CN113148963A - Method for separating and recovering tellurium and selenium - Google Patents

Method for separating and recovering tellurium and selenium Download PDF

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Publication number
CN113148963A
CN113148963A CN202110278427.8A CN202110278427A CN113148963A CN 113148963 A CN113148963 A CN 113148963A CN 202110278427 A CN202110278427 A CN 202110278427A CN 113148963 A CN113148963 A CN 113148963A
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tellurium
selenium
silver
reaction
content
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梁鉴华
王波
罗鑫
陈应红
刘威
陈秋旭
梅占强
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Guangdong Pioneer Precious Metals Material Co ltd
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Guangdong Pioneer Precious Metals Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/045—Leaching using electrochemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a method for separating and recovering tellurium and selenium, belonging to the technical field of rare and precious metal metallurgy. The method for separating and recovering tellurium and selenium comprises the following steps: (1) adding an oxidant into the tellurium-selenium material in the presence of acid to leach tellurium and selenium into a solution, and keeping silver in residues, (2) adding a reducing agent into a leaching solution to precipitate selenium, so as to realize the separation of tellurium and selenium; the tellurium selenium material contains silver or does not contain silver, and when the tellurium selenium material contains silver, crude silver solid is obtained after the reaction in the step (1) is finished. The invention controls the oxidation process by controlling the potential and acidity in the oxidation leaching process, and controls the reduction process by controlling the potential in the reduction process, thereby realizing the effective separation and recovery of tellurium and selenium (or tellurium, selenium and silver). The method has the advantages of simple required equipment, short flow, low cost and environmental friendliness, and is suitable for industrial application.

Description

Method for separating and recovering tellurium and selenium
Technical Field
The invention belongs to the technical field of rare and precious metal metallurgy, and particularly relates to a method for separating and recovering tellurium and selenium.
Background
After the selenium-containing raw material is oxidized and roasted to recover selenium dioxide, the main components of the residual material are enriched tellurium and silver and a small amount of unrecovered selenium. The selenium and the tellurium are rare metals, and the silver is a noble metal, so the method has high value, and the separation and the recovery of the tellurium, the selenium and the silver have very important significance for the comprehensive utilization of resources and the reduction of the production cost.
Chinese patent CN 106222426A discloses a method for separating silver, selenium and tellurium from flue dust of an alloy converting converter, which comprises leaching selenium and tellurium into a solution by pressure oxidation, putting silver into leaching slag, smelting and electrolyzing the leaching slag to obtain a silver product, adding alkali into the leaching solution to adjust the pH value to 4-5, precipitating tellurium, and then adding hydrazine hydrate to precipitate selenium. The method needs smelting and pressurizing equipment, and has higher requirement on the equipment; firstly adding alkali to precipitate tellurium, which can cause partial selenium precipitation, and the purity of the obtained tellurium dioxide is not high; the selenium precipitation step does not allow the selenium in the solution to be completely precipitated.
Chinese patent CN 103407975A aims at the high-selenium low-tellurium solution, sulfur dioxide is added twice under the condition that chloride ions exist, the first reduction is carried out to obtain a crude selenium product with higher grade, and the second reduction is carried out to obtain a selenium-tellurium mixture. This method is only suitable for solutions with high selenium content, and the selenium and tellurium cannot be completely separated during the second reduction.
Aiming at the technical problems existing in the prior art for separating tellurium and selenium, a tellurium and selenium separation and recovery method which is simpler, has better separation and recovery effects and lower equipment requirements is needed to be developed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the method for separating and recovering tellurium and selenium, which not only can realize better separation and recovery of selenium and tellurium, but also has the advantages of simple required equipment, short flow, low cost, environmental friendliness and suitability for industrial application.
In order to achieve the purpose, the invention provides a method for separating and recovering tellurium and selenium, which comprises the following steps:
(1) adding an oxidant into the tellurium-selenium material in the presence of acid until the system potential is more than or equal to 600mV, and obtaining a solution A after the reaction is finished, wherein H in the acid+The concentration is 4-6 mol/L, and the ratio of the tellurium-selenium material to the acid is 1 g: (3-6) mL;
(2) adding a reducing agent into the solution A until the potential is 450-550 mV, and carrying out solid-liquid separation after the reaction is finished to obtain a solution B and a crude selenium solid;
the tellurium selenium material contains silver or does not contain silver, and when the tellurium selenium material contains silver, a coarse silver solid is also obtained after the reaction in the step (1) is finished.
