhodium 0.0046%, platinum 0.076%, tellurium 8.64%, selenium 16.9%).

[0106] (2) The chlorination solution obtained in step (1) is neutralized to pH=2 by adding sodium hydroxide, and the neutralized solution 278L (containing gold 51.96g / L, palladium 4.212g / L, platinum 0.514g / L, rhodium 0.0236g / L, tellurium 61.746g / L, selenium 5.38g / L) is obtained by filtration, and the neutralization residue 4.8kg contains gold 21.95%, palladium 4.7%, platinum 0.15%, rhodium 0.0011%, tellurium 23.64%, and selenium 0.34%.

[0107] (3) The neutralized solution produced in step (2) is heated to 90℃, and 5kg of oxalic acid is added to reduce to obtain about 14.446kg of gold powder with gold grade of 99.9%, and 273L of reduced solution is produced

[0108] (4) The reduced solution produced in step (3) is controlled at a temperature of 59℃, and 6kg of sodium chlorate is slowly added to produce 4.2kg of ammonium chloropalladate containing gold 0.281%, palladium 24.73%, platinum 3.0%, rhodium 0.083%, tellurium 0.41%, and selenium 0.22%. The palladium precipitation solution contains gold 1.86g / L, platinum 0.06g / L, palladium 0.49g / L, rhodium 0.011g / L, tellurium 63.517g / L, and selenium 34.7g / L.

[0109] Effect comparison of Example 2:

[0110] From the rare and precious material containing selenium 11.9%, tellurium 17.8%, gold 15.0%, platinum 0.146%, palladium 11.93%, and rhodium 0.0064, gold powder with 99.99% is recovered, and palladium platinum rhodium rich solution is recovered, and the metal direct recovery rate is shown in Table 2. The direct recovery rate and recovery rate of each metal in Example 2 are better than those in Comparative Example 2. In addition, by using the method of Example 2, no nitric acid, cyanide, sulfur dioxide, alkali and other reagents are used, and the acid is truly regenerated and used, achieving the purpose of zero emission. The specific implementation technical and economic indicators are shown in Table 2.

[0111] Table 2 Effect comparison of Example 2 and Comparative Example 2

[0112] Example 3

[0113] For 100 kg of precious and rare material containing 19.2% selenium, 3.2% tellurium, 51.1% gold, 0.35% platinum, 2.17% palladium, and 0.0071% rhodium, the operation steps of Example 3 are as follows:

[0114] Step 1: Chlorination dissolution, 365 kg of 36% hydrochloric acid is added at a liquid-solid ratio of 6:1, water is added in the reaction kettle to prepare 600 L of hydrochloric acid solution containing 6 mol / L of hydrochloric acid, stirring is started, and the complex precious and rare material is slowly added for stirring. The complex precious and rare material and the hydrochloric acid-containing aqueous solution are stirred and reacted in the reaction kettle, the temperature is raised to 70°C, 48 kg of 30% perchloric acid is slowly added, the temperature of the oxidation process is controlled at 95°C, and after the reaction is completed, 3 kg of complex precious and rare material is added for stirring to remove chlorine. After stopping stirring and clarifying, the upper chlorination liquid is extracted into the gold upper load, and the chlorination residue precipitated is left in the kettle for chlorination dissolution with the next batch of material. After four cycles in turn, 2.4 kg of chlorination residue is obtained by filtration, which is used as a raw material for recovering silver. The composition of the chlorination residue obtained by filtration is: 1.98% gold, 0.003% platinum, 0.196% palladium, 0.005% rhodium, 2.37% tellurium, 3.3% selenium, 34.1% silver, and 2.92% lead. The chlorination liquid clarified liquid obtained is 597 L (containing 88.20 g / L of gold, 0.60 g / L of platinum, 3.74 g / L of palladium, 0.012 g / L of rhodium, 5.43 g / L of tellurium, and 33.03 g / L of selenium).

[0115] Step 2: Gold recovery: The loading agent is prepared by MIBK: TBP: sulfonated kerosene: chloroform = 40%: 5%: 50%: 5%. The chlorination solution of step 1 is loaded with gold by countercurrent loading in two stages (stage 1 and stage 2) at a flow ratio of loading agent to chlorination solution of 1:0.8. A potential meter is installed at the water phase outlet of the loading reactor in stage 1 to monitor the potential value of the water phase. When the potential value decreases to 503 mV, the chlorination solution is stopped. At this time, the gold-loaded solution in stage 1 is pumped into the reduction reactor for reduction, and stage 2 is switched to stage 1. After loading, 745 L of gold-loaded solution and 596 L of post-loading solution are obtained, with gold content of 70.55 g / L, platinum, palladium, and rhodium content all <0.001 g / L. The gold-loaded solution is sent to the reducer for reduction. The reducer is oxalic acid, prepared as an 85 g / L oxalic acid solution of 62 L. The reduction temperature is 93°C. The gold content of the post-loading solution at the end of reduction is 0.014 g / L. After reduction to the end point, static separation is performed for more than 10 minutes. The organic phase and the post-reduction solution mixed with coarse gold powder are separated by filtration to obtain 61 L of post-reduction solution and 52.647 kg of sponge gold with a gold grade of 99.996%. The post-reduction solution is evaporated in an evaporator to produce concentrated solution 1 (37 L) and condensate (706 L). The concentrated solution 1 is returned to the reduction process, and the condensate is returned to step 1.

