CN112174099B - Method for separating tellurium from copper-tellurium-containing complex acidic solution - Google Patents

Method for separating tellurium from copper-tellurium-containing complex acidic solution Download PDF

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CN112174099B
CN112174099B CN202010980828.3A CN202010980828A CN112174099B CN 112174099 B CN112174099 B CN 112174099B CN 202010980828 A CN202010980828 A CN 202010980828A CN 112174099 B CN112174099 B CN 112174099B
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tellurium
electrodeposition
solution
copper
stirring
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CN112174099A (en
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李栋
黎邹江
许志鹏
田庆华
李俊
郭学益
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Central South University
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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
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B7/00—Electrophoretic production of compounds or non-metals
    • 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

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Abstract

The invention discloses a method for separating tellurium from a complex acidic solution containing copper and tellurium, which comprises the following steps: placing the complex acid solution containing copper and tellurium in electrodeposition equipment, adding an oxidant into the solution and stirring; electrifying the electrodeposition equipment, carrying out electrodeposition under high current density, stirring with high strength, cutting off the electrodeposition equipment after the electrodeposition is carried out for 200min, continuously stirring the solution to ensure that the copper powder electrodeposited in the solution and tellurium in the solution completely react, and collecting a cathode product cuprous telluride after the reaction is finished. According to the method, the deposition amount of the copper powder is strictly controlled in the electrodeposition process, the copper powder is preferentially reacted with tellurium through oxidation, the deposition of impurity ions is reduced, complex solutions containing copper, tellurium, arsenic, lead, tin, bismuth, selenium, nickel and the like can be processed, the effective separation of tellurium is realized, the recovery rate of tellurium is high, side reactions in the electrodeposition process are few, the obtained product is low in impurity content and high in tellurium content, and the method is favorable for further extracting simple substance tellurium.