Preferably, in the step (1), an oxidant is added into the tellurium-selenium material until the system potential is 600-900 mV.
Preferably, in the step (1), the reaction temperature is 70-95 ℃, and the reaction is continued for 0.5-1 h after the addition of the oxidant is stopped.
Preferably, in the step (2), the reaction temperature is 70-85 ℃, and the reaction is continued for 0.5-1 h after the addition of the reducing agent is stopped.
Preferably, in the step (1), the oxidant is at least one of sodium chlorate, hydrogen peroxide and potassium permanganate.
Preferably, in the step (2), the reducing agent is at least one of sodium hypophosphite and hydroxylamine hydrochloride.
Preferably, the method further comprises step (3): and adding alkali into the solution B for reaction, and performing solid-liquid separation to obtain crude tellurium dioxide.
Preferably, in the step (3), after adding alkali to the solution B to adjust the pH value to 4-5, the reaction is continued for 0.5-1 h.
Preferably, in the tellurium-selenium material, the tellurium content is 50 wt% -80 wt%, the selenium content is 3 wt% -20 wt%, and the silver content is less than 10 wt%.
Preferably, the tellurium and selenium material is powder, and the particle size is preferably below 30 meshes.
Preferably, in the steps (1) to (2), each reaction is carried out under stirring.
Compared with the prior art, the invention has the beneficial effects that: the invention controls the oxidation process by controlling the potential and acidity in the oxidation leaching process, and controls the reduction process by controlling the potential in the reduction process, thereby realizing the effective separation and recovery of tellurium and selenium (or tellurium, selenium and silver); the method has the advantages of simple required equipment, short flow, low cost and environmental friendliness, and is suitable for industrial application.
Drawings
FIG. 1 is a flow chart of the separation and recovery of Te, Se and Ag in each example.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Herein, the oxidizing agent or the reducing agent is added to the potential to be a value, and the target potential value is not an instantaneous value but a value after stabilization, and usually takes 1 minute or more.
The method for separating and recovering tellurium and selenium controls the oxidation process by controlling the potential and the acidity in the oxidation leaching process, so that tellurium and selenium in a tellurium-selenium material are oxidized from 0 valence to +4 valence, and are leached into a solution; and adding a reducing agent into the leachate, and reducing the selenium by controlling the potential in the reduction process to obtain crude elemental selenium, wherein the tellurium is not reduced and still remains in the solution, so that the selenium and the tellurium are effectively separated. Specifically, the method for separating and recovering tellurium and selenium comprises the following steps:
(1) adding an oxidant into the tellurium-selenium material in the presence of acid until the system potential is more than or equal to 600mV, and obtaining a solution A after the reaction is finished, wherein H in the acid+The concentration is 4-6 mol/L, and the ratio of the tellurium-selenium material to the acid is 1 g: (3-6) mL;
(2) adding a reducing agent into the solution A until the potential is 450-550 mV, and carrying out solid-liquid separation after the reaction is finished to obtain a solution B and a crude selenium solid;
wherein the tellurium selenium material contains silver or does not contain silver, and when the tellurium selenium material contains silver, crude silver solid is also obtained after the reaction in the step (1) is finished.
