Method for efficiently leaching tellurium from copper oxide anode slime high-lead and high-barium copper separation slag

Abstract

The invention provides a method for efficiently leaching tellurium from copper oxide anode slime high-lead and high-barium copper separation slag, and belongs to the technical field of rare dispersed metal (rare dispersed metal) hydrometallurgy, and the method comprises the following steps: grinding a high-lead and high-barium copper separation slag raw material; a mixed solution of a sulfuric acid solution and a sodium chloride solution serves as a leaching solution, sodium chlorate or oxygen serves as an oxidizing agent, and the leaching solution and the raw materials are mixed to prepare mixed feed liquid; and the mixed material liquid is leached under the ultrasonic and mechanical stirring conditions, solid-liquid separation is conducted after leaching is finished, and tellurium-containing leaching liquid is obtained. The method disclosed by the invention has the advantages of high leaching efficiency (the tellurium leaching rate can reach 98% or above), low reagent consumption, low residual acid concentration and the like by utilizing the ultrasonic effect and mechanical stirring to assist in intensifying oxidation leaching.

Description

Technical Field

[0001] The invention belongs to the technical field of rare dispersed metal (dispersed metal) hydrometallurgy, and in particular relates to a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud. Background Art

[0002] Tellurium is widely used in photovoltaics, semiconductors, thermoelectrics, infrared detection, and other fields. High-purity tellurium is an indispensable key material for modern industry, national defense, and strategic emerging industries. However, the vast majority of tellurium resources are associated with large-tonnage, low-grade copper ores. Approximately 90% of the world's tellurium comes from copper smelting byproducts (such as copper anode mud). The development of efficient tellurium leaching technology from copper anode mud is of great significance and is an inevitable requirement for the development of high-purity tellurium materials.

[0003] Tellurium in copper anode slime primarily exists as intermetallic compounds with copper, silver, and gold, such as copper telluride, cuprous telluride, gold telluride, and silver telluride. Tellurium can also be encapsulated. To address this issue, a semi-wet process offers advantages for recovering tellurium from copper anode slime. In this process, mixed acid is first added for pre-leaching and impurity removal, allowing the main impurities, arsenic, antimony, and bismuth, to enter the leachate. Sulfuric acid is then added to the leached residue for roasting. The roasted residue is then washed with water or a dilute acid solution to remove the copper sulfate, leaving the tellurium in the washed residue. This residue typically contains high levels of lead and barium, with copper significantly lower than tellurium. Its composition is approximately 22.14 wt% Ba, 18.93 wt% Pb, 4.81 wt% Te, 8.91 wt% Ag, and 0.39 wt% Cu, hence the name "high-lead-barium-copper-depleted slag." Because the high-alkali solution converts a small amount of lead sulfate, barium sulfate, and calcium magnesium salts into hydroxides and forms a coating around some tellurium; the acidic residue consumes the effective alkali. In addition, problems such as alkali mass transfer efficiency directly lead to the tellurium leaching rate being difficult to exceed 90%. The comprehensive tellurium recovery rate in the semi-wet process is less than 80%.

[0004] CN109402392A uses a mixed solution of hydrochloric acid and sulfuric acid as the leachate and sodium chlorate as the oxidant to achieve efficient tellurium leaching, with the gold separation slag containing less than 0.5wt% tellurium. However, due to the high-concentration mixed acid leaching used in this patent, the residual acid concentration in the leachate is relatively high (approximately 0.5 mol / L), which affects the subsequent separation and extraction of tellurium from the leachate. CN111606308A uses hydrochloric acid as the leachate and sodium chlorate as the oxidant, achieving a tellurium leaching rate of over 90%. However, due to the high volatility of high-concentration hydrochloric acid (the required hydrochloric acid concentration is generally 3-5 mol / L), the use of hydrochloric acid is inefficient and poses a significant environmental burden. CN110550611A uses sodium hydroxide as the leaching solution and sodium chlorate as the oxidant, and achieves efficient leaching of tellurium at normal pressure under the external field enhancement effect of ultrasound, microwave, or ultrasound-microwave synergy. It involves multiple steps such as high-pressure pretreatment and normal-pressure leaching. The treatment process is complex and has high requirements on equipment.

