CN110438344A - The method of separation of Cu and Co recycling - Google Patents
The method of separation of Cu and Co recycling Download PDFInfo
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- CN110438344A CN110438344A CN201910769423.2A CN201910769423A CN110438344A CN 110438344 A CN110438344 A CN 110438344A CN 201910769423 A CN201910769423 A CN 201910769423A CN 110438344 A CN110438344 A CN 110438344A
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- cobalt
- copper
- separation
- acidleach
- liquid
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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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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 of separation of Cu and Co recycling.This method comprises: (1) adjusts the pH value of liquid after the acidleach of copper cobalt raw material to 2.5~5；(2) solution that step (1) obtains is mixed with oxidant, to precipitate cobalt oxidation；(3) solution obtained to step (2) is separated by solid-liquid separation, to obtain cobalt precipitating and copper-containing solution.This method is not only easy to operate and safe, low in cost, and can be realized efficiently separating and recycling for copper cobalt.
Description
Technical field
The invention belongs to chemical fields, in particular to the method for separation of Cu and Co recycling.
Background technique
Currently, carrying out copper extraction frequently with acidic leaching when recycling the copper in copper mine or cupric oxide ore and to liquid after leaching
Method, but there are some problems for the recycling of cobalt in copper mine or cupric oxide ore, and cobalt is very low in raw ore content, but in sulfuric acid leaching mistake
Cheng Zhong, with the leaching of copper, cobalt also come out it is very much, therefore after leaching in liquid apart from copper, there is also a small amount of cobalt, Zhi Houkuang
Slurry needs to carry out CCD countercurrent washing, and supernatant enters extraction process recycling copper, and cobalt stays in raffinate when extracting copper
In, and a part of raffinate containing cobalt neutralizes discharge together with CCD underflow, causes cobalt with tail back to process, another part is leached
Slag is lost.Wherein, it since acid leaching solution is that pH value is lower, according to neutralisation Call Provision, not only needs to consume a large amount of neutralizations
Agent also seriously affects liquid after leaching and recycles；And it cannot be returned using rotational-flow electrolysis method since the concentration of cobalt is lower
Receive cobalt.Therefore, the method for separation of Cu and Co recycling is still further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is a kind of method for proposing separation of Cu and Co recycling.This method is not only easy to operate and safe, low in cost, and
It can be realized efficiently separating and recycling for copper cobalt.
The present invention is that the following purpose and discovery based on inventor propose: since the value of cobalt is higher, former to copper cobalt
Material wishes that cobalt also can be recycled sufficiently when being handled.After carrying out acidleach processing to copper cobalt raw material, the cobalt in leachate is usually
Positive divalent, and the cobalt of positive divalent can be oxidized to trivalent cobalt under suitable acid condition and obtain stable precipitating, thus
The pH value of liquid after copper cobalt raw material acidleach, which can be pre-adjusted, precipitates cobalt oxidation to a certain range, then using oxidant, and copper is then
Retain and enter subsequent extraction process in the solution, i.e., is isolated cobalt in advance by the way of oxidation precipitation before copper extraction
Come, on the basis of not influencing water balance, the metal balance of integrated artistic, recycle cobalt, wherein cobalt slag can be using also
The mode Call Provision that original leaches.
For this purpose, according to the first aspect of the invention, a kind of method that the present invention proposes separation of Cu and Co recycling.According to this hair
Bright embodiment, this method comprises:
(1) pH value of liquid after the acidleach of copper cobalt raw material is adjusted to 2.5~5；
(2) solution that step (1) obtains is mixed with oxidant, to precipitate cobalt oxidation；
(3) solution obtained to step (2) is separated by solid-liquid separation, to obtain cobalt precipitating and copper-containing solution.
