CN106048216A - Method for leaching cobalt out from heterogenite - Google Patents
Method for leaching cobalt out from heterogenite Download PDFInfo
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- CN106048216A CN106048216A CN201610457948.9A CN201610457948A CN106048216A CN 106048216 A CN106048216 A CN 106048216A CN 201610457948 A CN201610457948 A CN 201610457948A CN 106048216 A CN106048216 A CN 106048216A
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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
- 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
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- 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
- C22B23/0423—Halogenated acids or salts thereof
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- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- 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
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- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
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- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
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Abstract
The invention discloses a method for leaching cobalt out from heterogenite. The method includes the ore grinding and mixing step, wherein a heterogenite material is mixed with water for wet grinding, ore pulp is obtained, then vulcanized cobalt slag and the ore pulp are mixed, and a mixed solution is obtained; the leaching-out step, wherein inorganic acid is added to the mixed solution for a reaction, liquid-solid separation is conducted after the reaction is completed, and a leaching-out solution is obtained; the copper extraction and removal step, wherein a copper extraction agent is added to the leaching-out solution for copper extraction and removal, and copper extraction and removal residual liquid is obtained; the impurity extraction and removal step, wherein an impurity removal extraction agent is added to the copper extraction and removal residual liquid for impurity extraction and removal; and the purification step, wherein the solution obtained after impurity extraction is purified, a cobalt chloride solution is obtained, and then cobalt chloride is obtained through evaporative crystallization. By the adoption of the method, the cobalt metal is leached out effectively and selectively from the heterogenite and the vulcanized cobalt slag, consumption of a reducing agent and an oxidizing agent is reduced, the situation that sulfur dioxide gas overflows and contaminates the environment can be avoided as well, and thus the problem that the vulcanized cobalt slag is difficult to treat is solved.
Description
Technical field
The present invention relates to hydrometallurgical processes, a kind of method having particularly related to heterogenite leaching cobalt.
Background technology
Cobalt is important strategy metal element, and Cobalt and compounds of cobalt is widely used in manufacture hard alloy, magnetic material, pottery
And storage battery material etc..Along with both at home and abroad to the growth the most at double of cobalt consumption figure, heterogenite raw material has become production cobalt salt, oxygen
Changing one of primary raw material of the cobalt series of products such as cobalt and electrolytic cobalt, it mainly originates in the country such as the Congo, South Africa, main chemical compositions
Including: CuO 10.2%, Co2O3 8.2%、Fe2O3 6.12%、MgO 4.5%、CaO 1.26%、NiO1.2%、MnO26.8% etc., institute
All exist with oxide form containing metal.Cobalt sulfide slag is then
Raw material production cobalt, nickel, zinc product technological process in P204 extraction and the solution of purification and impurity removal, add sulfuration under certain condition
The waste residue that sodium and precipitation by metallic ion obtain, metal therein mainly exists with CoS, NiS, MnS sulfides form, and metal contains
Amount height differs, the economic worth of product of having purified metals without individual processing, and needs to disappear in the leaching operation processing this product
Consume substantial amounts of oxidant (sodium chlorate, hydrogen peroxide etc.), the danger of production environment will be increased when using combustible and explosive articles sodium chlorate
Dangerous, have become as the common difficulty of many producers.
At present, using heterogenite to produce cobalt product majority and use hydrometallurgical processes, its technological principle is:
1, under atmospheric pressure state, with the presence of reduction reaction effect through reducing agent under conditions of certain acidity, cobalt sesquioxide
It is easier to be reduced into bivalence cobalt and enters in solution (cobalt sulfate solution), enter through the N902 remaining liquid of extraction copper removal → extraction
P204 abstraction impurity removal → P507 extraction cobalt, nickel separation → evaporative crystallization, precipitation of salts or electrolysis obtain highly purified cobalt series and produce
Product；
2, conventional use of mineral acid is sulphuric acid, and reducing agent has sodium sulfite, sodium pyrosulfite, sulfur dioxide, hydrogen sulfide, iron powder
Deng.
The shortcoming of this hydrometallurgical processes is: during reducing leaching, the consumption of reducing agent is often chemical reaction theoretical amount
2-3 times, causing consumption and the waste of reducing agent, increase production cost, if not increasing consumption, cobalt oxide can not reduce completely,
Being difficult to improve the leaching rate of cobalt, and the addition of excessive reductant, the sulfur dioxide of generation is not because participating in mineral timely and effectively
Middle metal reaction, causes sulfur dioxide gas to overflow leaching tanks, and recycling harmful gas uses in sodium carbonate absorption process, no
But the consumption of chemical materials to be increased, and easily cause environment and be contaminated.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of heterogenite leaching cobalt, and it can be effectively realized
Selectively leaching cobalt metal from heterogenite and cobalt sulfide slag, reduces reducing agent and the consumption of oxidant.
