CN109628953A - The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte - Google Patents
The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte Download PDFInfo
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- CN109628953A CN109628953A CN201811602137.9A CN201811602137A CN109628953A CN 109628953 A CN109628953 A CN 109628953A CN 201811602137 A CN201811602137 A CN 201811602137A CN 109628953 A CN109628953 A CN 109628953A
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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 present invention relates to cleaning copper electrolyte removal of impurities fields, for solve it is in the prior art for purifying copper electrolyte, go the problems such as method and step of arsenic removal antimony bismuth is many and diverse, effect is poor or cost is excessively high, the present invention provides a kind of methods that arsenic removal antimony bismuth is removed in copper electrolyte.It the described method comprises the following steps: 1) transition state sb oxide being added into copper electrolyte；2) reaction is stirred or stood to copper electrolyte, is filtered to remove sediment after fully reacting.The method of the present invention operating procedure is succinct, can quickly and efficiently remove the arsenic antimony bismuth in copper electrolyte；The removal rate of arsenic antimony bismuth is high, can almost remove antimony element；The recyclable recycling of transition state sb oxide, it is environmentally protective.
Description
Technical field
The present invention relates to the sides that arsenic removal antimony bismuth is removed in cleaning copper electrolyte removal of impurities field more particularly to a kind of copper electrolyte
Method.
Background technique
The purification of copper electrolyte recycles the important topic of always copper electrolyzing refining industry, especially with copper concentrate
Exhaustive exploitation, copper ore grade decline, and the impurities accumulation speed in copper electrolyte is speeded.Currently, this project annoyings China Copper
Smelting industry.Since copper smelting by pyrometallurgy can not remove many accompanying elements in copper mine, such as nickel, arsenic, bismuth, antimony, the elements such as gold, this
A little impurity are in subsequent electrorefining processes or lose electronics and enter copper electrolyte, or are directly entered the earth of positive pole.And enter copper
These foreign ions of electrolyte reach a timing in its concentration with the refining production constantly enrichment of copper, can be in electro-deposition
Cheng Yutong is co-deposited hence into tough cathode, so that the quality of tough cathode declines.
Currently, the major way for electrolyte purification is electrolysis induction decopper(ing) method, make arsenic while acid copper
The impurity such as antimony bismuth remove together.For the technique using extensively, good impurity removing effect has good industrial foundation.But its there are bright
Aobvious disadvantage: 1) using chloride plate, causes electrolytic cell pressure high, and energy consumption is larger, and stereotype easily deforms in use,
Manual synchronizing is needed, it is cumbersome to eventually lead to integrated artistic；2) poisonous and harmful gas is easily generated on electrolysis decopper(ing) latter stage, cathode plate
Body arsenic hydride, worker's operating environment are severe；3) cathode solid product black copper is difficult to directly utilize, general to return to copper pyrometallurgy stream
Journey；4) entire purification process technique includes electrolysis decopper(ing), and nickel sulfate recycles, the recycling of sulfuric acid, and process flow is long.In addition, all
Such as ion-exchange, barium salt, lead salt precipitation are also applied to the purification of copper electrolyte.But the above method exists obviously
Defect, not by large-scale use.
Patent Office of the People's Republic of China disclosed a kind of patent of invention Shen of purifying and impurity-removing method for copper electrolytic solution on September 10th, 2008
Please, application publication number CN101260539A.Relative mass ratio by the Sb/Bi in control anode copper is 0.8~8.0, copper
The concentration ratio that the concentration of As is As (III) and As (V) in 4.0g/L~15.0g/L and copper electrolyte in electrolyte be 0.01~
0.15, accelerate the speed that arsenic stibate deposits precipitation in copper electrolyte, and then improve the ability of copper electrolyte auto purification removal of impurities.
But copper electrolyte is carried out after purification and impurity removal in copper electrolyte still containing the bismuth element of higher concentration, institute by the technical solution
The purification and impurity removal effect played is poor, is unable to satisfy the step purification of copper electrolyte.
And in Xiao F X, Cao D, Mao J W, et al.Role of Sb (V) in removal of As, Sb and
Biimpurities from copper electrolyte[J].Transactions of Nonferrous Metals
Society of China, 2014,24 (1): it is also proposed that quinquevalence antimony and the harmful element in copper electrolyte in mono- text of 271-278
There are co-precipitations for arsenic, antimony, bismuth.Therefore, before antimony pentoxide being rich in industrial application as a kind of cleaning copper electrolyte agent
Scape.
On this basis, Patent Office of the People's Republic of China disclosed a kind of method of copper electrolyte precipitation to remove impurities on September 15th, 2017
Application for a patent for invention, application publication number CN107164786A.The patent is made by the way that antimonial is added into copper electrolyte
For precipitating reagent, arsenic, antimony, bismuth co-precipitation removing in copper electrolyte are realized.Copper electrolyte can directly return to copper electricity after removing impurities
Rectification systems are solved, and the precipitating waste residue containing arsenic, antimony, bismuth generated passes through gradient temperature control pyrogenic process synthetical recovery.Waste residue is first lazy
Property gas shield under, carry out low-temperature decomposition and obtain low-temperature decomposition gas and low-temperature decomposition slag, low-temperature decomposition gas is obtained through condensation
Arsenic compound；Low-temperature decomposition slag carries out pyrolytic under control climate, obtains bismuth compound and pyrolysis gases；High temperature point
Solution gas obtains antimonial through condensation, can be used as precipitating reagent and returns to copper electrolyte precipitation to remove impurities process.In the technical scheme,
The precipitating reagent being added is one of antimony oxide, antimony tetroxide, antimony pentoxide or a variety of.However, the antimony chemical combination
Object precipitating reagent is prepared by high temperature pyrogenic process process, and ingredient and structure are more difficult to control, and resulting sb oxide activity is low, to cupric electrolysis
The clean-up effect of liquid is to be improved.
Summary of the invention
For solve it is in the prior art for purifying copper electrolyte, go that the method and step of arsenic removal antimony bismuth is many and diverse, effect is poor
And cost it is excessively high the problems such as, the present invention provides a kind of methods that arsenic removal antimony bismuth is removed in copper electrolyte.Its head of the method for the present invention
It first to realize the purpose of arsenic antimony bismuth in simplified step, efficiently removal copper electrolyte, and improve remove arsenic removal antimony bismuth on this basis
Effect.
To achieve the above object, the present invention uses following technical scheme.
A kind of method that arsenic removal antimony bismuth is removed in copper electrolyte, the described method comprises the following steps:
1) transition state sb oxide is added into copper electrolyte；
2) reaction is stirred or stood to copper electrolyte, is filtered to remove sediment after fully reacting.
The method of the present invention adds transition state sb oxide into copper electrolyte as precipitating reagent, passes through precipitating reagent and cupric electrolysis
Three kinds of harmful element reactions of arsenic antimony bismuth or absorption or co-precipitation in liquid are to fast implement deimpurity purpose.Holistic approach letter
It is clean, it is not necessarily to remaining equipment, it is only necessary to it launches and filters two steps, it is extremely efficiently and succinct.
Preferably, step 1) the transition state sb oxide is the pyrochlore constitution with Sb (III, V) mixed valence
Single-phase sb oxide.