The method of separation of Cu and Co recycling according to the above embodiment of the present invention, inventors have found that can be directly in acid item
The divalent cobalt oxide in liquid after copper cobalt raw material acidleach is turned into trivalent cobalt under part and forms it into stable precipitating, and extracts it in copper
It is preceding by cobalt precipitation and separation come out individually recycling, if but pH value it is too low, be difficult that divalent cobalt oxide is made to turn to trivalent cobalt, and if pH value mistake
Height, and it is easy to cause the copper precipitating after copper cobalt raw material acidleach in liquid, influence the rate of recovery of copper and the purity of cobalt precipitating.And when in pH
When value is carries out oxidation processes to divalent cobalt under 2.5~5 acid condition, cobalt can be made to be oxidized to trivalent cobalt and form precipitating
And copper does not precipitate, and the precipitating that cobalt is formed can exist in the stable under acidic conditions.This method is not only easy to operate as a result,
And it is safe, low in cost, the effective of copper cobalt can also be realized on the basis of not influencing water balance, the metal balance of integrated artistic
Separation and recycling, significantly reduce the dosage of neutralizer and the acid in copper-containing solution are made to be fully used.
In addition, the method for separation of Cu and Co recycling according to the above embodiment of the present invention can also have following additional technology
Feature:
In some embodiments of the invention, in step (1), liquid is using the concentrated sulfuric acid to institute after the copper cobalt raw material acidleach
Copper cobalt raw material is stated to carry out acidleach processing and be separated by solid-liquid separation to obtain.
In some embodiments of the invention, the pH value of liquid is 0.5~2.0 after the copper cobalt raw material acidleach.
In some embodiments of the invention, the copper cobalt raw material is selected from copper mine, copper cobalt ore, cupric oxide ore, copper-containing substance
At least one of material and copper-bearing waste material.
In some embodiments of the invention, to the copper cobalt raw material carry out acidleach processing when, the concentrated sulfuric acid with it is described
The sour mine ratio of copper cobalt raw material is 100~250Kg/t dry mine, and extraction time is 0.5~4h, and extraction temperature is 20~80 DEG C.
In some embodiments of the invention, in step (1), using described in hydroxide and/or metal oxide adjusting
The pH value of liquid after copper cobalt raw material acidleach.
In some embodiments of the invention, in step (2), the oxidant is selected from sodium peroxydisulfate, potassium permanganate, height
At least one of potassium ferrite and Na2Fe04.
In some embodiments of the invention, in step (2), the use level coefficient of the oxidant is 1~4, preferably 1.2~
2.5, more preferable 1.2~1.8.
In some embodiments of the invention, in step (2), the mixed time is 0.5~4h, and temperature is 20~80
℃。
In some embodiments of the invention, described be separated by solid-liquid separation is realized by filtering or concentrator.
In some embodiments of the invention, separation of Cu and Co recycling method further comprise: (4) to the cobalt precipitate into
The processing of row reducing leaching carries out extraction processing to the copper-containing solution, so that cobalt and copper is separately recovered.
In some embodiments of the invention, in step (4), the reducing leaching processing is to make to restore in acid condition
What agent and cobalt precipitating hybrid reaction were realized.
In some embodiments of the invention, the reducing agent be selected from sodium sulfite, sodium pyrosulfite, sulfur dioxide and
At least one of hydrogen peroxide.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow diagram of separation of Cu and Co recycling according to an embodiment of the invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
According to the first aspect of the invention, a kind of method that the present invention proposes separation of Cu and Co recycling.It is according to the present invention
Embodiment, this method comprises: (1) adjusts the pH value of liquid after the acidleach of copper cobalt raw material to 2.5~5；(2) step (1) is obtained molten
Liquid is mixed with oxidant, to precipitate cobalt oxidation；(3) solution obtained to step (2) is separated by solid-liquid separation, to obtain cobalt
Precipitating and copper-containing solution.Inventors have found that can be directly in acid condition by the divalent cobalt oxide in liquid after copper cobalt raw material acidleach
It turns to trivalent cobalt and forms it into stable precipitating, and cobalt precipitation and separation is come out into individually recycling before copper extraction, if but pH
Be worth too low, be difficult that divalent cobalt oxide is made to turn to trivalent cobalt, and if pH value is excessively high, and be easy to cause the copper after copper cobalt raw material acidleach in liquid
Precipitating influences the rate of recovery of copper and the purity of cobalt precipitating.And divalent cobalt is carried out when in the case where pH value is 2.5~5 acid condition
When oxidation processes, cobalt can be made to be oxidized to trivalent cobalt and form precipitating and copper does not precipitate, and the precipitating that cobalt is formed can be
The stable under acidic conditions exists.This method is not only easy to operate and safe, low in cost as a result, can also do not influence it is whole
Efficiently separating and recycling for copper cobalt is realized on the basis of the water balance of body technology, metal balance, significantly reduces the dosage of neutralizer
And the acid in copper-containing solution is made to be fully used.
