CN110438344A - The method of separation of Cu and Co recycling - Google Patents

The method of separation of Cu and Co recycling Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
cobalt
copper
separation
acidleach
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910769423.2A
Other languages
Chinese (zh)
Inventor
孙宁磊
刘苏宁
姚心
李诺
刘国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China ENFI Engineering Corp
Original Assignee
China ENFI Engineering Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China ENFI Engineering Corp filed Critical China ENFI Engineering Corp
Priority to CN201910769423.2A priority Critical patent/CN110438344A/en
Publication of CN110438344A publication Critical patent/CN110438344A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0071Leaching or slurrying with acids or salts thereof containing sulfur
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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

The method of separation of Cu and Co recycling
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.
CN201910769423.2A 2019-08-20 2019-08-20 The method of separation of Cu and Co recycling Pending CN110438344A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910769423.2A CN110438344A (en) 2019-08-20 2019-08-20 The method of separation of Cu and Co recycling

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910769423.2A CN110438344A (en) 2019-08-20 2019-08-20 The method of separation of Cu and Co recycling

Publications (1)

Publication Number Publication Date
CN110438344A true CN110438344A (en) 2019-11-12

Family

ID=68436657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910769423.2A Pending CN110438344A (en) 2019-08-20 2019-08-20 The method of separation of Cu and Co recycling

Country Status (1)

Country Link
CN (1) CN110438344A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110898985A (en) * 2019-11-14 2020-03-24 中国恩菲工程技术有限公司 Method for treating copper-cobalt ore
CN110898984A (en) * 2019-11-14 2020-03-24 中国恩菲工程技术有限公司 Method for treating copper-cobalt sulfide ore
CN111961850A (en) * 2020-09-11 2020-11-20 长沙海创金源工程技术有限公司 Treatment method of copper-cobalt ore

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838736A (en) * 2010-06-01 2010-09-22 河南豫光锌业有限公司 Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
US20140023572A1 (en) * 2011-01-25 2014-01-23 The University Of Queensland Method of ore processing
CN105567999A (en) * 2015-12-31 2016-05-11 郴州丰越环保科技有限公司 Method for recycling valuable metal from zinc hydrometallurgy purified cobalt and nickel residues
CN105779777A (en) * 2016-02-29 2016-07-20 河南工信环保科技有限公司 Method for separating and recycling nickel and cobalt from nickel and cobalt slag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838736A (en) * 2010-06-01 2010-09-22 河南豫光锌业有限公司 Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
US20140023572A1 (en) * 2011-01-25 2014-01-23 The University Of Queensland Method of ore processing
CN105567999A (en) * 2015-12-31 2016-05-11 郴州丰越环保科技有限公司 Method for recycling valuable metal from zinc hydrometallurgy purified cobalt and nickel residues
CN105779777A (en) * 2016-02-29 2016-07-20 河南工信环保科技有限公司 Method for separating and recycling nickel and cobalt from nickel and cobalt slag

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘媛媛等: "《提高复杂铜钴矿浸出率的试验研究》", 《有色冶金节能》 *
徐晓辉等: "《氧化沉淀法从稀溶液中分离锌钴》", 《有色金属(冶炼部分)》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110898985A (en) * 2019-11-14 2020-03-24 中国恩菲工程技术有限公司 Method for treating copper-cobalt ore
CN110898984A (en) * 2019-11-14 2020-03-24 中国恩菲工程技术有限公司 Method for treating copper-cobalt sulfide ore
CN111961850A (en) * 2020-09-11 2020-11-20 长沙海创金源工程技术有限公司 Treatment method of copper-cobalt ore

Similar Documents

Publication Publication Date Title
CN110438344A (en) The method of separation of Cu and Co recycling
CA2632923C (en) Method for recovering rare metals in a zinc leaching process
CN107012324B (en) A kind of method and its system recycling main accompanying element from cu-ni sulphide ore
CN101278064B (en) Method for processing nickel bearing raw material in chloride-based leaching
CN102051478B (en) Wet process for treating lead copper matte
CN107058730B (en) A kind of method and its system to cu-ni sulphide ore comprehensive utilization
CN102994747B (en) Technology for recovering metallic copper from high-lead copper matte
EP1412557A2 (en) Process for direct electrowinning of copper
CN103484694A (en) Method for extracting bismuth from copper-bismuth concentrate
US4423011A (en) Selective recovery of base metals and precious metals from ores
CN106521555B (en) A kind of method of antimony electrolyte selectivity iron removaling
CN105177307A (en) Method for recycling copper-nickel-cobalt from low grade nickel matte through abrasive flotation separation
CN102859012B (en) The method of process nickel-bearing raw material
KR20210105406A (en) Method for recovering metal from multimetal nodules
CN105200242B (en) A kind of method that cadmium is reclaimed from containing arsenic refining lead oxygen bottom blown furnace cigarette ash
CN102864305A (en) Separation and purification technology of cobalt-copper alloy lixivium
CN104762483B (en) A kind of method that copper bismuth slag produces copper sulphate
CN109554539A (en) A kind of method of bismuth and copper and iron in pressurized acid leaching separation of Bismuth concentrate
CN106756004A (en) The method of hydrometallurgy
CN100406593C (en) Preparation of zinc chemicals from the minor flow of a process
RU2741429C1 (en) Method and system for complete reprocessing of copper-nickel sulphide ore
CN110079676A (en) A kind of zinc oxide fumes step extract technology rich in germanium
RU2573306C1 (en) Processing method of sulphide pyrrhotine-pentlandite concentrates containing precious metals
AU734903B2 (en) Metal recovery process
CN110117723A (en) A kind of richness germanium zinc oxide fumes leaching method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination