CN108486606A - A kind of cyclone electrolytic cell step recycles the method and products thereof of copper, selenium and tellurium - Google Patents
A kind of cyclone electrolytic cell step recycles the method and products thereof of copper, selenium and tellurium Download PDFInfo
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- CN108486606A CN108486606A CN201810252588.8A CN201810252588A CN108486606A CN 108486606 A CN108486606 A CN 108486606A CN 201810252588 A CN201810252588 A CN 201810252588A CN 108486606 A CN108486606 A CN 108486606A
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- tellurium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- 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 discloses the methods and products thereof of a kind of cyclone electrolytic cell step recycling copper, selenium and tellurium.It includes cyclone electrolytic cell reaction：It is electrochemically reacted being placed in cyclone electrolytic cell reaction unit containing copper, selenium, the solution of tellurium ion and hydrochloric acid or sulfuric acid, adjusts current potential successively, adjusted current potential every time and all carry out a cyclone electrolytic cell reaction, obtain tellurium, copper, selenium solid mixture successively；Separation：The solid mixture is washed into drying, obtains the simple substance or oxide of copper, selenium and tellurium successively.The cathode that the present invention uses includes the titanium sheet by oxidation processes, titanium plate surface molecule is in netted stepped construction, not only increase the specific surface area of electrode, and overall structure dense uniform, it can preferably be contacted with solution with compared with the stainless steel substrates that traditional cyclone electrolytic cell uses, adsorption capacity is greatly improved, and obtained product purity has larger promotion, yield to be also substantially improved.
Description
Technical field
The invention belongs to rare (non-) metal recovery and pollutant process technical fields, and in particular to a kind of cyclone electrolytic cell
Step recycles the method and products thereof of copper, selenium and tellurium.
Background technology
Copper is the non-ferrous metal very close with human relation, be widely used in it is electrical, light industry, machine-building, build
Build the fields such as industry, national defense industry.Copper is a kind of " green " metal, and it is relatively low to be primarily due to its fusing point, easy re-melting, again smelting
Refining, so recycling considerably cheap.But meanwhile containing a large amount of copper in there is a large amount of waste in China, how to the greatest extent most
Big effect recycling copper metal is also a problem.
Selenium is widely used in the industrial circles such as glass, ceramics, dyestuff, rubber, petrochemical industry, metallurgy, plating, especially high
Scientific and technological industry department, such as semiconductor equipment, photoelectricity equipment, Se solar cell, laser device, laser and infrared ray optical direction material
Manufacture.It deepens continuously to the understanding of selenium and research now with the continuous development of scientific and technological level, people.Selenium is in national economy
Critical role it is more and more prominent, application of the selenium in industrial and agricultural production and human health industry is more extensive, and the market demand has
Increase nothing to subtract.China is also long-term one of the country for relying on import selenium product.
The 80% of tellurium consumption figure is applied in metallurgical industry：A small amount of tellurium is added in steel and copper alloy, can improve its cutting and add
Work performance simultaneously increases hardness；Tellurium is used as carbide stabilizer in white cast-iron, keeps surface firm wear-resisting；It is added in lead few
The tellurium of amount can be improved the wearability, corrosion resistance and intensity of material, may be used as the sheath on submarine cable；Tellurium is set to be added to lead
The middle hardness that can increase lead can be used for making the pole plate and printing type of battery.Tellurium also serves as adding for petroleum cracking catalyst
Add agent, also can be used as the catalyst for producing ethylene glycol.High purity tellurium can also be used as the alloy compositions of thermoelectric material, the compound of tellurium
Bismuth telluride is good refrigerating material, and tellurium and several tellurides are all semi-conducting materials, and ultrapure tellurium single-crystal is novel infrared material
Material.
Selenium and tellurium are industrially largely present among the earth of positive pole of electrodeposition refined copper, but detach each comparison of ingredients
Complicated and low separation efficiency, is unable to reach expected separation requirement, so better way and method are needed, as short as possible
Raw material are more effectively utilized in duration, reach the double effects of economy and efficiency.
Therefore, this field needs a kind of efficient and environmentally friendly method so that the utilization rate of same raw material improves, reduce at
This, increases yield, increases economic benefit.
Invention content
The purpose of this part is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferably to implement
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of above-mentioned technological deficiency, it is proposed that the present invention.
Therefore, as one aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides a kind of rotation
The method that galvanic electricity solution step recycles copper, selenium and tellurium.