The method for separating and recovering tellurium and selenium can recover selenium with higher recovery rate, is suitable for tellurium and selenium materials with various selenium contents, and can well separate selenium and tellurium in materials with lower selenium contents (such as the selenium content is below 20 wt%). When the tellurium and selenium material contains silver, the silver is left in the slag in the form of simple substance and/or silver chloride in the oxidation leaching process, and the effective separation of the silver, the tellurium and the selenium can be realized by controlling the potential and the acidity in the process to be within the specific range. The reactions involved in steps (1) to (2) are described below, taking the acid as hydrochloric acid, the oxidizing agent as sodium chlorate, and the reducing agent as sodium hypophosphite for example:
in the step (1), under the conditions of proper acidity and oxidant addition to the potential of more than or equal to 600mV, the reaction formula is as follows:
3Te+12HCl+2NaClO3→3TeCl4+2NaCl+6H2O，
3Se+12HCl+2NaClO3→3SeCl4+2NaCl+6H2O；
in the step (2), under the condition that a reducing agent is added to the potential of 450-550 mV, the reaction formula is as follows:
SeCl4+NaH2PO2+2H2O→NaH2PO4+Se↓+4HCl；
if the reducing agent is added to the potential lower than 450mV in the step (2), then the tellurium is also reduced, so that the obtained crude selenium contains higher tellurium, and the reaction formula for reducing the tellurium is as follows:
TeCl4+NaH2PO2+2H2O→NaH2PO4+Te↓+4HCl。
in some embodiments, in the step (1), an oxidant is added to the tellurium-selenium material until the system potential is 600-900 mV, so that not only is effective leaching of tellurium and selenium into the solution ensured, but also the dosage of the oxidant is reduced, and waste of the oxidant and the reducing agent is avoided.
In the step (1), the potential of the system is controlled by controlling the reaction temperature and the rate of adding the oxidant. In some preferred embodiments, the reaction temperature in step (1) is 70 to 95 ℃. The rate of oxidant addition can be adjusted depending on the scale of the process. The time for continuing the reaction after the addition of the oxidant is stopped can be adjusted according to the actual situation. In some embodiments, the reaction is continued for 0.5 to 1 hour after the addition of the oxidizing agent is stopped.
In some embodiments, the oxidizing agent in step (1) is at least one of sodium chlorate, hydrogen peroxide and potassium permanganate, such as sodium chlorate, or hydrogen peroxide, or potassium permanganate, or sodium chlorate and hydrogen peroxide, or sodium chlorate and potassium permanganate, or hydrogen peroxide and potassium permanganate, or sodium chlorate, hydrogen peroxide and potassium permanganate. However, the kind of the oxidizing agent in the step (1) is not limited thereto.
In some embodiments, the acid in step (1) is at least one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, and formic acid, such as one, two, three, four, five, or six thereof.
In the step (2), the potential of the system is controlled by controlling the reaction temperature and the rate of adding the reducing agent. In some preferred embodiments, the reaction temperature in step (2) is 70 to 85 ℃. The rate of addition of the reducing agent can be adjusted depending on the scale of the process. The time for continuing the reaction after stopping adding the reducing agent can be adjusted according to the actual situation.
In some embodiments, the reaction is continued for 0.5 to 1 hour after the addition of the reducing agent is stopped. In some embodiments, the reducing agent in step (2) is at least one of sodium hypophosphite and hydroxylamine hydrochloride, such as sodium hypophosphite, or hydroxylamine hydrochloride, or sodium hypophosphite and hydroxylamine hydrochloride. However, the kind of the reducing agent in the step (2) is not limited thereto.
The obtained solution B is treated, and the recovery of tellurium can be realized. As in some embodiments, the method for separating and recovering tellurium and selenium further comprises the step (3): and adding alkali into the solution B for reaction, and performing solid-liquid separation to obtain crude tellurium dioxide. The involved reaction formula is: TeCl4+2H2O→TeO2↓ +4 HCl. Preferably, in the step (3), adding alkali into the solution B to adjust the pH value to 4-5, and then continuing to react for 0.5-1 h.
In some embodiments, the tellurium and selenium material to be separated has a tellurium content of 50 wt% to 80 wt%, a selenium content of 3 wt% to 20 wt%, and a silver content of < 10 wt%.
Before the tellurium and selenium materials are separated and recovered, the materials can be firstly crushed. In some embodiments, the tellurium and selenium material to be separated and recovered is a powder. The grain size of the tellurium and selenium material to be separated and recovered is preferably below 30 meshes.
In some embodiments, each reaction is carried out under agitation in steps (1) - (3). Each stirring speed can be adjusted according to actual conditions, for example, each stirring speed is set to be 100-1000 r/min.