[0116] Step 3: The concentrated solution 1 is cooled to 24°C and stirred to crystallize. After filtration, the crystallized solution and residual oxalic acid are obtained. The crystallized solution is returned to the gold loading process of step 2, and the residual oxalic acid is returned to the reduction process of the gold-loaded solution of step 2.

[0117] Step 4: Low-temperature distillation: The post-loading solution of step 2 is pumped into a low-temperature vacuum evaporator. The liquid temperature in the low-temperature distillation column is controlled at 62°C, and the pressure in the distillation column is 58 kPa. Low-acid condensate 325 L (containing gold 0.0001 g / L, platinum 0.0001 g / L, palladium 0.0001 g / L, rhodium 0.0001 g / L, tellurium 0.08 g / L, selenium 0.539 g / L) and high-acid condensate 184 L (containing gold <0.0001 g / L, palladium <0.0001 g / L, rhodium <0.0001 g / L, tellurium 0.211 g / L, selenium 1.50 g / L, H + 2.2 g / L) are distilled. The high-acid condensate is returned to step 1 as hydrochloric acid, and the low-acid condensate is used for washing in step 6. Concentrated solution 2 (87 L) is produced, containing gold 0.042 g / L, platinum 4.116 g / L, palladium 25.68 g / L, rhodium 0.082 g / L, tellurium 36.39 g / L, and selenium 221.04 g / L.

[0118] Step 5: High-temperature distillation: The concentrated solution 2 of step 4 is transferred to a high-temperature evaporator, and the temperature is further increased to 98°C. The pressure in the evaporator is controlled at 71 kPa to remove residual water until crystals are produced, resulting in concentrated solution 3.

[0119] Step 6: directional crystallization and centrifugal filtration: the concentrated solution 3 (62 L) discharged in step 5 contains gold 0.058 g / L, platinum 5.78 g / L, palladium 36.01 g / L, rhodium 0.114 g / L, tellurium 48.62 g / L, selenium 309.66 g / L, and the discharge is cooled to 71°C for directional crystallization, and crystalline residue 27.36 kg (containing gold 0.035%, platinum 0.544%, palladium 4.467%, rhodium 0.023%, tellurium 63.407%, selenium 3.504%) and selenous acid 16.83 L (containing gold 0.0004 g / L, platinum 0.04 g / L, palladium 0.159 g / L, rhodium 0.0067 g / L, tellurium 50.64 g / L, selenium 606.25 g / L) are obtained by centrifugal filtration.

[0120] Step 7: washing the crystalline residue in step 6 with cold water or low-acid condensate produced in step 4, controlling the pH during the washing process to be 2-3, and filtering after washing to obtain tellurium residue 5.8 kg (containing gold <0.0001%, platinum <0.0001, palladium 0.001%, rhodium <0.0001%, tellurium 50.48%, selenium 14.24%) and palladium-platinum-rhodium-rich liquid (containing gold 0.117 g / L, platinum 13.70 g / L, palladium 85.52 g / L, rhodium 0.269 g / L, tellurium 2.65 g / L, selenium 27.61 g / L).

[0121] Comparative Example 3: implementation method:

[0122] For the composition of the waste acid treated in Example 3, the water solution chlorination method is used to dissolve to obtain a chlorinated solution containing noble metals - neutralize and adjust pH - reduce and precipitate gold - precipitate platinum palladium with ammonium chloropalladate, and the specific operation steps are as follows:

[0123] (1) According to the liquid-solid ratio of 6:1, 60 g / L hydrochloric acid, sodium chlorate 22 kg, control the temperature to 90°C, stir for 4 hours after dissolution, obtain chlorinated solution 596 L (containing gold 82.85 g / L, platinum 0.554 g / L, palladium 3.84 g / L, rhodium 0.011 g / L, tellurium 5.11 g / L, selenium 25.78 g / L), chlorinated residue 14.2 kg (gold 23.38%, platinum 0.21%, palladium 1.15%, rhodium 0.0059%, tellurium 1.79%, selenium 31.23%).