In order to solve the above technical problems, the present invention provides following technical solutions：A kind of cyclone electrolytic cell step recycling copper, selenium
With the method for tellurium comprising,
Cyclone electrolytic cell reacts：It will be placed in cyclone electrolytic cell reaction unit containing copper, selenium, the solution of tellurium ion and hydrochloric acid or sulfuric acid
In be electrochemically reacted, adjust current potential successively, adjust current potential every time and all carries out cyclone electrolytic cell and react, obtain successively tellurium,
Copper, selenium solid mixture；
Separation：The solid mixture is washed into drying, obtains the simple substance or oxide of copper, selenium and tellurium successively.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
State the solution containing copper, selenium, tellurium ion, wherein the hydrochloric acid or sulfuric acid, a concentration of 1M~4M.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction unit is stated including a cyclone electrolytic cell slot, working electrode and to electrode, the cyclone electrolytic cell slot is normal-pressure electric
Solve slot.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
It includes the titanium sheet or 316L type stainless steel substrates with high-specific surface area by oxidation processes to state working electrode, described to be to electrode
Graphite electrode.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction is stated to carry out under the conditions of 25~140 DEG C.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction is stated, the time that adjustment current potential is reacted every time is 4~8h.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out tellurium cell reaction is -0.18V~-0.25V.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out cupric electrolysis reaction is -0.38V~-0.42V.
A kind of preferred embodiment of method as cyclone electrolytic cell step of the present invention recycling copper, selenium and tellurium, wherein：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out selenium cell reaction is -0.48V~-0.50V.
As another aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provide a kind of copper, selenium,
Tellurium, wherein：The copper purity is 90% or more, and the selenium purity is 89% or more, and the tellurium purity is 92% or more.
Beneficial effects of the present invention：
(1) cathode of the method for cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium is by oxidation processes
Titanium sheet, titanium plate surface molecule is in netted stepped construction, not only increases the specific surface area of electrode, and overall structure is fine and close
It is even, it can preferably be contacted with solution compared with the stainless steel substrates that traditional cyclone electrolytic cell uses, adsorption capacity has prodigious
It is promoted, obtained product purity has larger promotion, yield to be also substantially improved.
(2) method of cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium uses atmospheric operation, reaction temperature low
(minimum reaction temperature is only 25 DEG C), reduces reaction temperature, to reduce energy consumption compared with traditional technique.
(3) method of cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium is not drawn in terms of reflection medium in system
Enter impurity, is convenient for subsequent separation；Acid concentration used is greatly reduced, and reduces sour consumption；
(4) method of cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium does not add any auxiliary material, compares
In traditional technique, blowdown flow rate can reduce 20wt%~50wt%；
(5) the method cyclone electrolytic cell operation automation of cyclone electrolytic cell step recycling copper, selenium and tellurium provided by the invention
Degree is high, reduces human input, convenient for producing in enormous quantities, can bring good economic benefit and social benefit, have good
Good application prospect.
(6) method of cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium carries out step using rotational-flow electrolysis method
Recycling, obtained product are that one kind receives powder body, have good plasticity with processing for subsequent application, facilitate follow-up
Use.
(7) method of cyclone electrolytic cell step recycling copper provided by the invention, selenium and tellurium is by mantoquita, selenium salt and tellurium salt same
Integrated treatment in one solution offers convenience for later engineering practice, when not only reducing the dosage of raw material, and reducing reaction
Between and equipment dosage.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is the processing technological flow that the cyclone electrolytic cell step that one embodiment of the present invention provides recycles copper, selenium and tellurium
Figure.
The recovery rate curve graph of the copper that Fig. 2 is provided by embodiment 1 at any time.
The recovery rate curve graph of the selenium that Fig. 3 is provided by embodiment 1 at any time.