The technical problem to be solved is achieved by the following technical programs: the side of a kind of heterogenite leaching cobalt
Method, comprises the following steps:
Ore grinding step: heterogenite material is mixed with water and carries out wet milling, it is thus achieved that ore pulp；
Blend step, then cobalt sulfide slag and ore pulp are mixed, it is thus achieved that mixed liquor；
Leach step: add to mineral acid mixed liquor reacts, carry out solid-liquor separation after having reacted, it is thus achieved that leach molten
Liquid；
Extraction steps for copper removal: add copper extractant at infusion solution and carry out extracting copper removal, it is thus achieved that liquid more than extraction copper removal；
Abstraction impurity removal step: add remove impurity extractant in liquid more than extraction copper removal and carry out extraction removing impurity；
Purification step: by the purified solution after extracting impurities, obtains cobalt chloride solution, then obtains chlorination through evaporative crystallization
Cobalt.
Further, described ore grinding and blend step specifically include: mixed with water 1:3 by volume by heterogenite material and carry out
Wet milling, it is thus achieved that ore pulp, is stirred mixing 1h by weight in the input agitator tank of 3:1 ~ 2 by cobalt sulfide slag and ore pulp, obtains
Obtain mixed liquor.
Further, described pulp granularity is-80 ~-100 mesh, percent of pass 80 ~ 90%.
Further, described leaching step specifically includes: by mozzle by the flow velocity of 100L ~ 120L/min mineral acid
Adding to mixed liquor, being kept stirring for speed is 75～130r/min, and the concentration of initial sulphuric acid is 150 ~ 180g/L, is controlling temperature
Carrying out reacting 7 ~ 12h under conditions of spending 50 ~ 90 DEG C, sample analysis, when in pH=3 ~ 4 and slag of solution, the mass percent of cobalt contains
During amount≤0.1 ~ 0.25%, then stopped reaction, carry out solid-liquor separation through pressure filter, it is thus achieved that infusion solution.
Further, leach in step, be additionally added in steam extremely described mixed liquor.
Further, described extraction steps for copper removal specifically includes: by dense with containing percent by volume for the infusion solution of acquisition
N902 extractant that degree is 25%-30% and sulfonated kerosene that concentration of volume percent is 75%-70% are through hybrid extraction, clarification point
From rear, obtain the first load organic phases；With the sulphuric acid containing 180～220g/L, the first load organic phases is carried out back extraction and obtain sulphuric acid
Liquid more than copper solution and extraction copper removal.
Further, described abstraction impurity removal step specifically includes: will be the P204 of 15%-20% containing concentration of volume percent
Extractant and the sulfonated kerosene that concentration of volume percent is 85%-80% and sodium hydroxide or the quality that mass percent is 8%-10%
Percent concentration is that the ammonia of 6-12% carries out saponification, then with extraction copper removal more than liquid carry out hybrid extraction remove impurity.
Further, described purification step specifically includes: by the solution after abstraction impurity removal and containing percent by volume
Concentration is the P507 extractant of 20%-25% and sulfonated kerosene that concentration of volume percent is 75%-80% and through percent mass
Specific concentration is that the organic facies after the sodium hydroxide of 8%-10% or ammonia saponification that mass percent concentration is 6-12% carries out mixing extraction
Take, respectively obtain the second load organic phases and the remaining liquid of extraction, then with the hydrochloric acid containing 2-2.5mol/L, the second load organic phases is entered
Row back extraction obtains cobalt chloride solution；Cobaltous chloride is obtained through evaporative crystallization.
Further, described mineral acid is sulphuric acid or hydrochloric acid.
There is advantages that ore pulp that heterogenite worn into by the present invention and cobalt sulfide slag mix, reach
Produce sulfur dioxide gas to mix homogeneously and prevention and overflow the purpose of pollution environment；Make full use of oxidized metal thing in heterogenite
Play in acid condition with metal sulphide in cobalt sulfide slag aoxidize → reduce and be reduced → oxidation chemistry reaction effect, subtract
Lack the consumption of reducing agent and oxidant, reduced production cost, the most effectively prevent generation sulfur dioxide gas to overflow dirt
The accident of dye environment occurs；The farthest valuable metal in selective solvent extraction of heterogenite with and cobalt sulfide slag；Solve production
The cobalt sulfide slag that cobalt, nickel, Xin Deng enterprise produce in purification process is not suitable for a difficult problem for individual processing, it is to avoid the wave of resource
Take, it is achieved that resource comprehensive recycles.Further, extract technology is simple, and cost is relatively low, the most easy.