The single-phase sb oxide of pyrochlore constitution with Sb (III, V) mixed valence wherein contains Sb (III) and Sb
(V).During the reaction, the bismuth element in the quinquevalence antimony and copper electrolyte that transition state sb oxide is released forms Bi3SbO7
Precipitating, and reacting for arsenic, be pentavalent arsenic As (V) directly formed with quinquevalence antimony Sb (V) arsenic metaantimmonic acid again with remaining trivalent impurity ion
Arsenic stibate precipitating is formed, and is then to realize induced precipitation by improving antimony concentration with the antimony element in copper electrolyte.It crosses
Crossing state sb oxide makes part of Sb (V) autoreduction trivalent antimony Sb by calcining by the antimony pentoxide fine powder hydrolyzed
(III) mode is formed, and the powder that partial size is about 60~120nm can be formed by being formed by transition state sb oxide.The partial size model
The transition state sb oxide enclosed have great specific surface area, can rapid dispersion, play good reaction precipitating and absorption is total to
The effect of precipitating, and partial size is too small can not provide the forming core active site in coprecipitation process, weaken co-precipitation speed and not
Conducive to filter operation later；And partial size is excessive, specific surface area reduces, reduces the contact of itself and impurity component in copper electrolyte
Probability, dispersion difficulty increase.During autoreduction, partial reduction and the crystallization water of quinquevalence antimony has occurred in sb oxide simultaneously
Lose so that contain a large amount of defect and hole in transition state sb oxide powder, the thus ratio table of transition state sb oxide
Area is greatly improved, and increases the chance contacted with copper electrolyte, and since the generation of defect improves it in copper electricity
The solubility in liquid is solved, the antimony concentration of solution system can be improved in a short time in copper electrolyte, is efficiently gone with realizing
The purpose of arsenic removal antimony bismuth.
Preferably, the molar ratio of Sb (III) and Sb (V) are (0.3~0.8) in the transition state sb oxide: 2.
Sb (III) too high levels then will lead to the decline of solubility and crystal defect, and reduce effective component Sb's (V)
Ratio causes the effect of arsenic removal antimony bismuth to decline, and Sb (III) content can not then be effectively formed defect and hole less excessively, together
Sample can reduce the effect of arsenic removal antimony bismuth.
Preferably, the solid-to-liquid ratio of transition state sb oxide and copper electrolyte used in step 1) are as follows: (5~35) g:1L.
Only need less dosage that the removal to arsenic antimony bismuth in copper electrolyte, and the transition state antimony oxygen after absorption can be realized
The recyclable recycling of compound.
Preferably, the step 2) reaction temperature is 25~80 DEG C.
Using transition state sb oxide as cleanser, arsenic antimony bismuth at least can be 10~95 DEG C of this poles in removal copper electrolyte
Carried out within the scope of big temperature, by within the scope of 25~80 DEG C, reaction rate is very fast and reaction carry out it is more complete, it is less very
Side reaction will not extremely occur, optimal reaction temperature is 60 DEG C.
Preferably, the copper electrolyte also can be replaced any acidic bodies of water.
The method of the present invention can be used for removing the arsenic antimony bismuth in acidic bodies of water, all have preferably using effect.
The beneficial effects of the present invention are:
1) operating procedure is succinct, can quickly and efficiently remove the arsenic antimony bismuth in copper electrolyte；
2) removal rate of arsenic antimony bismuth is high, can almost remove antimony element；
3) the recyclable recycling of transition state sb oxide, it is environmentally protective.
Detailed description of the invention
Fig. 1 is the TEM figure of transition state sb oxide used in the embodiment of the present invention；
Fig. 2 is the xps energy spectrum of transition state sb oxide used in the embodiment of the present invention.
Specific embodiment
Further clear detailed description explanation is made to the present invention below in conjunction with specific embodiment and Figure of description.This
Field those of ordinary skill will realize the present invention based on these explanations.In addition, being related in following the description
The embodiment of the present invention be generally only an of the invention branch embodiment, instead of all the embodiments.Therefore, it is based on this hair
Embodiment in bright, those of ordinary skill in the art's every other reality obtained without making creative work
Example is applied, should fall within the scope of the present invention.
Unless otherwise specified, in the embodiment of the present invention it is raw materials used be commercially available or those skilled in the art obtained by original
Material；Unless otherwise specified, the conventional method that method therefor is grasped by those skilled in the art in the embodiment of the present invention.