Example 1
Embodiment 1 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) carrying out crushing ball milling on the tellurium-selenium-silver material (containing 75.2 wt% of tellurium, 5.3 wt% of selenium and 8.5 wt% of silver) by adopting crushing ball milling equipment, and then sieving by using a 30-mesh sieve to obtain tellurium-selenium-silver powder with the particle size of below 30 meshes;
(2) 165mL of 31 wt% hydrochloric acid and 235mL of water were added to the reactor to prepare H+Adding 100g of tellurium-selenium silver powder obtained in the step (1) into a solution with the concentration of 4mol/L at the stirring speed of 300r/min, heating to 60 ℃, and slowly adding NaClO3Controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 600mV, continuously reacting for 0.5h at 75-85 ℃, then performing suction filtration to obtain 395mL of filtrate, and drying filter residues to 11.9g, wherein the tellurium content of the filtrate is 180g/L, the selenium content of the filtrate is 13.3g/L, and the silver content of the filtrate is 135 ppm; the silver content of the filter residue is 71.2 wt%, the tellurium content is 1737ppm, the selenium content is 560ppm, and the direct silver yield (namely the ratio of the silver in the filter residue obtained in the step (2) to the silver in the tellurium-selenium-silver material, the same below) is 99.7%;
(3) taking the filtrate obtained in the step (2), heating to 70 ℃, adding sodium hypophosphite at a stirring speed of 300r/min, controlling the temperature to be 70-80 ℃ in the process, stopping adding when the potential reaches 450mV, continuously stirring and reacting at 70-80 ℃ for 0.5h, and then performing suction filtration to obtain 390mL of filtrate, wherein the filter residue is dried to be 5.8g, the tellurium content of the filtrate is 179g/L, and the selenium content is 5 ppm; the selenium content of the filter residue is 89.6 wt%, the tellurium content is 2.4 wt%, and the direct selenium yield (namely the ratio of the selenium in the filter residue obtained in the step (3) to the selenium in the tellurium-selenium-silver material, the same below) is 98.1%;
(4) taking the filtrate obtained in the step (3), adding NaOH to adjust the pH value to be 4, controlling the temperature to be lower than 80 ℃, continuing to stir at the temperature lower than 80 ℃ for reaction for 0.5h after the NaOH is added, then performing suction filtration to obtain 380mL of filtrate, and drying filter residues to be 99.2g, wherein the tellurium content of the filtrate is 62 ppm; the tellurium content of the filter residue is 75.1 percent, and the direct tellurium yield (namely the ratio of the tellurium in the filter residue obtained in the step (4) to the tellurium in the tellurium-selenium-silver material, the same below) is 99.1 percent.
Example 2
Embodiment 2 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) carrying out crushing ball milling on the tellurium-selenium-silver material (containing 75.2 wt% of tellurium, 5.3 wt% of selenium and 8.5 wt% of silver) by adopting crushing ball milling equipment, and then sieving by using a 30-mesh sieve to obtain tellurium-selenium-silver powder with the particle size of below 30 meshes;
(2) 31 wt% hydrochloric acid 205mL and water 195mL are added into the reactor to prepare H+Adding 100g of the tellurium-selenium-silver powder obtained in the step (1) into a solution with the concentration of 5mol/L at a stirring speed of 400r/min, heating to 60 ℃, slowly adding hydrogen peroxide, controlling the temperature to be 80-90 ℃ in the process, stopping adding when the potential reaches 800mV, continuously reacting for 1h at 80-90 ℃, and then performing suction filtration to obtain 400mL of filtrate, and drying filter residues to 11.8g, wherein the tellurium content of the filtrate is 182g/L, the selenium content of the filtrate is 13.1g/L, and the silver content of the filtrate is 156 ppm; the silver content of the filter residue is 71.5 wt%, the tellurium content is 1431ppm, the selenium content is 480ppm, and the silver direct recovery rate is 99.3%;
(3) taking the filtrate obtained in the step (2), heating to 75 ℃, adding sodium hypophosphite at a stirring speed of 400r/min, controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 500mV, continuously stirring and reacting at 75-85 ℃ for 1h, then performing suction filtration to obtain 395mL of filtrate, and drying filter residues to 5.9g, wherein the tellurium content of the filtrate is 180g/L, and the selenium content of the filtrate is 1 ppm; the selenium content of the filter residue is 88.5 wt%, the tellurium content is 2.2 wt%, and the selenium direct yield is 98.5%;
(4) adding NaOH into the filtrate obtained in the step (3) to adjust the pH value to be 5, controlling the temperature to be lower than 80 ℃, continuing to stir at the temperature lower than 80 ℃ for reaction for 1h after the NaOH is added, then performing suction filtration to obtain 385mL of filtrate, and drying filter residues to be 98.5g, wherein the tellurium content of the filtrate is 67 ppm; the tellurium content of the filter residue is 76.2 percent, and the direct tellurium yield is 99.8 percent.