The recovery rate curve graph of the tellurium that Fig. 4 is provided by embodiment 1 at any time.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to specific embodiment pair
The specific implementation mode of the present invention is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Implemented different from other manner described here using other, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Secondly, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
The chemical reaction that electrochemical reaction process of the present invention includes has：
Cu2++2e→Cu (1)
SeO3 2-+6H++4e-→Se+3H2O (2)
TeO3 2-+6H++4e-→Te+3H2O (3)
Embodiment 1：
A kind of cyclone electrolytic cell step detaches the processing method of copper, selenium and tellurium, includes the following steps：
(1) dispensing：Solution, wherein copper ion concentration 1g/L, plasma selenium concentration 1g/L and tellurium ion concentration 1g/L are configured, it is molten
Concentration of hydrochloric acid in liquid is 1M；
(2) cyclone electrolytic cell reacts：The solution of step (1) is fitted into the fluid reservoir of swirl electrolysis device, electricity is then adjusted
Position is the titanium sheet for having high-specific surface area by oxidation processes, is the eddy flow of graphite electrode to electrode in -0.2V in working electrode
It is reacted in electrolysis unit, reaction time 8h, reaction temperature is adjusted to 25 DEG C；Reaction replaces working electrode after completing,
Current potential is adjusted to -0.4V, reaction temperature is constant, is reacted, reaction time 8h；After reaction is completed, working electrode is replaced,
Current potential is adjusted to -0.5V, temperature-resistant to be reacted, reaction time position 8h.It can be collected into successively in the electrode titanium sheet of replacement
The simple substance or oxide of tellurium, copper and selenium.
The processing mode of Ti electrode is：Titanium sheet is placed in hydrofluoric acid and carries out pickling 1h, to remove the oxidation of titanium plate surface
Film.Titanium sheet after pickling is cleaned and is dried in vacuo.H2O2 and H2SO4 mixed solutions are configured, configuration is than being 1:3, then
Titanium sheet is placed in the solution, reacts 40min in the environment of temperature is 80 DEG C.
(3) product detaches：The collection of product progressive, washing and the drying that step (2) is obtained, are utilized with a small amount of sample
XRD and EDS spectrum tests purity therein.The purity that copper is calculated is 98%, the purity of selenium is 99% and the purity of tellurium is
98%.It is calculated that the yield of copper is 99%, the yield of selenium is 98% and the yield of tellurium is 98% by weighing.
Embodiment 2：
A kind of cyclone electrolytic cell step recycles the processing method of copper, selenium and tellurium, includes the following steps：
(1) solution is configured, wherein copper ion concentration is 2.5g/L, a concentration of 1.7g/L of plasma selenium and tellurium ion concentration are
1g/L, concentration of hydrochloric acid 4M；
(2) solution of configuration is put into the fluid reservoir of swirl electrolysis device, setting temperature is 140 DEG C, and current potential is adjusted
To -0.22V, it is the titanium sheet that there is high-specific surface area by oxidation processes, is the eddy flow of graphite electrode to electrode in working electrode
It is reacted in electrolysis unit, reaction time 4h；Reaction electrode is replaced after reaction, and it is anti-to -0.41V progress to adjust point
It answers, reaction time 4h；Electrode is replaced after reaction, is adjusted current potential to -0.49V, is reacted, reaction time 4h.
The simple substance or oxide of tellurium, copper and selenium can be collected on the electrode of replacement successively.
The processing mode of Ti electrode is：Titanium sheet is placed in hydrofluoric acid and carries out pickling 1h, to remove the oxidation of titanium plate surface
Film.Titanium sheet after pickling is cleaned and is dried in vacuo.H2O2 and H2SO4 mixed solutions are configured, configuration is than being 1:3, then
Titanium sheet is placed in the solution, reacts 40min in the environment of temperature is 80 DEG C.
(3) reaction product that step (2) obtains is detached, washed and is dried, a small amount of sample is taken to utilize XRD and EDS
Each product purity of spectrum test, the purity that copper in product, selenium and tellurium is calculated are 95%, 94% and 92%.Pass through weightometer
Calculation obtains that the yield of copper is 99%, the yield of selenium is 96% and the yield of tellurium is 97%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, mantoquita used replaces with copper sulphate, uses identical survey
Amount method obtains copper, selenium and tellurium purity and is followed successively by 92%, 93% and 93%, and yield is followed successively by 97%, 96% and 96%.
Embodiment 3：
A kind of cyclone electrolytic cell step recycles the processing method of copper, selenium and tellurium, includes the following steps：
(1) solution is configured, wherein copper ion concentration is 1.8g/L, a concentration of 1.8g/L of plasma selenium and tellurium ion concentration are
1.5g/L, concentration of hydrochloric acid 4M；
(2) solution of configuration is put into the fluid reservoir of swirl electrolysis device, setting temperature is 60 DEG C, and current potential is adjusted
To -0.22V, it is the titanium sheet that there is high-specific surface area by oxidation processes, is the eddy flow of graphite electrode to electrode in working electrode
It is reacted in electrolysis unit, reaction time 8h；Reaction electrode is replaced after reaction, and it is anti-to -0.41V progress to adjust point
It answers, reaction time 8h；Electrode is replaced after reaction, is adjusted current potential to -0.50V, is reacted, reaction time 8h.