Accompanying drawing explanation
Fig. 1 is the flow chart of the method for heterogenite leaching cobalt of the present invention.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combine mutually, with specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
As it is shown in figure 1, a kind of method that the invention provides heterogenite leaching cobalt, comprise the following steps:
1) ore grinding: by heterogenite material with water by solid: the volume ratio of liquid=1:3 is mixed into ball mill and carries out wet milling, wears into
Ore pulp, it meets granularity-80 ~-100 mesh, the requirement of 80 ~ 90% percent of pass ore pulps；
2) mixing: carry out mixing 1h by weight in the input agitator tank of 3:1 ~ 2 by cobalt sulfide slag and ore pulp, it is thus achieved that mixed liquor, its
Utilize and carry out mixing the principle that chemical reaction does not occurs under conditions of there is no acid, reach mix homogeneously and prevention produces titanium dioxide
The purpose of sulfur gas overflowing；
3) leach: press the flow of 100-120L/min by mozzle and mineral acid is added extremely equipped with in the agitator tank of mixed liquor,
Being kept stirring for speed is 75～130r/min, and initial acidity is 150 ~ 180g/L, is the most preferably improved instead by addition steam
Answer temperature and increase the activity of metal ion, making reaction more abundant；Carry out aoxidizing → going back under conditions of controlling temperature 50 ~ 90 DEG C
Former reaction 7 ~ 12h, after making cobalt and other metals enter solution with ionic condition, sampling detection is analyzed, when solution terminal acidity pH=
3～4 and slag in mass percentage content≤0.1 ~ 0.25% of cobalt time, then stopped reaction, its main chemical reactions formula:
MeS+H2SO4=MeSO4+H2S ↑, (1)
Me2O3+3H2S=2MeS+3H2O+S↓；(2)
Carrying out solid-liquor separation through pressure filter, leached mud, after washing, delivers to Bricks and Tiles Plant's building material product, and infusion solution enters
Next procedure processes；
4) extraction copper removal: the infusion solution obtained after filter pressing passes through with containing the N902 extractant of 30% and the 260# kerosene of 70%
After hybrid extraction, clarified separation, the first load organic phases obtained, organic to the first load with the sulphuric acid containing 180～220g/L
Carry out back extraction mutually to obtain the high copper-bath of purity and be sent directly into cathode copper operation and be electrolysed, be extracted more than copper removal simultaneously
Liquid, its main chemical reactions formula:
Extractive reaction formula: 2RH+Cu2+ = CuR2+2H+, (3)
Back extraction reaction equation: CuR2+H2SO4=CuSO4+ 2RH (4)
Indicate；RH represents N902, CuR2Represent the complex that extractant is formed with copper；
5) abstraction impurity removal: will be 85% containing the P204 extractant that concentration of volume percent is 15% and concentration of volume percent
260# kerosene and mass percent concentration be 10% sodium hydroxide solution carry out saponification, then with extraction copper removal more than liquid mix
Extraction, according to each foreign metal (Fe3+、Mn2+) etc. and Ni2+、Co2+Extraction yield and the pH value of stock solution and extraction order different,
Foreign metal is made to enter organic facies, Ni respectively2+、Co2+Metal ion is stayed in aqueous phase, reaches to remove the mesh of metal impurities
, its main chemical reactions formula (HX represents extractant):
Saponification formula: HX+NaOH=NaX+H2O, (5)
Extractive reaction formula: NaX+CoSO4=CoX2+Na2SO4, (6)
Back extraction reaction equation: CoX2+HCl=CoCl2+2HX；(7)
6) purify: the solution after P204 extracting impurities with containing the P507 extractant that concentration of volume percent is 20%～25%
And sulfonated kerosene that concentration of volume percent is 80%～75% and through sodium hydroxide that mass percent concentration is 8%～10%
Or mass percent concentration be the organic facies after 6-12% ammonia saponification through hybrid extraction, respectively obtain the second load organic phases
Liquid remaining with extraction, then with the hydrochloric acid containing 2～2.5mol/L, the second load organic phases is carried out back extraction and obtain the cobaltous chloride that purity is high
Solution input next procedure, obtains cobaltous chloride product through evaporative crystallization, and (HX represents in its main chemical reactions formula: P507 extraction
Extractant),
Soda soap: HX+NaOH=NaX+H2O, (8)
Extraction: NiX2+Co2+=CoX2+Ni2+, (9)
Back extraction: CoX2+2HCI=CoCl2+ 2HX (10).