It is described in detail below with reference to method of the Fig. 1 to the separation of Cu and Co recycling of the above embodiment of the present invention.
S100: the pH value of liquid after the acidleach of copper cobalt raw material is adjusted to 2.5~5
According to an embodiment of the invention, adjusting the pH value of liquid after the acidleach of copper cobalt raw material to 2.5~5.Inventors have found that working as
When carrying out oxidation processes to divalent cobalt under the acid condition that pH value is 2.5~5, cobalt can be oxidized to trivalent cobalt and be formed sink
It forms sediment, and the precipitating formed can exist in the stable under acidic conditions, so as to realize efficiently separating for copper cobalt.
A specific embodiment according to the present invention, the source of copper cobalt raw material is not particularly restricted in the present invention, ability
Field technique personnel can select according to actual needs.For example, copper cobalt raw material can be the copper-contained material or useless of various grades
Material, such as can be for selected from least one of copper mine, copper cobalt ore, cupric oxide ore, copper-contained material and copper-bearing waste material or other each
The poor cobalt copper raw material of kind.
Another specific embodiment according to the present invention, liquid can use the concentrated sulfuric acid pair after copper cobalt raw material acidleach in the present invention
Copper cobalt raw material carries out acidleach processing and separation of solid and liquid obtains, wherein when carrying out acidleach processing to copper cobalt raw material, the concentrated sulfuric acid and copper cobalt
The sour mine ratio of raw material can be 100~250Kg/t dry mine, preferably 140~200Kg/t dry mine, extraction time can for 0.5~
4h, extraction temperature can be 20~80 DEG C.Inventors have found that needing to control acid adding since copper ore grade containing cobalt oxidation is not high and existing
Within a certain range, if excessive acid adding, the impurity such as iron aluminium leach excessively, subsequent removal of impurities burden can be aggravated, but acid adding is very few again
It is too low to will lead to copper cobalt leaching rate；And if extraction time is too long, equipment scale is too big, and extraction time is too short, and nickel cobalt leaching rate is again
Optimum level is not achieved；If in addition, although extraction temperature is excessively high can to improve leaching kinetics, it is subsequent need it is prolonged
Cooling processing just can enter copper extraction process, if otherwise extraction temperature is too low and to will lead to reaction rate slow, soaked in limiting time
Optimum level is not achieved in extracting rate, and by controlling above-mentioned leaching condition in the present invention, can not only make copper in copper cobalt raw material and
Cobalt leaching rate with higher, can also significantly improve leaching efficiency.Further, the pH value of copper cobalt raw material acidleach terminal can be with
It is 0.5~2.0, i.e., the pH value of liquid can be 0.5~2.0 after the acidleach of copper cobalt raw material, it is possible thereby to further increase copper cobalt raw material
The leaching rate and leaching rate of middle copper and cobalt.In addition, being separated by solid-liquid separation can be realized by filtering or concentrator.
Another specific embodiment according to the present invention can adjust copper cobalt using hydroxide and/or metal oxide
The pH value of liquid after raw material acidleach, suitably to neutralize the acidic environment of liquid after copper cobalt raw material acidleach.Wherein, hydroxide and/or
The type of metal oxide is not particularly restricted, and those skilled in the art can select according to actual needs, for example, can
To adjust pH value using selected from least one of sodium hydroxide, magnesia, calcium oxide, calcium hydroxide and sodium carbonate.