The simple substance or oxide of tellurium, copper and selenium can be collected on the electrode of replacement successively.
The processing mode of Ti electrode is：Titanium sheet is placed in hydrofluoric acid and carries out pickling 1h, to remove the oxidation of titanium plate surface
Film.Titanium sheet after pickling is cleaned and is dried in vacuo.H2O2 and H2SO4 mixed solutions are configured, configuration is than being 1:3, then
Titanium sheet is placed in the solution, reacts 40min in the environment of temperature is 80 DEG C.
(3) reaction product that step (2) obtains is detached, washed and is dried, a small amount of sample is taken to utilize XRD and EDS
Each product purity of spectrum test, the purity that copper in product, selenium and tellurium is calculated are 96%, 94% and 95%.Pass through weightometer
Calculation obtains that the yield of copper is 97%, the yield of selenium is 96% and the yield of tellurium is 94%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, mantoquita used replaces with copper sulphate, uses identical survey
Amount method obtains copper, selenium and tellurium purity and is followed successively by 90%, 89% and 92%, and yield is followed successively by 97%, 93% and 92%.
Embodiment 4：
In addition to the cyclone electrolytic cell reaction in step (2) is replaced with general electrolytic reaction, remaining is same as Example 1.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 68%, 54% and 49%.It is calculated that the yield of copper is 78%, the yield of selenium is 77% and the yield of tellurium by weighing
It is 78%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 63%, 50% and 45%, and yield is followed successively by 67%, 73% and 78%.
Embodiment 5：
In addition to the titanium sheet in the cyclone electrolytic cell slot in step (2) is replaced with 304 type stainless steel substrates, remaining and embodiment 1
It is identical.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 73%, 62% and 50%.It is calculated that the yield of copper is 93%, the yield of selenium is 90% and the yield of tellurium by weighing
It is 94%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 70%, 63% and 54%, and yield is followed successively by 91%, 93% and 91%.
Embodiment 6：
In addition to the titanium sheet in the cyclone electrolytic cell slot in step (2) is replaced with 321 type stainless steel substrates, remaining and embodiment 1
It is identical.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 95%, 96% and 92%.It is calculated that the yield of copper is 97%, the yield of selenium is 95% and the yield of tellurium by weighing
It is 93%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 89%, 92% and 94%, and yield is followed successively by 97%, 96% and 93%.
Embodiment 7：
Except will in the cyclone electrolytic cell slot in step (2) by oxidation processes have high-specific surface area titanium sheet replace with
Outside 316L type stainless steel substrates, remaining is same as Example 1.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 96%, 94% and 93%.It is calculated that the yield of copper is 98%, the yield of selenium is 96% and the yield of tellurium by weighing
It is 96%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 95%, 92% and 94%, and yield is followed successively by 97%, 98% and 96%.
Embodiment 8：
Except will in the cyclone electrolytic cell slot in step (2) by oxidation processes have high-specific surface area titanium sheet replace with
Outside 201 type stainless steel substrates, remaining is same as Example 1.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 50%, 47% and 49%.It is calculated that the yield of copper is 85%, the yield of selenium is 84% and the yield of tellurium by weighing
It is 86%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 68%, 61% and 71%, and yield is followed successively by 84%, 86% and 87%.
Embodiment 9：
A kind of cyclone electrolytic cell step recycles the processing method of copper, selenium and tellurium, includes the following steps：
(1) solution is configured, wherein copper ion concentration is 2.5g/L, a concentration of 1.7g/L of plasma selenium and tellurium ion concentration are
1g/L, concentration of hydrochloric acid 4M；
(2) solution of configuration is put into the fluid reservoir of swirl electrolysis device, setting temperature is 140 DEG C, and current potential is adjusted
To -0.22V, working electrode be 316L types stainless steel, be to electrode graphite electrode swirl electrolysis device in react, instead
It is 4h between seasonable；Reaction electrode is replaced after reaction, and adjusting point to -0.41V is reacted, reaction time 4h；Reaction
After replace electrode, adjust current potential to -0.49V, reacted, reaction time 4h.It can be received successively on the electrode of replacement
Collect the simple substance or oxide of tellurium, copper and selenium.