[0124] (2) The chlorinated solution obtained in step (1) is neutralized to pH=2 by adding sodium hydroxide, and filtered to obtain a neutralized solution 278 L (containing gold 51.96 g / L, platinum 0.514 g / L, palladium 4.212 g / L, rhodium 0.0236 g / L, tellurium 61.746 g / L, selenium 5.38 g / L), neutralized residue 9.2 kg, containing gold 36.50%, platinum 0.136%, palladium 0.835%, rhodium 0.0006%, tellurium 1.72%, selenium 2.51%.

[0125] (3) The neutralized solution from step (2) is heated to 90°C, and 15 kg of oxalic acid is added to reduce the gold to a gold powder having a gold grade of 99.9% about 46.02 kg (after washing), and a reduced solution of 593 L is produced.

[0126] (4) The reduced solution from step (3) is controlled at a temperature of 59°C, and 6 kg of sodium chlorate is slowly added to produce 7.2 kg of ammonium chloropalladate containing 0.015% gold, 24.62% palladium, 3.90% platinum, 0.0476% rhodium, 0.04% tellurium, and 0.21% selenium, and a reduced solution of 591 L is produced containing 0.126 g / L gold, 0.061 g / L platinum, 0.38 g / L palladium, 0.005 g / L rhodium, 4.48 g / L tellurium, and 25.60 g / L selenium.

[0127] Effect comparison of Example 3:

[0128] From the rare and precious material containing 19.2% selenium, 3.2% tellurium, 51.1% gold, 0.35% platinum, 2.17% palladium, and 0.0071% rhodium, a gold powder having a gold grade of 99.99% is produced, and a palladium-platinum-rhodium rich solution is recovered, and the direct recovery rate of each metal is shown in Table 3. The direct recovery rate and recovery rate of each metal in Example 3 are overall superior to those of Comparative Example 3. In addition, by using the method of Example 3, no nitric acid, cyanide, sulfur dioxide, alkali, and other reagents are used, and the acid is truly regenerated and used, achieving the purpose of zero discharge. The specific implementation technical and economic indicators are shown in Table 3.

[0129] Table 3: Effect comparison of Example 3 and Comparative Example 3 is shown in the following table:

[0130] In order to further prove the beneficial effects of the present application and better understand the present application, the technical features disclosed in the present application are further illustrated by the following comparative examples, but can not be understood as limiting the present application. Other improvements without creative work made by those skilled in the art based on the above disclosure are also considered to fall within the scope of the present application.

[0131] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

[0132] The above examples are only used to illustrate the technical solutions of the present application, but not limit the same; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application. Industrial applicability

[0133] The present application has strong adaptability to complex materials containing gold, platinum, palladium, rhodium, selenium and tellurium, and is particularly suitable for materials with high selenium and tellurium and low noble metals. Higher direct recovery and recovery can be obtained, selenium and tellurium are separated from the solution, and higher concentration of platinum, palladium, rhodium and rhodium noble liquid is obtained, which is convenient for further extraction of these metals.

Claims

1. A process for the hydrometallurgical recovery of a plurality of metals from complex precious material, characterized in that, It comprises the following steps: Step 1: chlorination dissolution, adding hydrochloric acid aqueous solution and complex rare and precious material into a reaction kettle, stirring and reacting, heating to 60-70℃, slowly adding oxidant, after the reaction is completed, adding a small amount of complex rare and precious material to stir and remove chlorine, stopping stirring to clarify, then pumping the upper chlorination liquid into gold loading, and the chlorination residue is used as raw material for recovering silver; the technical conditions are controlled as follows: the concentration of hydrochloric acid aqueous solution is 5-7 mol / L, the liquid-solid ratio is 3-6:1, and the oxidation process temperature is 80-95℃; Step 2: gold loading, using two-stage countercurrent gold loading, after the chlorination liquid is loaded, loaded gold liquid and post-loading liquid are obtained, the loaded gold liquid is reduced to the end point, static separation is carried out, the organic phase is clarified, and the precipitate is filtered to separate the post-reduction liquid and sponge gold; the post-reduction liquid is evaporated and concentrated to produce concentrated liquid 1 and condensate; Step 3: cooling the concentrated liquid 1 in step 2 to <30℃, stirring and crystallizing, and then filtering to obtain crystallized liquid and residual oxalic acid, wherein the crystallized liquid returns to the gold loading process in step 2, and the residual oxalic acid returns to the reduction process of the loaded gold liquid in step 2; Step 4: low-temperature distillation, the post-loading liquid in step 2 is subjected to low-temperature distillation to distill low-acid condensate and high-acid condensate, the high-acid condensate returns to step 1 as hydrochloric acid, the low-acid condensate enters step 6 for washing, and the post-distillation residue is concentrated liquid 2; Step 5: high-temperature distillation, the concentrated liquid 2 in step 4 is subjected to high-temperature distillation to remove residual water to obtain concentrated liquid 3; Step 6: directional crystallization and centrifugal filtration, the concentrated liquid 3 is subjected to directional crystallization and centrifugal filtration to obtain crystallization residue and selenous acid; Step 7: washing, the crystallization residue is washed by cold water or the low-acid condensate produced in step 4, and then filtered to obtain tellurium residue and palladium-platinum-rhodium rich liquid.