S200: precipitate cobalt oxidation using oxidant
According to an embodiment of the invention, adjust the pH value of liquid after the acidleach of copper cobalt raw material to being mixed after 2.5~5 with oxidant,
To precipitate cobalt oxidation, for example, the pH value of liquid after copper cobalt raw material acidleach can be adjusted to 3.2~4.8 or 3.5~4.5 etc.
It is mixed again with oxidant afterwards.Wherein, for using sodium peroxydisulfate as oxidant, reaction process equation when to cobalt progress oxidation precipitation
Formula is as follows: Na2S2O8+2CoSO4+ 6NaOH=Co2O3+3H2O+4Na2SO4, which needs after copper cobalt raw material acidleach liquid to be added
Oxidant and alkali maintain reaction system pH in above-mentioned level, to make in reaction process cobalt be oxidized precipitating, and copper be retained in it is molten
In liquid, if but pH it is too low, cobalt cannot be substantially oxidized to form precipitating, and it is relatively low to will cause the cobalt rate of recovery, and if pH is excessively high, and can make
At the chemical precipitation of copper, copper content is higher in cobalt slag, and the rate of recovery for causing copper to be united in copper system is relatively low；And when pH value be 3.2~
When carrying out oxidation processes to divalent cobalt under 4.8 or 3.5~4.5 acid condition, it can further be conducive to copper cobalt raw material acidleach
The divalent cobalt in liquid, which is substantially oxidized, afterwards precipitates and avoids generating copper precipitating, so as to further be conducive to separation of Cu and Co and mention
The rate of recovery of high cobalt and copper.
A specific embodiment according to the present invention, the type of oxidant is not particularly restricted in the present invention, this field
Technical staff can select according to actual needs, for example, oxidant can be for selected from sodium peroxydisulfate, potassium permanganate, high-speed rail
At least one of sour potassium and Na2Fe04, it is possible thereby to realize the oxidation precipitation of cobalt, wherein the group of cobalt precipitating becomes the oxygen of cobalt
Compound.
Another specific embodiment according to the present invention, when precipitating cobalt oxidation, the use level coefficient of oxidant can for 1~
4, such as can be 1.2~2.5,1,1.3,1.6,1.9,2.1,2.4,2.7,3,3.3,3.6,3.9 or 4 etc., it needs to illustrate
It is that the use level coefficient of oxidant refers to the actual amount of oxidant and the ratio of theoretical amount.Inventors have found that working as oxidant
Use level coefficient less than 1 when, divalent cobalt cannot be substantially oxidized precipitating, influence the rate of recovery of cobalt；And work as the dosage system of oxidant
When number is greater than 4, it not can be further improved the rate of recovery of cobalt, will increase the cost of oxidant, and too many oxidant instead
Can also degrade subsequent copper extractant, seriously affect the rate of recovery of copper, and the use level coefficient for passing through control oxidant in the present invention is 1
~4, not only cobalt can be made to be substantially oxidized precipitating, and avoid the generation of other contamination precipitations as far as possible, significantly improve returning for cobalt
Yield and quality can also improve the utilization rate of oxidant and significantly reduce the adverse effect that oxidant extracts subsequent copper.It is excellent
Selection of land, the use level coefficient of oxidant can be 1.2~2.5, it is highly preferred that the use level coefficient of oxidant can be 1.2~1.8,
It is possible thereby to further increase the utilization rate of oxidant on the basis of ensuring the cobalt rate of recovery, it is ensured that oxidant is non-degradable subsequent
Copper extractant, achieve the effect that reduce cost of material and improve copper, the cobalt rate of recovery.