Ore pulp and cobalt sulfide slag that heterogenite is worn into by the present invention mix, and reach mix homogeneously and prevention produces dioxy
Change sulfur gas overflowing and pollute the purpose of environment；Make full use of in heterogenite in oxidized metal thing and cobalt sulfide slag metal sulphide in acid
Play under the conditions of property and aoxidize → reduce and be reduced → the effect of oxidation chemistry reaction, decrease disappearing of reducing agent and oxidant
Consumption, reduces production cost, the most effectively prevents the accident producing sulfur dioxide gas spilling pollution environment to occur；Maximum journey
Valuable metal in degree ground selective solvent extraction of heterogenite with and cobalt sulfide slag, wherein the leaching rate of cobalt reaches 99%；Solve production
The cobalt sulfide slag that cobalt, nickel, Xin Deng enterprise produce in purification process is suitable for a difficult problem for individual processing, it is to avoid the waste of resource,
Achieve resource comprehensive to recycle.Extract technology is simple, and cost is relatively low, the most easy.
The specific implementation process of the present invention is further illustrated below by way of several embodiments.
Embodiment 1:
1) ball milling: after being mixed with a certain proportion of water (heterogenite material and water volume ratio 1:3) by heterogenite material, pass through autofeed
Device enters ball mill and carries out wet milling, wears into pulp granularity and reaches-100 mesh, the requirement of 80% percent of pass ore pulp；
2) mixing: ore pulp is put into after carrying out in agitator tank mixing 1h by ore slurry pump and cobalt sulfide slag according to the weight ratio of 3:1,
Make two kinds of former cobalt material mix homogeneously；
3) leach: concentrated sulphuric acid is added to equipped with in the agitator tank of mixed liquor by the flow of 100～120L/min by mozzle,
Being kept stirring for speed is 75 ~ 100r/min, and initial sulfuric acid concentration is 180/L, adds steam and improves reaction temperature, is controlling temperature
Carry out aoxidizing → reduction reaction 8 ~ 10h under conditions of spending 80 ~ 90 DEG C, after making cobalt and other metals enter solution with ionic condition,
Sampling detection is analyzed, when mass percentage content≤0.1% of cobalt in terminal pH value of solution=3～4 and slag, then and stopped reaction；Warp
Crossing pressure filter and carry out solid-liquor separation, leached mud is after washing, and leached mud delivers to Bricks and Tiles Plant's building material product after washing,
Entering next procedure to infusion solution, after measured, infusion solution contains: Co30.2g/L, Cu32.5g/L, Ni1.4g/L, Fe4g/
L、Ca2.1g/L、Mg5.6g/L；
4) extraction copper removal: the infusion solution obtained after filter pressing, is entered and be 30% containing concentration of volume percent by infusion pump
N902 extractant and sulfonated kerosene that concentration of volume percent is 70% after hybrid extraction, clarified separation, respectively obtain
One load organic phases and the remaining liquid of extraction, then with the sulphuric acid containing 180～220g/L, the first load organic phases is carried out back extraction and contained
The copper-bath of Co0.5g/L, Cu45.9g/L, Ni0.003g/L, Fe0.05g/L, Ca0.005g/L, Mg0.008g/L is direct
Being input to electrowinning process be electrolysed, be extracted liquid more than copper removal simultaneously, after measured, more than this extraction copper removal, liquid contains:
Co28.5g/L、Cu0.05g/L、Ni0.1.2g/L、Fe3.8g/L、Ca1.8g/L、Mg4.6g/L；
5) abstraction impurity removal: entering liquid more than extraction copper removal containing concentration of volume percent is P204 extractant and the body of 15% concentration
Long-pending percent concentration is sulfonated kerosene and the having after the sodium hydroxide solution soap that mass percent concentration is 10% of 85%
Machine carries out hybrid extraction mutually, removes foreign metal Fe3+、Mn2+Plasma, obtains raffinate, and after measured, raffinate contains:
Co27.6g/L、Ni0.72g/L；
6) purify: the raffinate after abstraction impurity removal is entered containing P507 extractant and the volume that concentration of volume percent is 20%
Percent concentration is the sulfonated kerosene of 80% and the organic facies after the sodium hydroxide saponification that mass percent concentration is 8% is entered
Row hybrid extraction, clarification, the load organic phases obtained, the hydrochloric acid containing 2.5mol/L is carried out back extraction to the second load organic phases and obtains
To cobalt chloride solution input next procedure, after measured, cobalt chloride solution contains: Co130g/L, Cu0.005g/L,
Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, Mg0.003g/L, cobalt chloride solution obtains cobaltous chloride through evaporative crystallization
Product, the remaining liquid of extraction enters nickel purification process.