[0005] While existing technologies for leaching tellurium from high-lead, barium, and copper slag have achieved some improvement in tellurium leaching rates, alkaline extraction methods suffer from lengthy and complex processes. Acid extraction methods also suffer from low chlorination efficiency, acid volatilization, and high acid residues during the leaching process. Therefore, a new, efficient method for leaching tellurium from high-lead, barium, and copper slag is needed to address these issues. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention proposes a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud.

[0007] To achieve the above object, the present invention provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, comprising the following steps:

[0008] Drying, grinding, and sieving the high-lead-barium-copper slag to obtain a high-lead-barium-copper slag raw material;

[0009] A mixed solution of sulfuric acid and sodium chloride solution is used as a leaching solution, sodium chlorate or oxygen is used as an oxidant, and the mixture is mixed with the high-lead-barium copper slag raw material to obtain a mixed liquid;

[0010] Leaching the mixed liquid under ultrasonic and mechanical stirring conditions;

[0011] After the leaching is completed, the solid and liquid are separated, and the separated liquid is a tellurium-containing solution (tellurium-containing leaching solution).

[0012] Principle of the Invention: The method provided herein for leaching tellurium from copper anode slime containing high-lead and barium content copper slag uses sodium chloride as a chlorinating agent and sodium chlorate or oxygen as an oxidant for selective oxidative leaching. This method addresses the technical challenge of separating tellurium from base metals in high-impurity copper anode slime containing copper slag. Ultrasonic waves and mechanical agitation are simultaneously employed to enhance the oxidative leaching process, significantly reducing the amount of leaching reagents required, shortening the reaction equilibrium time, achieving a high tellurium leaching rate, and a low residual acid concentration in the leachate (less than 0.41 mol / L). Consequently, the method provides a low production cost and achieves efficient tellurium leaching from copper anode slime containing high-lead and barium content copper slag. The tellurium leaching rate in the tellurium-containing solution of the present invention is 93.01-98.71%, and the residual acid concentration is 0.20-0.41 mol / L.

[0013] Exemplarily, the drying temperature is 110-130° C. and the drying time is 10-12 hours;

[0014] And / or, the grinding time is 25 to 35 minutes;

[0015] And / or, the mesh size of the sieving is 200 meshes.

[0016] Furthermore, the concentration of the sulfuric acid solution is 90-250 g / L; and / or the concentration of the sodium chloride solution is 0-100 g / L, wherein the concentration of the sodium chloride solution is not 0. Preferably, the concentration of the sulfuric acid solution is 120-250 g / L, and the concentration of the sodium chloride solution is 40-100 g / L; more preferably, the concentration of the sulfuric acid solution is 120-180 g / L, and the concentration of the sodium chloride solution is 60-100 g / L. The volume ratio of the sulfuric acid solution to the sodium chloride solution is 1:1.

[0017] Furthermore, the mass ratio of the high-lead-barium copper slag raw material to sodium chlorate is 1:0.03; and / or the flow rate of the oxygen is 40 to 120 L / h, preferably the flow rate of the oxygen is 80 to 120 L / h.

[0018] Furthermore, the liquid-to-solid ratio during the leaching is 4 mL:1 g.

[0019] Furthermore, the leaching temperature is 85-100°C and the leaching time is 15-60 minutes. Preferably, the leaching temperature is 90°C and the leaching time is 30-60 minutes.

[0020] Furthermore, the power of the ultrasound is 100-450W; and / or the speed of the mechanical stirring is 300rpm. Preferably, the power of the ultrasound is 200-450W; and / or the speed of the mechanical stirring is 300rpm.

[0021] Compared with the prior art, the present invention has the following advantages and technical effects:

[0022] The present invention achieves efficient leaching of tellurium from copper anode mud high-lead-barium copper slag by enhancing oxidative leaching; ultrasonic enhancement and mechanical stirring work synergistically to improve the tellurium leaching rate (the tellurium leaching rate is 93.01-98.71%), shorten the leaching time, and effectively reduce reagent consumption and residual acid concentration (the residual acid concentration is 0.20-0.41 mol / L). DETAILED DESCRIPTION

[0023] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0024] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0025] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0026] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0027] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0028] An embodiment of the present invention provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, comprising the following steps:

[0029] Drying, grinding, and sieving the high-lead-barium-copper slag to obtain a high-lead-barium-copper slag raw material;

[0030] A mixed solution of sulfuric acid and sodium chloride solution is used as a leaching solution, sodium chlorate or oxygen is used as an oxidant, and the mixture is mixed with a high-lead-barium copper slag raw material to obtain a mixed liquid;

[0031] Leaching the mixed liquid under ultrasonic and mechanical stirring conditions;

[0032] After the leaching is completed, the solid and liquid are separated, and the separated liquid is a tellurium-containing solution.