Example 3
Embodiment 3 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) carrying out crushing ball milling on the tellurium-selenium-silver material (containing 75.2 wt% of tellurium, 5.3 wt% of selenium and 8.5 wt% of silver) by adopting crushing ball milling equipment, and then sieving by using a 30-mesh sieve to obtain tellurium-selenium-silver powder with the particle size of below 30 meshes;
(2) 245mL of 31 wt% hydrochloric acid and 155mL of water were added to the reactor to prepare H+Adding 100g of the tellurium-selenium-silver powder obtained in the step (1) into a solution with the concentration of 6mol/L at a stirring speed of 500r/min, heating to 60 ℃, slowly adding potassium permanganate, controlling the temperature to be 80-90 ℃ in the process, stopping adding when the potential reaches 900mV, continuously reacting for 1h at 80-90 ℃, and then performing suction filtration to obtain 390mL of filtrate, wherein the residue is dried to 11.5g, the tellurium content of the filtrate is 184g/L, the selenium content of the filtrate is 13.7g/L, and the silver content of the filtrate is 188 ppm; the silver content of the filter residue is 73.5 wt%, the tellurium content is 1251ppm, the selenium content is 450ppm, and the silver direct recovery rate is 99.4%;
(3) taking the filtrate obtained in the step (2), heating to 75 ℃, adding hydroxylamine hydrochloride at a stirring rate of 500r/min, controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 550mV, continuing stirring and reacting at 75-85 ℃ for 1h, then performing suction filtration to obtain 390mL of filtrate, and drying filter residues to 5.9g, wherein the tellurium content of the filtrate is 183g/L, and the selenium content is 8 ppm; the selenium content of the filter residue is 88.9 wt%, the tellurium content is 1.5 wt%, and the selenium direct yield is 98.9%;
(4) taking the filtrate obtained in the step (3), adding NaOH to adjust the pH value to be 5, controlling the temperature to be lower than 80 ℃, continuing to stir at the temperature lower than 80 ℃ for reaction for 1h after the NaOH is added, then performing suction filtration to obtain 380mL of filtrate, and drying filter residues to be 99.2g, wherein the tellurium content of the filtrate is 72 ppm; the tellurium content of the filter residue is 75.1 percent, and the direct tellurium yield is 99.1 percent.