Embodiment 2:
1) ball milling: after being mixed with a certain proportion of water (heterogenite material and water volume ratio 1:3) by heterogenite material, pass through autofeed
Device enters ball mill and carries out wet milling, wears into pulp granularity and reaches-100 mesh, the requirement of 80% percent of pass ore pulp；
2) mixing: ore pulp is put into after carrying out in agitator tank mixing 1h by ore slurry pump and cobalt sulfide slag according to the weight ratio of 3:1,
Make two kinds of former cobalt material mix homogeneously；
3) leach: the flow being pressed 100-120L/min by mozzle is added hydrochloric acid to equipped with in the agitator tank of mixed liquor, protects
Holding mixing speed is 75～110r/min, and initial sulfuric acid concentration is 165g/L, carry out aoxidizing under conditions of temperature 50-75 DEG C →
Reduction reaction 8 ~ 10h, after making cobalt and other metals enter solution with ionic condition, sampling detection is analyzed, when terminal solution PH=3
～4 and slag in mass percentage content≤0.2% of cobalt, then stopped reaction, carry out solid-liquor separation, leached mud warp through pressure filter
After crossing washing, delivering to Bricks and Tiles Plant's building material product, the infusion solution obtained enters next procedure, contains after measured in infusion solution
Have: Co29.4g/L, Cu30.5g/L, Ni1.2g/L, Fe3.8g/L, Ca1.9g/L, Mg4.6g/L；
4) extraction copper removal: the infusion solution obtained after filter pressing, is entered and be 30% containing concentration of volume percent by infusion pump
N902 extractant and after sulfonated kerosene that concentration of volume percent is 70% carries out hybrid extraction, clarified separation, respectively obtain
One load organic phases and the remaining liquid of extraction, then with the sulphuric acid containing 180～220g/L, the first load organic phases is carried out back extraction and contained
The copper-bath of Co0.5g/L, Cu50.4g/L, Ni0.004g/L, Fe0.06g/L, Ca0.002g/L, Mg0.01g/L is direct
Be input to electrowinning process be electrolysed, obtain simultaneously containing Co27.2g/L, Cu0.5g/L, Ni0.64g/L, Fe2.8g/L,
Liquid more than the extraction of Ca1.02g/L, Mg3.06g/L；
5) abstraction impurity removal: by extraction copper removal more than liquid enter containing concentration of volume percent be 15% P204 extractant and volume hundred
Proportion by subtraction concentration is the sulfonated kerosene of 85% and the organic facies after the ammonia saponification that mass percent concentration is 10% is mixed
Close extraction, remove foreign metal Fe3+、Mn2+Plasma, the raffinate containing Co24.2g/L, Ni0.68g/L obtained；
6) purify: the raffinate after abstraction impurity removal enters containing P507 extractant and the volume hundred that concentration of volume percent is 20%
Proportion by subtraction concentration is the sulfonated kerosene of 80% and the organic facies after the sodium hydroxide saponification that mass percent concentration is 8% is carried out
Hybrid extraction, clarification, the second load organic phases obtained；With the hydrochloric acid containing 2.5mol/L, the second load organic phases is carried out back extraction
Obtain the cobaltous chloride containing Co135g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, Mg0.003g/L
Solution input next procedure, obtains cobaltous chloride product through evaporative crystallization, and the remaining liquid of extraction enters nickel purification process.