Another specific embodiment according to the present invention, it is mixed with oxidant after the pH value of liquid after adjusting copper cobalt raw material acidleach
It closes, the mixed time can be 0.5~4h, and temperature can be 20~80 DEG C, inventors have found that if incorporation time is too long, equipment
Scale is too big, otherwise incorporation time is too short, and optimum level is not achieved again in cobalt oxidation precipitating, and the cobalt rate of recovery is lower；And mixing temperature
Although excessively high can be improved reaction rate, subsequent, the processing that needs to cool down for a long time just can enter copper extraction process, on the contrary
Mixing temperature is too low and will lead to that reaction rate is slow, and optimum level is not achieved in cobalt rate of deposition in limiting time.Pass through in the present invention
Above-mentioned mixing condition is controlled, the divalent cobalt in solution can be made to be substantially oxidized precipitating under the premise of ensuring production efficiency, into
And realize the rate of recovery of copper cobalt efficiently separated and improve cobalt.
S300: separation of solid and liquid obtains cobalt precipitating and copper-containing solution
According to an embodiment of the invention, being separated by solid-liquid separation to the solution that S200 is obtained, to obtain cobalt precipitating and cupric
Solution.Wherein, separation of solid and liquid can be realized by filtering or concentrator.
The method of a specific embodiment according to the present invention, separation of Cu and Co recycling may further include: precipitate to cobalt
Reducing leaching processing is carried out, extraction processing is carried out to copper-containing solution, so that cobalt and copper is separately recovered.Specifically, at reducing leaching
Reason can make reducing agent and cobalt precipitate hybrid reaction to realize in acid condition, wherein the type of reducing agent is not in the present invention
It is particularly limited, those skilled in the art can select according to actual needs, for example, reducing agent can be for selected from sulfurous acid
It is at least one in sodium, sodium pyrosulfite, sulfur dioxide and hydrogen peroxide；Copper-containing solution is back to the acid of copper cobalt raw material after extracting
Property leach, to make the acid in extract liquor be fully used, and significantly reduce the dosage of the concentrated sulfuric acid.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that following
Embodiment is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or item are not specified in embodiment
Part, it described technology or conditions or is carried out according to the literature in the art according to product description.Agents useful for same or instrument
Production firm person is not specified in device, and being can be with conventional products that are commercially available.
Embodiment 1
Acidleach processing is carried out to cupric oxide ore using the concentrated sulfuric acid, sour mine ratio is 150kg/t dry mine, extraction time 2h, temperature
50 DEG C of degree, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 2 institute of table
Show, the pH value of liquid is 1.5 after acidleach.
The ingredient of 1 cupric oxide ore of table
| Element | Cu | Co |
| % | 3 | 0.06 |
The leaching rate of table 2 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 80 | 70 |
After the pH value of liquid after acidleach is adjusted to 3.5 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 1.5, wherein oxidizing temperature is 50 DEG C, oxidization time
For 3h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 85wt%.It should be noted that direct yield is
By what is calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 2
Acidleach processing is carried out to cupric oxide ore using the concentrated sulfuric acid, sour mine ratio is 100kg/t dry mine, extraction time 4h, temperature
40 DEG C of degree, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 3 institute of table
Show, the pH value of liquid is 2.5 after acidleach.
The leaching rate of table 3 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 50 | 30 |
After the pH value of liquid after acidleach is adjusted to 5 with sodium carbonate, be added sodium peroxydisulfate to cobalt carry out oxidation precipitation, process after
Continuous that sodium carbonate maintenance system pH is added, the use level coefficient of sodium peroxydisulfate is 1, wherein oxidizing temperature is 80 DEG C, and oxidization time is
0.5h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 80wt%.It should be noted that direct yield is
By what is calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 3
Using the concentrated sulfuric acid to cupric oxide ore carry out acidleach processing, sour mine ratio be 250kg/t dry mine, extraction time 0.5h,
80 DEG C of temperature, filtering obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 4 institute of table
Show, the pH value of liquid is 1.0 after acidleach.