Example 4
Embodiment 4 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) carrying out crushing ball milling on the tellurium-selenium-silver material (containing 75.2 wt% of tellurium, 5.3 wt% of selenium and 8.5 wt% of silver) by adopting crushing ball milling equipment, and then sieving by using a 30-mesh sieve to obtain tellurium-selenium-silver powder with the particle size of below 30 meshes;
(2) 124mL of 31 wt% hydrochloric acid and 176mL of water were added to the reactor to prepare H+Adding 100g of tellurium-selenium silver powder obtained in the step (1) into a solution with the concentration of 4mol/L at the stirring speed of 300r/min, heating to 60 ℃, and slowly adding NaClO3Controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 600mV, continuously reacting for 0.5h at 75-85 ℃, then performing suction filtration to obtain 295mL of filtrate, and drying filter residues to 11.7g, wherein the tellurium content of the filtrate is 252g/L, the selenium content is 17.5g/L, and the silver content is 145 ppm; the silver content of the filter residue is 72.4 wt%, the tellurium content is 1820ppm, the selenium content is 576ppm, and the silver direct recovery rate is 99.7%;
(3) taking the filtrate obtained in the step (2), heating to 70 ℃, adding sodium hypophosphite at a stirring speed of 300r/min, controlling the temperature to be 70-80 ℃ in the process, stopping adding when the potential reaches 450mV, continuously stirring and reacting at 70-80 ℃ for 0.5h, and then performing suction filtration to obtain 290mL of filtrate, wherein the filter residue is dried to be 5.7g, wherein the tellurium content of the filtrate is 250g/L, and the selenium content is 4 ppm; the selenium content of the filter residue is 91.3 wt%, the tellurium content is 2.3 wt%, and the selenium direct yield is 98.2%;
(4) taking the filtrate obtained in the step (3), adding NaOH to adjust the pH value to be 4, controlling the temperature to be lower than 80 ℃, continuing to stir at the temperature lower than 80 ℃ for reaction for 0.5h after the NaOH is added, then performing suction filtration to obtain 280mL of filtrate, and drying filter residues to 98.9g, wherein the tellurium content of the filtrate is 71 ppm; the tellurium content of the filter residue is 75.3 percent, and the direct yield of tellurium is 99.0 percent.
Example 5
Embodiment 5 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) carrying out crushing ball milling on the tellurium-selenium-silver material (containing 75.2 wt% of tellurium, 5.3 wt% of selenium and 8.5 wt% of silver) by adopting crushing ball milling equipment, and then sieving by using a 30-mesh sieve to obtain tellurium-selenium-silver powder with the particle size of below 30 meshes;
(2) 368mL of 31 wt% hydrochloric acid and 232mL of water are added into a reactor to prepare H+Adding 100g of the tellurium-selenium-silver powder obtained in the step (1) into a solution with the concentration of 6mol/L at the stirring speed of 500r/min, heating to 60 ℃, and slowly adding potassium permanganate into the solutionControlling the temperature to be 80-90 ℃, stopping adding when the potential reaches 900mV, continuously reacting for 1h at 80-90 ℃, and then performing suction filtration to obtain 590mL of filtrate, and drying filter residues to 11.7g, wherein the filtrate has a tellurium content of 126g/L, a selenium content of 8.8g/L and a silver content of 130 ppm; the silver content of the filter residue is 72.1 wt%, the tellurium content is 1191ppm, the selenium content is 475ppm, and the silver direct recovery rate is 99.2%;
(3) taking the filtrate obtained in the step (2), heating to 75 ℃, adding hydroxylamine hydrochloride at a stirring speed of 500r/min, controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 550mV, continuing stirring and reacting at 75-85 ℃ for 1h, then performing suction filtration to obtain 585mL of filtrate, and drying filter residues to be 5.9g, wherein the tellurium content of the filtrate is 123g/L, and the selenium content is 9 ppm; the selenium content of the filter residue is 88.8 wt%, the tellurium content is 1.6 wt%, and the selenium direct yield is 98.9%;
(4) adding NaOH into the filtrate obtained in the step (3) to adjust the pH value to be 5, controlling the temperature to be lower than 80 ℃, continuing to stir at the temperature lower than 80 ℃ for reaction for 1h after the NaOH is added, then performing suction filtration to obtain 580mL of filtrate, and drying filter residues to be 99.4g, wherein the tellurium content of the filtrate is 82 ppm; the tellurium content of the filter residue is 75.0 percent, and the direct yield of tellurium is 99.1 percent.
Comparative example 1
Comparative example 1 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) same as in step (1) of example 1;
(2) 165mL of 31 wt% hydrochloric acid and 235mL of water were added to the reactor to prepare H+Adding 100g of tellurium-selenium silver powder obtained in the step (1) into a solution with the concentration of 4mol/L at the stirring speed of 300r/min, heating to 60 ℃, and slowly adding NaClO3Controlling the temperature to be 75-85 ℃ in the process, stopping adding when the potential reaches 500mV, continuously reacting for 0.5h at 75-85 ℃, and then performing suction filtration to obtain 400mL of filtrate, wherein the filter residue is dried to 40.5g, the filtrate has the tellurium content of 130g/L, the selenium content of 25g/L and the silver content of 112 ppm; the silver content of the filter residue is 21.1 wt%, the tellurium content is 57.1 wt% and the selenium content is 13.1 wt%.