Description

Method for separating tellurium from copper-tellurium-containing complex acidic solution
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for separating tellurium from a complex acidic solution containing copper and tellurium.
Background
Tellurium is an important rare dispersion element, has non-metallic characteristics, and has partial metallic characteristics. Tellurium has important application in the industries of metallurgy, petrochemical industry, electronic and electric products, glass ceramics, medicine and the like, and with the continuous development of science and technology, the tellurium consumption field is transferred to the emerging semiconductor industry, such as thermoelectric materials, thin-film solar energy, infrared detectors and the like. In recent years, the development of emerging industries, particularly thin film solar energy, is increasing, so that the demand for tellurium in China and even in the world is continuously increasing.
At present, more than 90% of tellurium comes from copper electrolytic refining anode slime, the copper anode slime contains a large amount of valuable metals such as copper, tellurium, lead, tin, nickel, selenium and noble metals, and in the process of recovering the valuable metals from the copper anode slime, a large amount of acid waste solutions containing copper, tellurium, arsenic, lead, selenium, bismuth, nickel and other complex components are generated, and the copper and tellurium content in the solutions is high, so that the recovery value is high. At present, the method for industrially separating and recovering tellurium from a tellurium-containing solution mainly comprises the steps of purifying and removing impurities, replacing tellurium in the solution with copper powder to obtain cuprous telluride slag, and further recovering tellurium. The method has simple principle and mature process, but the impurity removal process before the replacement operation is complex, the requirement on impurity removal is high, and the consumption of copper powder is large and the time is long during the replacement operation. For example, patent CN102219193A discloses a method for separating and recovering tellurium from a copper-tellurium-containing solution, which comprises electrodepositing part of copper in the copper-tellurium solution, supplementing chloride ions into the solution, and reducing tellurium in the solution by sulfur dioxide or sulfite. The method for separating and recovering tellurium from copper-tellurium waste liquid disclosed in patent CN109485023A is characterized in that copper powder is prepared by direct electrodeposition, and then the copper powder is added into the solution to reduce tellurium in the solution after electrodeposition to obtain tellurium-copper slag, but in the method, the copper powder after electrodeposition is separated by a scraper and then added with a copper removing solution, the operation is complex, moreover, impurity ions are easy to codeposit with copper ions in the electrodeposition process, and the obtained tellurium-copper slag contains impurities such As As, Se and the like, which are not beneficial to subsequent further extraction of tellurium simple substances, so that the method has certain disadvantages when being applied to complex solution with multiple impurities; in addition, the method has the advantages of more copper powder addition in the replacement process, higher heating temperature in the reduction process, and increased cost and energy consumption.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the above mentioned disadvantages and drawbacks of the background art and to provide a method for separating tellurium from a complex acidic solution.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a process for separating tellurium from a complex acidic solution containing copper and tellurium, comprising the steps of:
(1) placing the complex acidic solution containing copper and tellurium in an electrodeposition device, adding an oxidant into the solution and stirring;
(2) electrifying an electrodeposition device, electrodepositing under high current density and high-intensity stirring, wherein the high current density is 1000-1500A/m2The high-intensity stirring speed is 300-500 rpm;
(3) and (4) powering off the electrodeposition equipment after electrodeposition is carried out for 200min, continuously stirring the solution to ensure that the copper powder electrodeposited in the solution and tellurium in the solution completely react, and collecting a cathode product cuprous telluride after the reaction is finished.
In the process of electrodeposition, the current density is controlled to be 1000-1500A/m2If the current density is too low, the cathode obtains a copper plate or a copper block, and active copper powder cannot be generated, and if the current density is too high, the copper powder is deposited too fast and cannot react with tellurium completely in time. The current density is kept in the range, the micron-sized copper powder obtained by the cathode has small particle size, no oxide film on the surface and high activity, and can directly reduce tellurium in the solution, and the reaction process is as follows:
Cu2++2e-＝Cu
5Cu+H6TeO6+3H2SO4＝Cu2Te+3CuSO4+6H2O。
stirring with high strength during the electrodeposition process, wherein the high-strength stirring is beneficial to the falling off of the copper powder deposited by the cathode and the copper powder fully reacts with the telluric acid in the solution; meanwhile, the high-intensity stirring is favorable for eliminating concentration polarization of electrolyte during electrodeposition, ensures that copper ions near a cathode keep high concentration, reduces the overpotential of impurity ion precipitation, reduces codeposition of the impurity ions and copper, and improves the product purity and tellurium content.
In the above method, preferably, the complex acidic solution containing copper and tellurium contains a plurality of impurity ions of arsenic, lead, tin, bismuth, nickel and selenium.
The above method, preferably, in the step (2), the electrodeposition process is carried out at normal temperature.
In the method, preferably, in the step (3), the electrodeposition time is accurately calculated according to the current density and the amount of copper powder required by tellurium in the replacement solution, and is usually 100-.
In the above method, preferably, in the step (1), the oxidant is one or more of hydrogen peroxide, potassium permanganate and nitric acid. More preferably, the oxidant is hydrogen peroxide, and other impurity ions are not introduced while the oxidation is thorough. The addition of the oxidant respectively oxidizes telluric acid and selenious acid in the solution into telluric acid and selenic acid, copper powder preferentially reacts with telluric acid, the reaction is faster and more thorough, side reactions of telluric acid and selenious acid are reduced, the product purity is improved, and the oxidation reaction is as follows (taking hydrogen peroxide as an example):
H2TeO3+H2O2+H2O＝H6TeO6
H2SeO3+H2O2＝H2SeO4+H2O。
in the above method, preferably, the amount of the oxidizing agent added is 1.1 times the theoretical molar amount.
In the above method, preferably, in the step (1), the stirring speed is 100-200 rpm, and the stirring time is 5-10 min, so as to ensure that tellurite and selenious acid in the solution are fully oxidized.
In the method, in the step (3), the solution is preferably continuously stirred for 10 to 20 min.
Compared with the prior art, the invention has the advantages that:
(1) according to the method, the deposition amount of the copper powder is strictly controlled in the electrodeposition process, the copper powder is preferentially reacted with tellurium through oxidation, the deposition of impurity ions is reduced, complex solutions containing copper, tellurium, arsenic, lead, tin, bismuth, selenium, nickel and the like can be processed, the effective separation of tellurium is realized, the recovery rate of tellurium is high, side reactions in the electrodeposition process are few, the obtained product is low in impurity content and high in tellurium content, and the method is favorable for further extracting simple substance tellurium.
(2) The method firstly oxidizes the acid solution, and the telluric acid in the oxidized solution and copper react at a high speed, so that the replacement reaction is ensured to be carried out, heat is released in the electrodeposition process, the tellurium can be efficiently recovered without heating, the current efficiency in the whole electrodeposition process is high, the energy consumption is reduced, and the cost is saved.
(3) According to the method, copper powder generated by electrodeposition is stirred at high strength and then falls off, and fully reacts with telluric acid in the solution, so that copper powder or other displacing agents are not required to be added in the tellurium displacing process, and the method is clean, efficient, green and environment-friendly.
(4) The method has the advantages of short flow, simple operation, low operation cost and strong industrial adaptability.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the complex acid solution obtained in the process of recovering noble metals from copper anode slime of a certain enterprise at home comprises the following main components in concentration (g/L): cu 35.47, Te 13.35, As 8.62, Pb 1.13, Sn 0.43, Bi 2.34, Ni 0.19, Te and Se exist mainly in the forms of tellurite and selenite.
The method for separating tellurium from the complex acid solution containing copper and tellurium comprises the following steps:
(1) placing 2L of acid solution in an electrodeposition device, adding 230mL of 1mol/L hydrogen peroxide into the solution, and stirring for 5min at the stirring speed of 200 rpm;
(2) electrifying the electrodeposition equipment, wherein the current density is 1500A/m2Increasing the stirring speed to 500rpm, electrifying for 115min, and carrying out the electrodeposition process at normal temperature;
(2) and (3) continuing stirring for 10min after power failure to enable copper and tellurium to fully react, and collecting a cathode product after the reaction is finished to obtain 53.42g of cuprous telluride.
Through calculation, the cathode current efficiency is 97.25%, the tellurium recovery rate in the whole process is 99.88%, and the tellurium content in the product cuprous telluride is 49.92%.
Example 2:
a method of the invention for separating tellurium from a complex acidic solution (same solution as in example 1) containing copper and tellurium, comprising the steps of:
(1) 2L of the acidic solution is placed in an electrodeposition device, 230mL of 1mol/L potassium permanganate is added into the solution, and the solution is stirred for 10min at the stirring speed of 100 rpm.
(2) Electrifying the electrodeposition equipment with the current density of 1400A/m2The stirring speed was increased to 400rpm, and the energization time was 120 min.
(3) And (3) continuing stirring for 15min after power failure to enable the copper and the tellurium to fully react, and collecting a cathode product after the reaction is finished to obtain 53.40g of cuprous telluride.
Through calculation, the cathode current efficiency is 99.81%, the tellurium recovery rate in the whole process is 99.85%, and the tellurium content in the product cuprous telluride is 49.92%.
Example 3:
a method of the invention for separating tellurium from a complex acidic solution (same solution as in example 1) containing copper and tellurium, comprising the steps of:
(1) putting 2L of the acidic solution into an electrodeposition device, adding 230mL of 1mol/L hydrogen peroxide into the solution, and stirring for 5min at the stirring speed of 200 rpm.
(2) Electrifying the electrodeposition equipment with the current density of 1300A/m2The stirring speed was increased to 300rpm, and the energization time was 130 min.
(3) And (3) continuing stirring for 20min after power failure to enable the copper and the tellurium to fully react, and collecting a cathode product after the reaction is finished to obtain 53.45g of cuprous telluride.
Through calculation, the cathode current efficiency is 99.34%, the tellurium recovery rate in the whole process is 99.92%, and the tellurium content in the product cuprous telluride is 49.91%.
Example 4:
a method of the invention for separating tellurium from a complex acidic solution (same solution as in example 1) containing copper and tellurium, comprising the steps of:
(1) 2L of the acidic solution is placed in an electrodeposition device, 230mL of 1mol/L potassium permanganate is added into the solution, and the solution is stirred for 10min at the stirring speed of 100 rpm.
(2) Electrifying the electrodeposition equipment, wherein the current density is 1200A/m2The stirring speed was increased to 400rpm, and the energization time was 140 min.
(3) And (3) continuing stirring for 15min after power failure to enable copper and tellurium to fully react, and collecting a cathode product after the reaction is finished to obtain 53.41g of cuprous telluride.
Through calculation, the cathode current efficiency is 99.88%, the tellurium recovery rate in the whole process is 99.82%, and the tellurium content in the product cuprous telluride is 49.90%.