The leaching rate of table 4 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 87 | 80 |
After the pH value of liquid after acidleach is adjusted to 2.5 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 4, wherein oxidizing temperature is 20 DEG C, and oxidization time is
4h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 67wt%.It should be noted that direct yield be with
It is calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 4
Using the concentrated sulfuric acid to cupric oxide ore carry out acidleach processing, sour mine ratio be 200kg/t dry mine, extraction time 1.5h,
Temperature 60 C, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 5 institute of table
Show, the pH value of liquid is 1.3 after acidleach.
The leaching rate of table 8 bronze medal and cobalt
After the pH value of liquid after acidleach is adjusted to 2.8 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 2.5, wherein oxidizing temperature is 40 DEG C, oxidization time
For 2.5h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 70wt%.It should be noted that direct yield
It is to be calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 5
Acidleach processing is carried out to cupric oxide ore using the concentrated sulfuric acid, sour mine ratio is 175kg/t dry mine, extraction time 3h, temperature
40 DEG C of degree, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 6 institute of table
Show, the pH value of liquid is 1.3 after acidleach.
The leaching rate of table 6 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 83 | 75 |
After the pH value of liquid after acidleach is adjusted to 4.5 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 1.2, wherein oxidizing temperature is 60 DEG C, oxidization time
For 2h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 89wt%.It should be noted that direct yield is
By what is calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 6
Acidleach processing is carried out to cupric oxide ore using the concentrated sulfuric acid, sour mine ratio is 175kg/t dry mine, extraction time 3h, temperature
40 DEG C of degree, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 7 institute of table
Show, the pH value of liquid is 1.3 after acidleach.
The leaching rate of table 7 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 83 | 75 |
After the pH value of liquid after acidleach is adjusted to 4.8 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 1.2, wherein oxidizing temperature is 60 DEG C, oxidization time
For 2h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 93wt%.It should be noted that direct yield is
By what is calculated on the basis of cobalt ions content in liquid after acidleach.
Embodiment 7
Acidleach processing is carried out to cupric oxide ore using the concentrated sulfuric acid, sour mine ratio is 175kg/t dry mine, extraction time 3h, temperature
40 DEG C of degree, filtering, obtains liquid after acidleach, wherein the ingredient of cupric oxide ore is as shown in table 1, the leaching rate of copper and cobalt such as 8 institute of table
Show, the pH value of liquid is 1.3 after acidleach.
The leaching rate of table 8 bronze medal and cobalt
| Element | Cu | Co |
| Leaching rate % | 83 | 75 |
After the pH value of liquid after acidleach is adjusted to 3.2 with sodium carbonate, sodium peroxydisulfate is added, oxidation precipitation, process are carried out to cobalt
Sodium carbonate maintenance system pH is continuously added, the use level coefficient of sodium peroxydisulfate is 2.2, wherein oxidizing temperature is 60 DEG C, oxidization time
For 2h.Filtering obtains cobalt precipitating and copper-containing solution, wherein the direct yield of cobalt is 82wt%.It should be noted that direct yield is
By what is calculated on the basis of cobalt ions content in liquid after acidleach.
Comparative example 1
The difference from embodiment 1 is that sodium peroxydisulfate is added after the pH value of liquid after acidleach is adjusted to 5.5 with sodium carbonate
Oxidation precipitation is carried out to cobalt, wherein the direct yield of cobalt is 95wt%.
Comparative example 2
The difference from embodiment 1 is that sodium peroxydisulfate is added after the pH value of liquid after acidleach is adjusted to 2.2 with sodium carbonate
Oxidation precipitation is carried out to cobalt, wherein the direct yield of cobalt is 50wt%.
Comparative example 3
The difference from embodiment 1 is that the use level coefficient of sodium peroxydisulfate is 5, wherein the direct yield of cobalt is 89wt%.
Extraction and recovery copper, copper are carried out to the copper-containing solution that embodiment 1, comparative example 1 and comparative example 3 obtain under the same conditions
Copper recovery when recovery system recycles copper is distinguished as shown in table 9.