(3) reaction product that step (2) obtains is detached, washed and is dried, a small amount of sample is taken to utilize XRD and EDS
Each product purity of spectrum test, the purity that copper in product, selenium and tellurium is calculated are 91%, 86% and 81%.Pass through weightometer
Calculation obtains that the yield of copper is 99%, the yield of selenium is 96% and the yield of tellurium is 97%.
Embodiment 10：
A kind of cyclone electrolytic cell step recycles the processing method of copper, selenium and tellurium, includes the following steps：
(1) solution is configured, wherein copper ion concentration is 2g/L, a concentration of 1.5g/L of plasma selenium and tellurium ion concentration are
1.5g/L, concentration of hydrochloric acid 4M；
(2) solution of configuration is put into the fluid reservoir of swirl electrolysis device, setting temperature is 90 DEG C, and current potential is adjusted
Cyclone electrolytic cell reaction is carried out to -0.2V, is 316L types stainless steel, is the cyclone electrolytic cell dress of graphite electrode to electrode in working electrode
It is reacted in setting, reaction time 8h；Reaction electrode is replaced after reaction, is adjusted point and is reacted to -0.4V, is reacted
Time is 8h；Electrode is replaced after reaction, is adjusted current potential to -0.5V, is reacted, reaction time 8h.In the electricity of replacement
The simple substance or oxide of tellurium, copper and selenium can be collected on extremely successively.
(3) reaction product that step (2) obtains is detached, washed and is dried, a small amount of sample is taken to utilize XRD and EDS
Each product purity of spectrum test, the purity that copper in product, selenium and tellurium is calculated are 97%, 89% and 87%.Pass through weightometer
Calculation obtains that the yield of copper is 96%, the yield of selenium is 95% and the yield of tellurium is 98%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, mantoquita used replaces with copper sulphate, uses identical survey
Amount method obtains copper, selenium and tellurium purity and is followed successively by 96%, 86% and 84%, and yield is followed successively by 95%, 94% and 97%.
Embodiment 11：
It is general except by oxidation processes will there is the titanium sheet of high-specific surface area to replace in the cyclone electrolytic cell slot in step (2)
Outside logical titanium sheet, remaining is same as Example 1.
Each product purity of product utilization XRD and EDS spectrum test that will be obtained, is calculated copper in product, selenium and tellurium
Purity is 86%, 84% and 87%.It is calculated that the yield of copper is 91%, the yield of selenium is 90% and the yield of tellurium by weighing
It is 89%.
Change the hydrochloric acid in the embodiment into same concentration sulphuric acid, it is pure to obtain copper, selenium and tellurium using identical measurement method
Degree is followed successively by 87%, 85% and 85%, and yield is followed successively by 89%, 90% and 92%.
Thus embodiment is it is found that the cyclone electrolytic cell efficiency of common titanium sheet electrode is worse than 316L stainless steel substrates electrodes.
To sum up, the method for cyclone electrolytic cell step separation copper of the present invention, selenium and tellurium is utilized in swirl electrolysis device
Inner cathode electrochemistry is reduced directly to obtain product, which has shown and divided copper, selenium and tellurium successively from raw material under temperate condition
It leaves and, since cyclone electrolytic cell enables electrode preferably to be contacted with solution, liquid eliminates concentration polarization by high speed rotation, from
And can obtain high-purity receives powder body product, to realize copper, selenium and tellurium it is efficient using and purification.
Working electrode (cathode) in swirl electrolysis device is right using the titanium sheet by oxidation processes with high-specific surface area
Electrode (anode) enables to the method to reach optimum efficiency using graphite rod.