[0033] The present invention uses sodium chloride as a chlorinating agent and sodium chlorate or oxygen as an oxidant to selectively oxidize and leach tellurium, solving the technical problem of separating tellurium from base metals in copper slag fractionated from high-impurity copper anode slime. Ultrasonic waves and mechanical agitation are simultaneously used to enhance the oxidative leaching process, significantly reducing the amount of leaching reagents required, shortening the time it takes for the reaction to reach equilibrium, and improving the tellurium leaching rate (to over 98%). The residual acid concentration in the leachate is low (less than 0.41 mol / L), resulting in a low production cost and achieving efficient tellurium leaching from copper slag fractionated from high-lead and barium copper anode slime. The tellurium leaching rate in the resulting tellurium-containing solution is 93.01-98.71%, and the residual acid concentration is 0.20-0.41 mol / L.

[0034] In the method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud of the present invention, the main reactions occurring during the leaching process are as follows:

[0035] TeO2+4H + +6Cl - =TeCl6 2- +2H2O;

[0036] 3Te+2ClO3 - +16Cl - +12H + =3TeCl6 2- +6H2O;

[0037] Ag2Te+ClO3 - +7Cl - +6H + =TeCl6 2- +2AgCl↓+3H2O;

[0038] 3Cu2Te+4ClO3 - +14Cl - +24H + =3TeCl6 2- +6Cu 2+ +12H2O;

[0039] 6AuTe2+11ClO3 - +85Cl - +66H + =12TeCl6 2- +6AuCl4 - +33H2O.

[0040] Te+O2+6Cl - +4H + =TeCl6 2- +2H2O;

[0041] 2Ag2Te+3O2+16Cl - +12H + =2TeCl6 2- +4AgCl↓+6H2O;

[0042] Cu2Te+2O2+6Cl - +8H + =TeCl6 2- +2Cu 2+ +4H2O;

[0043] 4AuTe2+11O2+64Cl - +44H + =8TeCl6 2- +4AuCl4 - +22H2O.

[0044] In an embodiment of the present invention, the mass percentages of the main components of the high-lead-barium copper slag are: 22.14% Ba, 18.93% Pb, 8.91% Ag, 7.18% Sn, 4.81% Te, 2.03% Sb, and 0.39% Cu.

[0045] In an embodiment of the present invention, the drying temperature is 110-130°C, the time is 10-12h, preferably the drying temperature is 120°C, and the time is 12h; the grinding time is 25-35min, preferably the grinding time is 30min; the mesh size of the sieve is 200 mesh. High-lead-barium copper slag may contain crystallized water or adsorbed water, and drying can remove this water to avoid side reactions between water and chlorinating agents or oxidizing agents during the leaching process, thereby reducing reagent consumption and preventing the formation of by-products. The dried slag is easier to disperse, avoiding the problem of uneven reaction due to agglomeration during the leaching process, and ensuring that the leachate is in full contact with the slag. The drying process may remove some reducing components (such as metal Al, Zn, Fe 2+), reducing its consumption of oxidants (such as sodium chlorate). At the same time, the oxidized surface formed (such as Al and Fe oxides) may help to fix certain impurities and reduce their interference with tellurium leaching. If the slag contains water, during the subsequent grinding or leaching process, tellurium may be oxidized to insoluble substances such as TeO2 due to contact with water. Drying can reduce such risks. Grinding can crush the slag into finer particles, increase its specific surface area, thereby increasing the contact area with the leaching agent and increasing the reaction rate. Grinding can also destroy the crystal structure of the slag, exposing more active sites, making tellurium easier to leach. The fine particles after grinding are conducive to the diffusion of the leaching agent inside the slag, promote the mass transfer process, and improve the leaching efficiency. The dried slag is easier to grind to a fine particle size, and the fine particles after grinding are easier to dry thoroughly. The two promote each other and jointly optimize the physical and chemical properties of the slag. Drying and grinding work together on the slag to improve its reactivity, mass transfer efficiency and redox conditions, creating favorable conditions for subsequent leaching reactions and ultimately achieving efficient enrichment of tellurium.