Embodiment 3:
1) ball milling: after being mixed with a certain proportion of water (heterogenite material and water volume ratio 1:3) by heterogenite material, pass through autofeed
Device enters ball mill and carries out wet milling, wears into pulp granularity and reaches-80 mesh, the requirement of 95% percent of pass ore pulp；
2) mixing: ore pulp is put into after carrying out in agitator tank mixing 1h by ore slurry pump and cobalt sulfide slag according to the weight ratio of 3:2,
Make two kinds of former cobalt material mix homogeneously；
3) leach: the flow being pressed 100-120L/min by water conservancy diversion is added concentrated sulphuric acid to equipped with in the agitator tank of mixed liquor, protects
Holding mixing speed is 85～120r/min, and initial sulfuric acid concentration is 150g/L, carry out aoxidizing under conditions of temperature 70-90 DEG C →
Reduction reaction 7-9h, after making cobalt and other metals enter solution with ionic condition, sampling detection is analyzed, as terminal solution acidity PH
=3～4 and slag in mass percentage content≤0.25% of cobalt, then stopped reaction, carry out solid-liquor separation through pressure filter, leach
Slag, after washing, delivers to Bricks and Tiles Plant's building material product, obtains infusion solution and enters next procedure, contains after measured in infusion solution
Have: Co28.6g/L, Cu29.5g/L, Ni1.4g/L, Fe4.0g/L, Ca2.0g/L, Mg4.8g/L；
4) extraction copper removal: the infusion solution obtained after filter pressing, is entered and be 30% containing concentration of volume percent by infusion pump
N902 extractant and after sulfonated kerosene that concentration of volume percent is 70% carries out hybrid extraction, clarified separation, respectively obtain
One load organic phases and the remaining liquid of extraction, then with the sulphuric acid containing 180～220g/L, the first load organic phases is carried out back extraction and contained
The copper-bath of Co0.45g/L, Cu50.8g/L, Ni0.004g/L, Fe0.05g/L, Ca0.002g/L, Mg0.03g/L is direct
Be input to electrowinning process be electrolysed, obtain simultaneously containing Co26.8g/L, Cu0.4g/L, Ni0.74g/L, Fe3.g/L,
Liquid more than the extraction of Ca1.0g/L, Mg3.2g/L；
5) abstraction impurity removal: by extraction copper removal more than liquid enter containing concentration of volume percent be 15% P204 extractant and volume hundred
Proportion by subtraction concentration is the sulfonated kerosene of 85% and the organic facies after the sodium hydroxide saponification that mass percent concentration is 10% is entered
Row hybrid extraction, removes foreign metal Fe3+、Mn2+Plasma, the raffinate containing Co24.5g/L, Ni0.62g/L obtained；
6) purify: the raffinate after P204 extraction deep impurity-removing enters containing the P507 extractant that concentration of volume percent is 20%
And sulfonated kerosene that concentration of volume percent is 80% and having after the sodium hydroxide saponification that mass percent concentration is 8%
Machine carries out hybrid extraction mutually, clarification, the second load organic phases obtained；With the hydrochloric acid containing 2.5mol/L to the second load organic phases
Carry out back extraction to obtain containing Co128g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, Mg0.003g/
The cobalt chloride solution input next procedure of L, obtains cobaltous chloride product through evaporative crystallization, and the remaining liquid of extraction enters nickel purification process.
Embodiment 4:
1) ball milling: after being mixed with a certain proportion of water (heterogenite material and water volume ratio 1:3) by heterogenite material, pass through autofeed
Device enters ball mill and carries out wet milling, wears into pulp granularity and reaches-90 mesh, the requirement of 90% percent of pass ore pulp；
2) mixing: ore pulp is put into after carrying out in agitator tank mixing 1h by ore slurry pump and cobalt sulfide slag according to the weight ratio of 3:1,
Make two kinds of former cobalt material mix homogeneously；
3) leach: press the flow of 100-120L/min by mozzle and concentrated sulphuric acid is added extremely equipped with in the agitator tank of mixed liquor,
Being kept stirring for speed is 90～130r/min, and initial sulfuric acid concentration is 165g/L, adds steam and improves reaction temperature, is controlling
Carry out under conditions of temperature 85-90 DEG C aoxidizing → reduction reaction 7-12h, make cobalt and other metals enter solution with ionic condition
After, sampling detection is analyzed, when mass percentage content≤0.1% of cobalt, then stopped reaction, warp in terminal solution PH=3～4 and slag
Crossing pressure filter and carry out solid-liquor separation, leached mud, after washing, carries out solid-liquor separation through pressure filter, and leached mud is through washing
After, deliver to Bricks and Tiles Plant's building material product, obtain infusion solution and enter next procedure, after measured infusion solution contains:
Co30.8g/L、Cu32.9g/L、Ni1.8g/L、Fe3.8g/L、Ca1.8g/L、Mg4.6g/L；
4) extraction copper removal: the infusion solution obtained after filter pressing, is entered and be 30% containing concentration of volume percent by infusion pump
N902 extractant and sulfonated kerosene that concentration of volume percent is 70% after hybrid extraction, clarified separation, respectively obtain
One load organic phases and the remaining liquid of extraction, then with the sulphuric acid containing 180～220g/L, the first load organic phases is carried out back extraction and contained
The copper-bath of Co0.56g/L, Cu46.9g/L, Ni0.003g/L, Fe0.05g/L, Ca0.005g/L, Mg0.008g/L is straight
Connect and be input to electrowinning process and be electrolysed, obtain simultaneously containing Co29.5g/L, Cu0.04g/L, Ni0.1.0g/L, Fe3.2g/L,
Liquid more than the extraction copper removal of Ca1.2g/L, Mg4.1g/L；
5) abstraction impurity removal: by extraction copper removal more than liquid enter containing concentration of volume percent be 15% P204 extractant and volume hundred
Proportion by subtraction concentration is sulfonated kerosene and the organic facies after the sodium hydroxide solution soap that mass percent concentration is 10% of 85%
Carry out hybrid extraction, remove foreign metal Fe3+、Mn2+Plasma, the raffinate containing Co28.6g/L, Ni0.82g/L obtained；
6) purify: P204 is extracted the raffinate after deep impurity-removing and enters containing the P507 extraction that concentration of volume percent is 20%
Agent and sulfonated kerosene that concentration of volume percent is 80% and after the sodium hydroxide saponification that mass percent concentration is 8%
Organic facies carries out hybrid extraction, clarification, the second load organic phases obtained, and the hydrochloric acid containing 2.5mol/L is organic to the second load
Carry out mutually back extraction obtain containing Co135g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L,
The hydrochloric acid solution input next procedure of Mg0.003g/L, obtains cobaltous chloride product through evaporative crystallization, and the remaining liquid of extraction enters nickel and carries
Pure operation.