The cathode that cyclone electrolytic cell step provided by the invention recycles the method for copper, selenium and tellurium is the titanium by oxidation processes
Piece, titanium plate surface molecule are in netted stepped construction, not only increase the specific surface area of electrode, and overall structure dense uniform,
It can preferably be contacted with solution with compared with the stainless steel substrates that traditional cyclone electrolytic cell uses, adsorption capacity has prodigious carry
It rises, obtained product purity has larger promotion, yield to be also substantially improved.Cyclone electrolytic cell step recycling provided by the invention
The method of copper, selenium and tellurium uses atmospheric operation, and reaction temperature is low (minimum reaction temperature is only 25 DEG C), compared with traditional technique
Reaction temperature is reduced, to reduce energy consumption.The method of cyclone electrolytic cell step provided by the invention recycling copper, selenium and tellurium is from anti-
It reflects medium to see, impurity is not introduced into system, be convenient for subsequent separation；Acid concentration used is greatly reduced, and reduces acid
Consumption；The method that cyclone electrolytic cell step provided by the invention recycles copper, selenium and tellurium does not add any auxiliary material, compared to traditional
Technique, blowdown flow rate can reduce 20wt%~50wt%；The method that cyclone electrolytic cell step provided by the invention recycles copper, selenium and tellurium
Cyclone electrolytic cell operation high degree of automation, reduces human input, convenient for producing in enormous quantities, can bring good economy
Benefit and social benefit, have a good application prospect.Cyclone electrolytic cell step provided by the invention recycles the method profit of copper, selenium and tellurium
Step recycling is carried out with rotational-flow electrolysis method, obtained product is that one kind receives powder body, is had with processing for subsequent application
Good plasticity, facilitates subsequent use.The method of cyclone electrolytic cell step provided by the invention recycling copper, selenium and tellurium be by
Mantoquita, the integrated treatment in same solution of selenium salt and tellurium salt offer convenience for later engineering practice, not only reduce the use of raw material
Amount, and reduce the dosage of reaction time and equipment.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to preferable
Embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered in this hair
In bright right.
Claims (10)
1. a kind of method of cyclone electrolytic cell step recycling copper, selenium and tellurium, it is characterised in that：Including,
Cyclone electrolytic cell reacts：By containing copper, selenium, the solution of tellurium ion and hydrochloric acid or sulfuric acid be placed in cyclone electrolytic cell reaction unit into
Row electrochemical reaction, adjusts current potential successively, adjusts current potential every time and all carries out a cyclone electrolytic cell reaction, obtains tellurium, copper, selenium successively
Solid mixture；
Separation：The solid mixture is washed into drying, obtains the simple substance or oxide of copper, selenium and tellurium successively.
2. the method for cyclone electrolytic cell step recycling copper as described in claim 1, selenium and tellurium, it is characterised in that：It is described containing copper,
The solution of selenium, tellurium ion, wherein the hydrochloric acid or sulfuric acid, a concentration of 1M~4M.
3. the method for cyclone electrolytic cell step recycling copper as claimed in claim 1 or 2, selenium and tellurium, it is characterised in that：The eddy flow
For electrolysis reaction device including a cyclone electrolytic cell slot, working electrode and to electrode, the cyclone electrolytic cell slot is normal pressure electrolytic cell.
4. the method for cyclone electrolytic cell step recycling copper as claimed in claim 3, selenium and tellurium, it is characterised in that：The work electricity
Pole includes the titanium sheet or 316L type stainless steel substrates with high-specific surface area by oxidation processes, and described is graphite electricity to electrode
Pole.
5. the method for the cyclone electrolytic cell step recycling copper, selenium and tellurium as described in claim 1,2 or 4 are any, it is characterised in that：Institute
Cyclone electrolytic cell reaction is stated to carry out under the conditions of 25~140 DEG C.
6. the method for the cyclone electrolytic cell step recycling copper, selenium and tellurium as described in claim 1,2 or 4 are any, it is characterised in that：Institute
Cyclone electrolytic cell reaction is stated, the time that adjustment current potential is reacted every time is 4~8h.
7. the method for the cyclone electrolytic cell step recycling copper, selenium and tellurium as described in claim 1,2 or 4 are any, it is characterised in that：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out tellurium cell reaction is -0.18V~-0.25V.
8. the method for the cyclone electrolytic cell step recycling copper, selenium and tellurium as described in claim 1,2 or 4 are any, it is characterised in that：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out cupric electrolysis reaction is -0.38V~-0.42V.
9. the method for the cyclone electrolytic cell step recycling copper, selenium and tellurium as described in claim 1,2 or 4 are any, it is characterised in that：Institute
Cyclone electrolytic cell reaction is stated, the voltage when carrying out selenium cell reaction is -0.48V~-0.50V.
10. copper, selenium, tellurium made from the method as described in claim 1~9 is any, it is characterised in that：The copper purity is 90%
More than, the selenium purity is 89% or more, and the tellurium purity is 92% or more.
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