[0046] In an embodiment of the present invention, the concentration of the sulfuric acid solution is 90-250 g / L; the concentration of the sodium chloride solution is 0-100 g / L, wherein the concentration of the sodium chloride solution is not 0. Preferably, the concentration of the sulfuric acid solution is 120-250 g / L, and the concentration of the sodium chloride solution is 40-100 g / L; more preferably, the concentration of the sulfuric acid solution is 120-180 g / L, and the concentration of the sodium chloride solution is 60-100 g / L. The volume ratio of the sulfuric acid solution to the sodium chloride solution is 1:1. The sulfuric acid solution provides an acidic environment to promote the oxidation and dissolution of tellurium; the sodium chloride solution provides chloride ions to stabilize the dissolved form of tellurium through coordination. An appropriate increase in the concentration of sulfuric acid will increase the tellurium leaching rate. However, when the concentration of sulfuric acid is too high (such as exceeding 250 g / L), the leaching rate growth rate slows down or even decreases slightly, which may be due to the increase in solution viscosity leading to a decrease in mass transfer efficiency; at the same time, high concentration sulfuric acid will increase the leaching of impurities (such as Sn, Cu, As). In a high concentration sulfuric acid system, H + The consumption rate of chloride ions (Cl) may be lower than its initial concentration, resulting in the residual acid concentration in the leachate remaining at a high level. - ) forms a soluble complex ion (TeCl6 2- ), thereby promoting the dissolution of tellurium. Chloride ions may also catalyze oxidation reactions, accelerating the oxidation and leaching of tellurium.

[0047] In an embodiment of the present invention, the mass ratio of the high-lead-barium copper slag raw material to sodium chlorate is 1:0.03; the oxygen flow rate is 40 to 120 L / h, preferably 80 to 120 L / h. When the amount of sodium chlorate added is low, the tellurium leaching rate is low; as the amount of sodium chlorate increases, the tellurium leaching rate increases; further increasing the amount of sodium chlorate added has limited improvement in the tellurium leaching rate and may have some negative effects, such as increased costs and the introduction of more impurities. Furthermore, excessive sodium chlorate may react with sulfuric acid to produce Cl2, which not only consumes reagents but also poses hazards to the environment and operators.

[0048] In an embodiment of the present invention, the liquid-solid ratio during leaching is 4mL:1g. When the liquid-solid ratio is insufficient, the insufficient amount of liquid will cause the slurry viscosity to increase, increase the mass transfer resistance, and make it difficult for tellurium ions to diffuse from the solid particles into the solution, thereby reducing the tellurium leaching rate. When the liquid-solid ratio is insufficient, due to the high viscosity of the slurry and the large mass transfer resistance, the reaction may not be complete, resulting in less acid consumption and a relatively high residual acid concentration; when the liquid-solid ratio is too high, it may cause the reactants to form a saturated layer on the solid surface, hindering the further progress of the reaction. An appropriate liquid-solid ratio can reduce the viscosity of the slurry, improve the mass transfer conditions, and make it easier for tellurium ions to diffuse from the solid particles into the solution, thereby increasing the tellurium leaching rate. An appropriate liquid-solid ratio can also ensure that the reactants maintain a sufficient concentration in the solution to maintain the continuous progress of the reaction, while avoiding the saturated layer problem caused by excessive concentration.

[0049] In an embodiment of the present invention, the leaching temperature is 90°C and the leaching time is 15 to 60 minutes; preferably, the leaching time is 30 to 60 minutes. When the leaching temperature is low, the kinetic energy of the reactant molecules is low, resulting in insufficient collision frequency and intensity, slowing the chemical reaction rate and lowering the tellurium leaching rate. Simultaneously, due to the slow reaction rate, the acid consumption rate is also slow, resulting in a relatively high residual acid concentration. Low temperatures may also reduce the diffusion rate of ions in the solution, making it difficult for tellurium ions to diffuse from the solid particles into the solution, further reducing the tellurium leaching rate. An appropriate leaching temperature can increase the kinetic energy of the reactant molecules, increase the collision frequency and intensity, accelerate the chemical reaction rate, and significantly improve the tellurium leaching rate. It can also increase the diffusion rate of ions in the solution, making it easier for tellurium ions to diffuse from the solid particles into the solution, further improving the tellurium leaching rate. Excessively high leaching temperatures may lead to unwanted side reactions, such as the decomposition of sulfuric acid or sodium chlorate. These side reactions may consume the reactants or generate harmful substances, thereby reducing the tellurium leaching rate. High temperatures can also cause certain components in the solution (such as sulfuric acid) to volatilize more rapidly, leading to changes in solution concentration and affecting the reaction. High temperatures can also accelerate equipment corrosion and increase equipment maintenance costs.