The rate of recovery of 9 bronze medal of table
| Embodiment 1 | Comparative example 1 | Comparative example 3 | |
| Copper recovery (%) | 81 | 74 | 80 |
As a result with conclusion:
In conjunction with the embodiments 1, comparative example 2 is it is found that when carrying out oxidation precipitation to cobalt, and the pH value of solution is too low, the direct yield of cobalt
It declines to a great extent, this illustrates that the divalent cobalt in solution is not substantially oxidized precipitating；And 1, comparative example 1 and table 9 can in conjunction with the embodiments
Know, when carrying out oxidation precipitation to cobalt, if the pH value of solution is excessively high, the recycling rate of recovery of cobalt is significantly improved, but time of copper system system copper
Yield decline, this illustrates in cobalt oxidation precipitation process, and part copper is also precipitated and is mixed into cobalt precipitating；And it combines and implements
Example 1, comparative example 3 and table 9 are it is found that the rate of recovery of copper is substantially suitable in the rate of recovery with embodiment 1 of copper in comparative example 3, but needs
Illustrate, in extraction process, the extractant consumption in comparative example 3 is higher than embodiment 1, this illustrates that excessive oxidant can drop
Solve extractant.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method of separation of Cu and Co recycling characterized by comprising
(1) pH value of liquid after the acidleach of copper cobalt raw material is adjusted to 2.5~5；
(2) solution that step (1) obtains is mixed with oxidant, to precipitate cobalt oxidation；
(3) solution obtained to step (2) is separated by solid-liquid separation, to obtain cobalt precipitating and copper-containing solution.
2. the method for separation of Cu and Co recycling according to claim 1, which is characterized in that in step (1), the copper cobalt raw material
Liquid carries out acidleach processing and is separated by solid-liquid separation to obtain using the concentrated sulfuric acid to the copper cobalt raw material after acidleach,
Optionally, the pH value of liquid is 0.5~2.0 after the copper cobalt raw material acidleach,
Optionally, the copper cobalt raw material be in copper mine, copper cobalt ore, cupric oxide ore, copper-contained material and copper-bearing waste material at least
It is a kind of.
3. the method for separation of Cu and Co recycling according to claim 2, which is characterized in that carry out acidleach to the copper cobalt raw material
When processing, the sour mine ratio of the concentrated sulfuric acid and the copper cobalt raw material is 100~250Kg/t dry mine, and extraction time is 0.5~4h,
Extraction temperature is 20~80 DEG C.
4. the method for separation of Cu and Co recycling according to claim 1 or 3, which is characterized in that in step (1), using hydrogen-oxygen
Compound and/or metal oxide adjust the pH value of liquid after the copper cobalt raw material acidleach.
5. the method for separation of Cu and Co recycling according to claim 4, which is characterized in that in step (2), the oxidant is
Selected from least one of sodium peroxydisulfate, potassium permanganate, potassium ferrate and Na2Fe04.
6. the method for separation of Cu and Co recycling according to claim 1 or 5, which is characterized in that in step (2), the oxidation
The use level coefficient of agent is 1~4, preferably 1.2~2.5, more preferable 1.2~1.8.
7. the method for separation of Cu and Co according to claim 6 recycling, which is characterized in that in step (2), when described mixed
Between be 0.5~4h, temperature be 20~80 DEG C.
8. the method for separation of Cu and Co recycling according to claim 1 or claim 7, which is characterized in that the separation of solid and liquid passed through
Filter or concentrator are realized.
9. the method for separation of Cu and Co recycling according to claim 8, which is characterized in that further comprise:
(4) cobalt is precipitated and carries out reducing leaching processing, extraction processing is carried out to the copper-containing solution, so that cobalt is separately recovered
And copper.
10. the method for separation of Cu and Co recycling according to claim 9, which is characterized in that in step (4), the reduction leaching
Processing is to make reducing agent precipitate hybrid reaction with the cobalt in acid condition to realize out,
Optionally, the reducing agent is selected from least one of sodium sulfite, sodium pyrosulfite, sulfur dioxide and hydrogen peroxide.
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