Embodiment 1
Using antimony trichloride and hydrochloric acid as raw material, solid-to-liquid ratio 1kg:3L is mixed to prepare mixed solution, and is passed through into mixed solution
The chlorine of 2 times of moles of antimony trichloride carries out under the conditions of the water of mixed solution and 80 times of parts by volume is blended in 25 DEG C after ventilation
6h is hydrolyzed and be aged, then filters, the crystalline solid filtered is calcined, control calcination temperature is 300 DEG C, calcination time is
5h, calcining heating rate are 5 DEG C/min, the transition state sb oxide that then obtained average grain diameter is about 117nm.To transition state antimony
Oxide is detected, and wherein the molar ratio of Sb (III) and Sb (V) are 0.3:2.
Transition state sb oxide is added with solid-to-liquid ratio 5g:1L into low composition brass electrolyte, is stood under the conditions of 80 DEG C anti-
30min is answered, copper electrolyte is detected.Its copper electrolyte ingredient for purifying front and back is as shown in table 1.
The purification of table 1 front and back copper electrolyte ingredient
Embodiment 2
Using antimony trichloride and hydrochloric acid as raw material, solid-to-liquid ratio 1kg:3L is mixed to prepare mixed solution, and is passed through into mixed solution
The chlorine of 2 times of moles of antimony trichloride carries out under the conditions of the water of mixed solution and 80 times of parts by volume is blended in 25 DEG C after ventilation
6h is hydrolyzed and be aged, then filters, the crystalline solid filtered is calcined, control calcination temperature is 350 DEG C, calcination time is
6h, calcining heating rate are 10 DEG C/min, the transition state sb oxide that then obtained average grain diameter is about 72nm.The present embodiment institute
The TEM of transition state sb oxide obtained schemes as shown in Figure 1, XPS figure is as shown in Figure 2.According to Fig. 1, we can be found that this reality
Transition state sb oxide prepared by example is applied with meso-hole structure extremely abundant, improves its specific surface area.And from Fig. 2 we
It is 0.7:2 that the molar ratio of Sb (III) and Sb (V) in transition state sb oxide, which can be calculated,.
Transition state sb oxide is added with the solid-to-liquid ratio of solid-to-liquid ratio 15g:1L into low composition brass electrolyte, in 25 DEG C of conditions
Under 30min is stirred to react with the revolving speed of 20rpm, copper electrolyte is detected.Its copper electrolyte ingredient for purifying front and back
As shown in table 2.
The purification of table 2 front and back copper electrolyte ingredient
Embodiment 3
Using antimony trichloride and hydrochloric acid as raw material, solid-to-liquid ratio 1kg:3L is mixed to prepare mixed solution, and is passed through into mixed solution
The chlorine of 2 times of moles of antimony trichloride carries out under the conditions of the water of mixed solution and 80 times of parts by volume is blended in 25 DEG C after ventilation
6h is hydrolyzed and be aged, then filters, the crystalline solid filtered is calcined, control calcination temperature is 350 DEG C, calcination time is
6h, calcining heating rate are 5 DEG C/min, the transition state sb oxide that then obtained average grain diameter is about 95nm.
Transition state sb oxide is added with solid-to-liquid ratio 35g:1L into the copper electrolyte of high impurity content, in 60 DEG C of conditions
Lower standing reacts 30min, detects to copper electrolyte.Its copper electrolyte ingredient for purifying front and back is as shown in table 3.Transition state antimony
The molar ratio of Sb (III) and Sb (V) are 0.6:2 in oxide.
Table 3 purification front and back copper electrolyte at
Embodiment 4
Using antimony trichloride and hydrochloric acid as raw material, solid-to-liquid ratio 1kg:3L is mixed to prepare mixed solution, and is passed through into mixed solution
The chlorine of 2 times of moles of antimony trichloride carries out under the conditions of the water of mixed solution and 80 times of parts by volume is blended in 25 DEG C after ventilation
6h is hydrolyzed and be aged, then filters, the crystalline solid filtered is calcined, control calcination temperature is 350 DEG C, calcination time is
5h, calcining heating rate are 5 DEG C/min, the transition state sb oxide that then obtained average grain diameter is about 97nm.To transition state antimony
Oxide is detected, and wherein the molar ratio of Sb (III) and Sb (V) are 0.5:2.