[0050] In an embodiment of the present invention, the ultrasonic power is 100 to 450 W; the mechanical stirring rate is 300 rpm. Preferably, the ultrasonic power is 200 to 450 W; the mechanical stirring rate is 300 rpm. When the ultrasonic power is insufficient, the cavitation effect generated when the ultrasonic wave propagates in the liquid is weak, and it cannot effectively promote the decomposition and activation of the reactants. The mechanical effect is insufficient, the solution mixing effect is poor, and the mass transfer efficiency is low, resulting in a low tellurium leaching rate. Appropriate ultrasonic power can enhance the cavitation effect, create more local high temperature and high pressure environments, and promote the oxidation and dissolution of tellurium; at the same time, it can also enhance the mechanical effect, improve the solution mixing effect, and increase the mass transfer efficiency, making it easier for tellurium ions to diffuse from solid particles into the solution. Under the combined action of the cavitation effect and the mechanical effect, the tellurium leaching rate is significantly improved. Excessive ultrasonic power may lead to excessive cavitation effect, resulting in excessive bubbles and turbulence, which in turn hinder the effective contact of the reactants. Excessive ultrasonic power may also cause the solution temperature to rise significantly, triggering unnecessary side reactions (such as the decomposition of sulfuric acid and sodium chlorate), consuming reactants or generating harmful substances. Under the combined effects of excessive cavitation effect and significant thermal effect, the tellurium leaching rate may no longer increase or may even decrease.

[0051] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in this field and are not the focus of the present invention.

[0052] The technical solution of the present invention is further illustrated by the following examples.

[0053] Example 1

[0054] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0055] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0056] Step (2), 10 mL of 90 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0057] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 100W, the mechanical stirring rate to 300rpm, the ultrasonic and mechanical stirring to be carried out simultaneously, and the synergistic enhancement reaction time to 15min (the synergistic enhancement reaction time is the leaching time);

[0058] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 93.01%, and the residual acid concentration is 0.24 mol / L.

[0059] Example 2

[0060] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0061] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0062] Step (2), 10 mL of 90 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0063] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 15min;

[0064] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution. The tellurium leaching rate is 93.43% and the residual acid concentration is 0.23 mol / L.

[0065] Example 3

[0066] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0067] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0068] Step (2), 10 mL of 90 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0069] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 30min;

[0070] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 96.80%, and the residual acid concentration is 0.21 mol / L.

[0071] Example 4

[0072] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0073] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0074] Step (2), 10 mL of 120 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw material of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0075] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 450W, the mechanical stirring rate to 300rpm, performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 30min;

[0076] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 95.98%, and the residual acid concentration is 0.31 mol / L.

[0077] Example 5

[0078] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0079] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0080] Step (2), 10 mL of 120 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw material of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0081] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 60min;

[0082] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 97.69%, and the residual acid concentration is 0.32 mol / L.

[0083] Example 6

[0084] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0085] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0086] Step (2), 10 mL of 180 g / L sulfuric acid solution and 10 mL of 70 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw material of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0087] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 60min;

[0088] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 95.72%, and the residual acid concentration is 0.36 mol / L.

[0089] Example 7

[0090] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0091] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0092] Step (2), 10 mL of 250 g / L sulfuric acid solution and 10 mL of 40 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw material of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0093] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 60min;

[0094] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution. The tellurium leaching rate is 93.80% and the residual acid concentration is 0.41 mol / L.

[0095] Example 8

[0096] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0097] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0098] Step (2), mixing 10 mL of 90 g / L sulfuric acid solution and 10 mL of 40 g / L sodium chloride solution to prepare a leachate, introducing 40 L / h of oxygen as an oxidant, and mixing the mixture with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid is 4:1 (mL / g);

[0099] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 60min;

[0100] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 92.67%, and the residual acid concentration is 0.20 mol / L.

[0101] Example 9

[0102] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0103] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0104] Step (2), mixing 10 mL of 90 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution to prepare a leachate, introducing 120 L / h of oxygen as an oxidant, and mixing the mixture with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid is 4:1 (mL / g);

[0105] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 60min;

[0106] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 98.71%, and the residual acid concentration is 0.22 mol / L.