Comparative example 1 differs from steps (1) to (2) of example 1 in the potential at the end point of addition of only the oxidizing agent, and the other treatments and parameters are the same, but comparative example 1 is caused by addition of NaClO3To endThe point potential is too low to leach tellurium and selenium completely, and silver, selenium and tellurium in the tellurium-selenium-silver material cannot be effectively separated.
Comparative example 2
Comparative example 2 provides a method for separating and recovering tellurium, selenium and silver, which comprises the following steps:
(1) same as in step (1) of example 1;
(2) same as in step (2) of example 1;
(3) taking the filtrate obtained in the step (2), heating to 70 ℃, adding sodium hypophosphite at a stirring speed of 300r/min, controlling the temperature to be 70-80 ℃ in the process, stopping adding when the potential reaches 400mV, continuously stirring and reacting at 70-80 ℃ for 0.5h, and then performing suction filtration to obtain 390mL of filtrate, wherein the residue is dried to 12.8g, the tellurium content of the filtrate is 172g/L, and the selenium content is 1 ppm; the selenium content of the filter residue is 41.1 wt%, and the tellurium content is 58.3 wt%.
In the comparative example 1 and the steps (1) to (3) of the example 1, the potentials of the end points obtained by only adding the reducing agent are different, other treatments and parameters are the same, and as the potentials of the end points obtained by adding the sodium hypophosphite are too low, more tellurium is reduced, and the effective separation of tellurium and selenium cannot be realized.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The method for separating and recovering tellurium and selenium is characterized by comprising the following steps:
(1) adding an oxidant into the tellurium-selenium material in the presence of acid until the system potential is more than or equal to 600mV, and obtaining a solution A after the reaction is finished, wherein H in the acid+The concentration is 4-6 mol/L, and the ratio of the tellurium-selenium material to the acid is 1 g: (3-6) mL;
(2) adding a reducing agent into the solution A until the potential is 450-550 mV, and carrying out solid-liquid separation after the reaction is finished to obtain a solution B and a crude selenium solid;
the tellurium selenium material contains silver or does not contain silver, and when the tellurium selenium material contains silver, a coarse silver solid is also obtained after the reaction in the step (1) is finished.
2. The method according to claim 1, wherein in the step (1), an oxidant is added to the tellurium-selenium material until the system potential is 600-900 mV.
3. The method according to claim 1, wherein in the step (1), the reaction temperature is 70-95 ℃, and the reaction is continued for 0.5-1 h after the oxidant is stopped.
4. The method according to claim 1, wherein in the step (2), the reaction temperature is 70-85 ℃, and the reaction is continued for 0.5-1 h after the addition of the reducing agent is stopped.
5. The method according to claim 1, wherein in the step (1), the oxidant is at least one of sodium chlorate, hydrogen peroxide and potassium permanganate; in the step (2), the reducing agent is at least one of sodium hypophosphite and hydroxylamine hydrochloride.
6. The method according to claim 1, further comprising step (3): and adding alkali into the solution B for reaction, and performing solid-liquid separation to obtain crude tellurium dioxide.
7. The method according to claim 6, wherein in the step (3), after the pH value of the solution B is adjusted to 4-5 by adding alkali, the reaction is continued for 0.5-1 h.
8. The method of claim 1, wherein the tellurium-selenium material comprises 50 wt% to 80 wt% of tellurium, 3 wt% to 20 wt% of selenium, and less than 10 wt% of silver.
9. The method of claim 1, wherein the tellurium-selenium material is a powder, preferably having a particle size below 30 mesh.
10. The method according to claim 1, wherein each of the reactions in the steps (1) to (2) is carried out under stirring.
CN202110278427.8A 2021-03-15 2021-03-15 Method for separating and recovering tellurium and selenium Pending CN113148963A (en)

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