The present invention can Selectively leaching cobalt metal from heterogenite and cobalt sulfide slag effectively, decrease reducing agent and oxidation
The consumption of agent, it is to avoid sulfur dioxide gas overflows and pollutes environmental accident generation, solves the problem that cobalt sulfide Slag treatment is difficult, it is achieved that
Resource comprehensive recycles, and extract technology advantages of simple is easy, and cost is relatively low.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (9)
1. the method for a heterogenite leaching cobalt, it is characterised in that comprise the following steps:
Ore grinding step: heterogenite material is mixed with water and carries out wet milling, it is thus achieved that ore pulp；
Blend step, then cobalt sulfide slag and ore pulp are mixed, it is thus achieved that mixed liquor；
Leach step: add to mineral acid mixed liquor reacts, carry out solid-liquor separation after having reacted, it is thus achieved that leach molten
Liquid；
Extraction steps for copper removal: add copper extractant at infusion solution and carry out extracting copper removal, it is thus achieved that liquid more than extraction copper removal；
Abstraction impurity removal step: add remove impurity extractant in liquid more than extraction copper removal and carry out extraction removing impurity；
Purification step: by the purified solution after extracting impurities, obtains cobalt chloride solution, then obtains chlorination through evaporative crystallization
Cobalt.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described ore grinding and blend step are concrete
Including: heterogenite material is mixed with water 1:3 by volume and carries out wet milling, it is thus achieved that ore pulp, cobalt sulfide slag and ore pulp are pressed weight
Measure to put into than 3:1 ~ 2 and agitator tank is stirred mixing 1h, it is thus achieved that mixed liquor.
The method of heterogenite leaching cobalt the most according to claim 1 and 2, it is characterised in that described pulp granularity is-80 ~-
100 mesh, percent of pass 80 ~ 90%.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described leaching step specifically includes:
The flow velocity being pressed 100L ~ 120L/min by mozzle is added mineral acid to mixed liquor, and being kept stirring for speed is 75～130r/
Min, the concentration of initial sulphuric acid is 150 ~ 180g/L, carries out reacting 7 ~ 12h, sampling point under conditions of controlling temperature 50 ~ 90 DEG C
Analysis, when mass percentage content≤0.1 ~ 0.25% of cobalt in pH=3 ~ 4 and slag of solution, then stopped reaction, through pressure filter
Carry out solid-liquor separation, it is thus achieved that infusion solution.
5. according to the method for the heterogenite leaching cobalt described in claim 1 or 4, it is characterised in that leach in step, be additionally added steaming
In vapour extremely described mixed liquor.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described extraction steps for copper removal is specifically wrapped
Include: by the infusion solution of acquisition and containing the N902 extractant that concentration of volume percent is 25%-30% and concentration of volume percent
For the sulfonated kerosene of 75%-70% after hybrid extraction, clarified separation, obtain the first load organic phases；With containing 180～220g/L
Sulphuric acid the first load organic phases is carried out back extraction obtain copper-bath and extraction copper removal more than liquid.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described abstraction impurity removal step is specifically wrapped
Include: will be the sulfonated coal of 85%-80% containing the P204 extractant that concentration of volume percent is 15%-20% and concentration of volume percent
Oil and mass percent are the sodium hydroxide of 8%-10% or ammonia that mass percent concentration is 6-12% carries out saponification, then and extraction
Remove liquid more than copper and carry out hybrid extraction remove impurity.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described purification step specifically includes:
Solution after abstraction impurity removal is dense with containing the P507 extractant that concentration of volume percent is 20%-25% and percent by volume
Sulfonated kerosene that degree is 75%-80% and through sodium hydroxide that mass percent concentration is 8%-10% or mass percent concentration
Carry out hybrid extraction for the organic facies after the ammonia saponification of 6-12%, respectively obtain the second load organic phases and the remaining liquid of extraction, then use
Hydrochloric acid containing 2-2.5mol/L carries out back extraction to the second load organic phases and obtains cobalt chloride solution；Chlorination is obtained through evaporative crystallization
Cobalt.