[0107] Example 10

[0108] This embodiment provides a method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, the steps of which are as follows:

[0109] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0110] Step (2), 10 mL of 120 g / L sulfuric acid solution and 10 mL of 80 g / L sodium chloride solution were mixed to prepare a leachate, 40 L / h of oxygen was introduced as an oxidant, and the mixture was mixed with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0111] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 200W, the mechanical stirring rate to 300rpm, and performing ultrasonic and mechanical stirring simultaneously, and the synergistic enhancement reaction time to 40min;

[0112] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 94.77%, and the residual acid concentration is 0.30 mol / L.

[0113] Example 11

[0114] The same as Example 10, except that the oxygen flow rate is 60 L / h, the tellurium leaching rate in the tellurium-containing solution of this embodiment is 95.10%, and the residual acid concentration is 0.32 mol / L.

[0115] Example 12

[0116] The same as Example 10, except that the oxygen flow rate is 80 L / h, the tellurium leaching rate in the tellurium-containing solution of this embodiment is 97.54%, and the residual acid concentration is 0.29 mol / L.

[0117] Example 13

[0118] The same as Example 10, except that the oxygen flow rate is 120 L / h, the tellurium leaching rate in the tellurium-containing solution of this embodiment is 97.83%, and the residual acid concentration is 0.29 mol / L.

[0119] Comparative Example 1

[0120] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0121] Step (2), 10 mL of 400 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0.15 g of sodium chlorate was used as an oxidant to mix with the raw material of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0122] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 0W (i.e., no ultrasonic treatment), the mechanical stirring rate to 300rpm, and the reaction time to 60min;

[0123] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 89.03%, and the residual acid concentration is 0.96 mol / L.

[0124] Since the leaching process was not ultrasonically enhanced, the mass transfer effect was not as good as that of ultrasonic treatment, and some of the encapsulated tellurium compounds failed to react with the acid, resulting in incomplete leaching of tellurium and high residual acid.

[0125] Comparative Example 2

[0126] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0127] Step (2), 10 mL of 400 g / L sulfuric acid solution and 10 mL of 100 g / L sodium chloride solution were mixed to prepare a leachate, and 0 g of sodium chlorate was used as an oxidant (i.e., no oxidant was added), and the mixture was mixed with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid was 4:1 (mL / g);

[0128] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 0W (i.e., no ultrasonic treatment), the mechanical stirring rate to 300rpm, and the reaction time to 60min;

[0129] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution. The tellurium leaching rate is 42.51% and the residual acid concentration is 1.22 mol / L.

[0130] Since tellurium exists in the intermetallic compound phase in the copper separation slag, this part of tellurium needs to be oxidized into high-valent compounds before it can be leached. Therefore, in the absence of ultrasonic strengthening and oxidation strengthening treatment, the tellurium leaching rate is less than 50%.

[0131] Comparative Example 3

[0132] Step (1), drying the high-lead-barium copper slag at 120° C. for 12 h, grinding it in an agate mortar for 30 min, and then passing it through a 200-mesh sieve, taking 5 g of the high-lead-barium copper slag raw material after grinding it through a 200-mesh sieve;

[0133] Step (2), using 20 mL of 90 g / L sulfuric acid solution as a leachate and 0.15 g of sodium chlorate as an oxidant, mixed with the raw materials of step (1) to obtain a mixed liquid, wherein the liquid-to-solid ratio of the mixed liquid is 4:1 (mL / g);

[0134] Step (3), transferring the mixed liquid obtained in step (2) to an ultrasonic reaction workstation, connecting to 90°C circulating water for insulation, setting the ultrasonic power to 0W (i.e., no ultrasonic treatment), the mechanical stirring rate to 300rpm, and the reaction time to 60min;

[0135] Step (4): After the reaction time is reached, the mixed liquid obtained in step (3) is filtered to obtain a tellurium-containing solution, the tellurium leaching rate is 27.40%, and the residual acid concentration is 0.55 mol / L.

[0136] The low concentration of 90g / L sulfuric acid is insufficient for tellurium leaching, requiring a certain amount of chlorination agent to enhance leaching. Tellurium forms a multi-coordinated compound with chloride ions. Therefore, the tellurium leaching rate decreases significantly without the chlorination agent and ultrasonic treatment.