2. The process for recovering multiple metals in a complex precious material by a full wet method according to claim 1, characterized in that, In step 1, the complex rare and precious material comprises, in mass percentage, selenium 3-20%, tellurium 3-40%, gold ≥1%, platinum ≥0.1%, palladium ≥0.1%, rhodium ≥0.005%, and other impurities <30%.

3. A process for recovering multiple metals in a complex precious material by a full hydrometallurgical process according to claim 2, characterized in that, The selenium, tellurium, gold, platinum, palladium and rhodium are in the form of elemental phase.

4. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 3, characterized in that, In step 1, the oxidant is perchloric acid.

5. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 4, characterized in that, In step 1, the concentration of the oxidant is 26-30%.

6. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 5, characterized in that, In step 1, the oxidant is added in an amount of 2.5-4 times the total amount of gold, selenium and tellurium in the input material.

7. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 6, characterized in that, In step 2, the gold loading operation is as follows: the flow ratio of the loading agent to the chlorination liquid is 1:0.8-8, two-stage countercurrent gold loading is carried out by using loading counter-tower 1 and loading tower 2, and after loading, loaded gold liquid and post-loading liquid are obtained, the loaded gold liquid is sent to a reduction reaction kettle for reduction, static separation is carried out after reduction to the end point, the organic phase is clarified after static separation for more than 10 minutes, the precipitate is filtered to separate post-reduction liquid and sponge gold, the post-reduction liquid is evaporated and concentrated to produce concentrated liquid 1 and condensate, the concentrated liquid 1 returns to the reduction process, and the condensate returns to step 1 to supplement hydrochloric acid aqueous solution.

8. A process for recovering multiple metals in a complex precious material by a full hydrometallurgical process according to claim 7, characterized in that, The loading agent is a mixture of methyl isobutyl ketone (MIBK) and TBP.

9. The process as claimed in claim 7, wherein the process is a process for recovering multiple metals from complex precious material in a full wet process. The diluent is one of n-dodecane and sulfonated kerosene or a mixture of the two and chloroform.

10. The process as claimed in claim 7, wherein the process is a process for recovering multiple metals from complex precious material in a full wet process. The 2nd stage up-loading reactor includes a 1st stage up-loading reactor and a 2nd stage up-loading reactor.

11. The process for recovering multiple metals in a complex precious material by a full hydrometallurgical process according to claim 10, characterized in that, A potentiometer is installed at the water phase outlet of the 1st stage up-loading reactor to monitor the potential value of the water phase.

12. The process for recovering multiple metals in a full wet mode for complex and precious materials according to claim 11, characterized in that, When the potential value is reduced to <520mV, the input of the chlorination solution is stopped, and the 1st stage gold-loaded solution is pumped to the reduction reactor for reduction, and the 2nd stage up-loading reactor is switched to the 1st stage up-loading reactor.

13. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 12, characterized in that, In step 2, the gold-loaded solution is sent into the reactor for reduction.

14. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 13, characterized in that, In step 2, the temperature of the reduction is 90-95℃.

15. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 14, characterized in that, In step 2, the reduction end point of the gold-loaded solution after reduction contains <0.1g / L gold.

16. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 15, characterized in that, In step 2, the reducing agent of the reduction is oxalic acid.

17. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 16, characterized in that, In step 4, when the low-temperature distillation is performed, the liquid temperature in the low-temperature distillation column is controlled to be 60-75℃.

18. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 17, characterized in that, In step 4, when the low-temperature distillation is performed, the pressure in the low-temperature distillation column is controlled to be 55-65kPa.

19. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 18, characterized in that, In step 5, the temperature of the high-temperature distillation is 90-100℃, and the pressure in the evaporator is 60-80kPa.

20. A process for the hydrometallurgical recovery of multiple metals from complex precious material according to any one of claims 1 to 19, characterized in that, In step 6, the temperature of the directional crystallization is 75-80℃.

Images