The method of heterogenite leaching cobalt the most according to claim 1, it is characterised in that described mineral acid is sulphuric acid or salt
Acid.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106435176A (en) * | 2016-11-30 | 2017-02-22 | 沈阳有色金属研究院 | Two-stage selective heterogenite leaching method |
| CN107828975A (en) * | 2017-11-14 | 2018-03-23 | 上海格派新能源技术有限公司 | The technique of Centrifugical extraction copper in a kind of leachate from heterogenite |
| CN108342572A (en) * | 2018-03-20 | 2018-07-31 | 衢州华友钴新材料有限公司 | Using the technique of two-stage extraction method removal of impurities from copper-cobalt mine leachate |
| CN108677009A (en) * | 2018-05-21 | 2018-10-19 | 兰州金川新材料科技股份有限公司 | A kind of depth abstraction impurity removal method of cobalt chloride solution |
| CN110184455A (en) * | 2019-06-20 | 2019-08-30 | 东北大学 | A kind of leaching method of difficult leaching cobalt ore |
| CN110564961A (en) * | 2019-10-14 | 2019-12-13 | 湖南有色金属研究院 | Method for reducing leached hydrocobaltite |
| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN113044889A (en) * | 2021-03-11 | 2021-06-29 | 浙江中金格派锂电产业股份有限公司 | Co-production process of cobalt sulfate and cobalt chloride |
| CN113174493A (en) * | 2021-04-29 | 2021-07-27 | 大冶有色金属有限责任公司 | Method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag |
| CN114959299A (en) * | 2022-05-26 | 2022-08-30 | 重庆康普化学工业股份有限公司 | Method for recovering cobalt from copper extraction raffinate of cobalt-containing copper oxide ore |
| CN116654994A (en) * | 2023-06-08 | 2023-08-29 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt chloride |
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| CN106435176A (en) * | 2016-11-30 | 2017-02-22 | 沈阳有色金属研究院 | Two-stage selective heterogenite leaching method |
| CN107828975A (en) * | 2017-11-14 | 2018-03-23 | 上海格派新能源技术有限公司 | The technique of Centrifugical extraction copper in a kind of leachate from heterogenite |
| CN108342572A (en) * | 2018-03-20 | 2018-07-31 | 衢州华友钴新材料有限公司 | Using the technique of two-stage extraction method removal of impurities from copper-cobalt mine leachate |
| CN108677009A (en) * | 2018-05-21 | 2018-10-19 | 兰州金川新材料科技股份有限公司 | A kind of depth abstraction impurity removal method of cobalt chloride solution |
| CN110184455A (en) * | 2019-06-20 | 2019-08-30 | 东北大学 | A kind of leaching method of difficult leaching cobalt ore |
| CN110564961B (en) * | 2019-10-14 | 2021-08-31 | 湖南有色金属研究院 | Method for reducing leached hydrocobaltite |
| CN110564961A (en) * | 2019-10-14 | 2019-12-13 | 湖南有色金属研究院 | Method for reducing leached hydrocobaltite |
| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN113044889A (en) * | 2021-03-11 | 2021-06-29 | 浙江中金格派锂电产业股份有限公司 | Co-production process of cobalt sulfate and cobalt chloride |
| CN113174493A (en) * | 2021-04-29 | 2021-07-27 | 大冶有色金属有限责任公司 | Method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag |
| CN113174493B (en) * | 2021-04-29 | 2022-07-26 | 大冶有色金属有限责任公司 | Method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag |
| CN114959299A (en) * | 2022-05-26 | 2022-08-30 | 重庆康普化学工业股份有限公司 | Method for recovering cobalt from copper extraction raffinate of cobalt-containing copper oxide ore |
| CN114959299B (en) * | 2022-05-26 | 2023-08-22 | 重庆康普化学工业股份有限公司 | Method for recovering cobalt from copper raffinate of cobalt-containing copper oxide ore |
| CN116654994A (en) * | 2023-06-08 | 2023-08-29 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt chloride |
| CN116654994B (en) * | 2023-06-08 | 2023-11-14 | 科立鑫(珠海)新能源有限公司 | Environment-friendly process for producing cobalt chloride |
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