Claims (5)

1. A method for separating tellurium from a complex acidic solution containing copper and tellurium, comprising the steps of:
(1) placing the complex acidic solution containing copper and tellurium in an electrodeposition device, adding an oxidant into the solution and stirring; the addition amount of the oxidant is 1.1 times of the theoretical molar amount; the stirring speed is 100-200 rpm, and the stirring time is 5-10 min;
(2) electrifying an electrodeposition device, performing electrodeposition under high current density and high-intensity stirring, wherein the high current density is 1200-1500A/m2The high-intensity stirring speed is 300-500 rpm;
(3) and (4) powering off the electrodeposition equipment after electrodeposition is carried out for 200min, continuously stirring the solution to ensure that the copper powder electrodeposited in the solution and tellurium in the solution completely react, and collecting a cathode product cuprous telluride after the reaction is finished.
2. The method of claim 1, wherein the complex acidic solution containing copper and tellurium contains a plurality of impurity ions of arsenic, lead, tin, bismuth, nickel and selenium.
3. The method of claim 1, wherein in step (2), the electrodeposition process is carried out at room temperature.
4. The method according to any one of claims 1 to 3, wherein in the step (1), the oxidant is one or more of hydrogen peroxide, potassium permanganate and nitric acid.
5. The method according to any one of claims 1 to 3, wherein in the step (3), the solution is continuously stirred for 10 to 20 min.
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CN107447105A (en) * 2017-08-23 2017-12-08 中南大学 A kind of method that copper anode mud control current potential separates and is enriched with tellurium
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