[0137] Comparative Example 4

[0138] The same as Example 5, except that ultrasonic treatment was not performed during leaching in step (3), and the leaching was performed only under mechanical stirring. The tellurium leaching rate in the tellurium-containing solution of this comparative example was 87.29%, and the residual acid concentration was 0.56 mol / L.

[0139] Due to the lack of ultrasonic enhancement of particle surface activity, the mass transfer of the reaction reagents in the solution is hindered, and some of the encapsulated tellurium is not completely leached, so the tellurium leaching rate needs to be improved.

[0140] Comparative Example 5

[0141] The same as Example 5, except that only ultrasonic treatment was performed during leaching in step (3), without mechanical stirring. The tellurium leaching rate in the tellurium-containing solution of this comparative example was 90.15%, and the residual acid concentration was 0.53 mol / L.

[0142] This may be due to the uneven cavitation effect. During the reaction process, lead sulfate and barium sulfate particles agglomerate and wrap tellurium, and the tellurium leaching rate needs to be further improved.

[0143] Comparative Example 6

[0144] The same as Example 5, except that no oxidant was added when preparing the mixed solution in step (2). The tellurium leaching rate in the tellurium-containing solution of this comparative example was 39.62%, and the residual acid concentration was 0.52 mol / L.

[0145] Comparative Example 7

[0146] The same as Example 5, except that no sodium chloride solution was added when preparing the mixed solution in step (2). The tellurium leaching rate in the tellurium-containing solution of this comparative example was 25.58%, and the residual acid concentration was 0.47 mol / L.

[0147] It can be seen from Example 5, Comparative Example 6 and Comparative Example 7 that the oxidant and the chlorinating agent have a significant impact on the tellurium leaching rate. Most tellurium exists in the form of low-valent intermetallic compounds and needs to be oxidized before leaching. At the same time, tellurium can be better leached in the presence of a chlorinating agent at lower acidity.

[0148] The process parameters, tellurium leaching rates and residual acid concentrations of Examples 1-13 of the present invention and Comparative Examples 1-3 are compared in Table 1.

[0149] Table 1 Comparison of process parameters, tellurium leaching rate and residual acid concentration of Examples 1-13 and Comparative Examples 1-3

[0150]

[0151]

[0152] As can be seen from Table 1, the methods in the embodiments of the present invention, compared with traditional hydrometallurgy, can effectively reduce reagent consumption and residual acid concentration, and significantly improve the tellurium leaching rate by synergistically strengthening the oxidation of tellurium in high-lead-barium copper slag through ultrasonic strengthening and mechanical stirring.

[0153] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for efficiently leaching tellurium from high-lead-barium copper slag in enhanced copper oxide anode mud, characterized in that: The following steps are involved: Drying, grinding, and sieving the high-lead-barium-copper slag to obtain a high-lead-barium-copper slag raw material; A mixed solution of sulfuric acid solution and sodium chloride solution is used as a leaching solution, sodium chlorate or oxygen is used as an oxidant, and the mixture is mixed with the high-lead-barium copper slag raw material to obtain a mixed liquid; Leaching the mixed liquid under ultrasonic and mechanical stirring conditions; After the leaching is completed, the solid and liquid are separated, and the separated liquid is a tellurium-containing solution.

2. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The drying temperature is 110-130°C and the drying time is 10-12 hours; And / or, the grinding time is 25 to 35 minutes; And / or, the mesh size of the sieving is 200 meshes.

3. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The concentration of the sulfuric acid solution is 90-250 g / L; And / or, the concentration of the sodium chloride solution is 0-100 g / L, wherein the concentration of the sodium chloride solution is not 0.

4. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The mass ratio of the high lead barium copper slag raw material to sodium chlorate is 1:0.03; And / or, the flow rate of the oxygen is 40 to 120 L / h.

5. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The liquid-to-solid ratio during the leaching is 4 mL:1 g.

6. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The leaching temperature is 90° C. and the leaching time is 15 to 60 minutes.

7. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 6, characterized in that: The leaching temperature is 90° C. and the leaching time is 30 to 60 minutes.

8. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 1, characterized in that: The power of the ultrasound is 100-450W; And / or, the mechanical stirring rate is 300 rpm.

9. The method for efficiently leaching tellurium from enhanced copper oxide anode slime high lead and barium copper slag according to claim 8, characterized in that: The power of the ultrasound is 200-450W; And / or, the mechanical stirring rate is 300 rpm.

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