Transition state sb oxide is added with solid-to-liquid ratio 35g:1L into high impurity content copper electrolyte, under the conditions of 60 DEG C
It is stirred to react 30min with the revolving speed of 600rpm, copper electrolyte is detected.Its copper electrolyte ingredient for purifying front and back is such as
Shown in table 4.
The purification of table 4 front and back copper electrolyte ingredient
Embodiment 5
Using antimony trichloride and hydrochloric acid as raw material, solid-to-liquid ratio 1kg:3L is mixed to prepare mixed solution, and is passed through into mixed solution
The chlorine of 2 times of moles of antimony trichloride carries out under the conditions of the water of mixed solution and 80 times of parts by volume is blended in 25 DEG C after ventilation
6h is hydrolyzed and be aged, then filters, the crystalline solid filtered is calcined, control calcination temperature is 350 DEG C, calcination time is
5h, calcining heating rate are 5 DEG C/min, the transition state sb oxide that then obtained average grain diameter is about 96nm.To transition state antimony
Oxide is detected, and wherein the molar ratio of Sb (III) and Sb (V) are 0.8:2.
Transition state sb oxide is added with solid-to-liquid ratio 20g:1L into high impurity content copper electrolyte, under the conditions of 60 DEG C
It is stirred to react 30min with the revolving speed of 20rpm, copper electrolyte is detected.Its copper electrolyte ingredient for purifying front and back is such as
Shown in table 5.
The purification of table 5 front and back copper electrolyte ingredient
From table 1 in above-described embodiment 1~5 to table 5 it will be evident that the method for the present invention is for removing arsenic removal antimony in copper electrolyte
Bismuth has extremely excellent using effect, and copper electrolyte fully meets refining processing of copper electrolysis and prepares wanting for Cu-CATH-1 after purifying
It asks, realizes the step purification of impure copper electrolyte.
Claims (5)
1. going the method for arsenic removal antimony bismuth in a kind of copper electrolyte, which is characterized in that the described method comprises the following steps:
1) transition state sb oxide is added into copper electrolyte；
2) reaction is stirred or stood to copper electrolyte, is filtered to remove sediment after fully reacting.
2. going the method for arsenic removal antimony bismuth in a kind of copper electrolyte according to claim 1, which is characterized in that step 1) is described
Transition state sb oxide is the single-phase sb oxide of the pyrochlore constitution with Sb (III, V) mixed valence.
3. going the method for arsenic removal antimony bismuth in a kind of copper electrolyte according to claim 2, which is characterized in that the transition state
The molar ratio of Sb (III) and Sb (V) are (0.3~0.8) in sb oxide: 2.
4. going the method for arsenic removal antimony bismuth in a kind of copper electrolyte according to claim 1, which is characterized in that step 1) is used
The solid-to-liquid ratio of transition state sb oxide and copper electrolyte are as follows: (5~35) g:1L.
5. going the method for arsenic removal antimony bismuth in a kind of copper electrolyte according to claim 1, which is characterized in that step 2) is described
Reaction temperature is 25~80 DEG C.
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| CN111020634A (en) * | 2019-12-27 | 2020-04-17 | 中南大学 | Method for separating arsenic by copper electrolyte precipitation based on directional crystal form regulation |
| CN113529137A (en) * | 2021-07-16 | 2021-10-22 | 兰溪自立环保科技有限公司 | Copper-nickel-containing waste acid solution treatment and recycling process |
| CN113584324A (en) * | 2020-12-30 | 2021-11-02 | 中南大学 | Method for assisting precipitation of arsenic-containing crystals in copper electrolyte by ultrasonic external field |
| CN114540626A (en) * | 2022-03-22 | 2022-05-27 | 山东恒邦冶炼股份有限公司 | Method for gradient recovery of valuable metals in waste acid by using antimony electrodeposition barren solution |
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