CN106048216B - The method of heterogenite leaching cobalt - Google Patents

The method of heterogenite leaching cobalt Download PDF

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CN106048216B
CN106048216B CN201610457948.9A CN201610457948A CN106048216B CN 106048216 B CN106048216 B CN 106048216B CN 201610457948 A CN201610457948 A CN 201610457948A CN 106048216 B CN106048216 B CN 106048216B
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extraction
cobalt
heterogenite
leaching
concentration
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CN106048216A (en
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许开华
张云河
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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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
    • 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
    • C22B23/0423—Halogenated 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
    • 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
    • C22B3/04—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
    • 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
    • C22B3/04—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
    • 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
    • C22B3/30—Oximes
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The present invention discloses a kind of method of heterogenite leaching cobalt, including：Ore grinding and mixing step：Heterogenite material is mixed with water and carries out wet milling, obtains ore pulp, then cobalt sulfide slag and ore pulp are mixed, obtains mixed liquor；Leaching step：Inorganic acid is added in mixed liquor and is reacted, solid-liquor separation is carried out after the completion of reaction, obtains infusion solution；Extract steps for copper removal：Copper extractant is added in infusion solution and carries out extraction copper removal, obtains extraction copper removal extraction raffinate；Abstraction impurity removal step：Removal of impurities extractant is added in extracting copper removal extraction raffinate and carries out extraction removing impurity；Purification step：By the purified solution after extracting impurities, cobalt chloride solution is obtained, cobalt chloride is obtained using evaporative crystallization.The present invention effectively Selectively leaching cobalt metal from heterogenite and cobalt sulfide slag, reduces the consumption of reducing agent and oxidant, moreover it is possible to avoid sulfur dioxide gas from overflowing pollution environment, to solve the problems, such as that cobalt sulfide Slag treatment is difficult.

Description

The method of heterogenite leaching cobalt
Technical field
The present invention relates to hydrometallurgical processes, more particularly to a kind of method of 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, ceramics And storage battery material etc..With the growth both at home and abroad to cobalt consumption figure year by year at double, heterogenite raw material has become production cobalt salt, oxygen One of the primary raw material for changing the cobalts series of products such as cobalt and electrolytic cobalt, mainly originates in the countries 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 Exist with oxide form containing metal.And cobalt sulfide slag is then to come to be with heterogenite and processing lateritic nickel ore, zinc oxide etc. Raw material produce cobalt, nickel, zinc product technological process in P204 extraction and purification and impurity removal solution, under certain condition be added vulcanization The waste residue that sodium is obtained with precipitation by metallic ion, metal therein mainly exist in the form of CoS, NiS, MnS sulfides, and metal contains Amount height differs, the economic value for product of having purified metals without independent processing, and needs to disappear in the leaching process for handling the product Consume a large amount of oxidant（Sodium chlorate, hydrogen peroxide etc.), the danger of production environment will be increased when using combustible and explosive articles sodium chlorate It is dangerous, have become the common difficulty of many producers.
Currently, using heterogenite production cobalt product majority using hydrometallurgical processes, technological principle is：
1, it under normal pressure state, is acted on by the reduction reaction of reducing agent under the conditions of having existing for certain acidity, three oxidations Two cobalts, which are easier to be reduced into divalent cobalt, to be entered in solution（Cobalt sulfate solution）, by N902 extract copper removal → extraction extraction raffinate into Enter P204 abstraction impurity removals → P507 extractions cobalt, nickel separation → evaporative crystallization, precipitation of salts or electrolysis and obtains the cobalt series of high-purity Product；
2, conventional use of inorganic acid be sulfuric acid, reducing agent have sodium sulfite, sodium pyrosulfite, sulfur dioxide, hydrogen sulfide, Iron powder etc..
The shortcomings that hydrometallurgical processes is：The dosage of reducing agent often chemically reacts theoretical amount during reducing leaching 2-3 times, the consumption and waste of reducing agent are caused, increases production cost, if not increasing dosage, cobalt oxide cannot restore completely, It is difficult to improve the leaching rate of cobalt, and the addition of excessive reductant, the sulfur dioxide of generation is because cannot timely and effectively participate in mineral Middle metal reaction causes sulfur dioxide gas to overflow leaching tanks, and recovery processing pernicious gas uses in sodium carbonate absorption process, no But increase the consumption of chemical materials, and it is contaminated to be easy to cause environment.
Invention content
The technical problem to be solved by the present invention is to provide a kind of method of heterogenite leaching cobalt, can effectively realize The Selectively leaching cobalt metal from heterogenite and cobalt sulfide slag reduces the consumption of reducing agent and oxidant.
The technical problems to be solved by the invention are achieved by the following technical programs：A kind of side of heterogenite leaching cobalt Method includes the following steps：
Ore grinding step：Heterogenite material is mixed with water and carries out wet milling, obtains ore pulp；
Mixing step, then cobalt sulfide slag and ore pulp are mixed, obtain mixed liquor；
Leaching step：Inorganic acid is added in mixed liquor and is reacted, solid-liquor separation is carried out after the completion of reaction, is leached Solution；
Extract steps for copper removal：Copper extractant is added in infusion solution and carries out extraction copper removal, obtains extraction copper removal extraction raffinate；
Abstraction impurity removal step：Removal of impurities extractant is added in extracting copper removal extraction raffinate and carries out extraction removing impurity；
Purification step：By the purified solution after extracting impurities, cobalt chloride solution is obtained, is obtained using evaporative crystallization Cobalt chloride.
Further, the ore grinding and mixing step specifically include：By heterogenite material and water by volume 1：3 mixing carry out Wet milling obtains ore pulp, by cobalt sulfide slag and ore pulp by weight 3:It is stirred mixing 1h in 1 ~ 2 input stirred tank, is obtained Obtain mixed liquor.
Further, the pulp granularity is -80 ~ -100 mesh, percent of pass 80 ~ 90%.
Further, the leaching step specifically includes：By diversion pipe by the flow velocity of 100L ~ 120L/min inorganic acid It is 75~130r/min to be added to speed in mixed liquor, is kept stirring, and the inorganic acid is sulfuric acid, initial sulfuric acid it is a concentration of 150 ~ 180g/L carries out 7 ~ 12h of reaction, sampling analysis, pH=3 ~ 4 when solution and slag under conditions of controlling 50 ~ 90 DEG C of temperature When mass percentage content≤0.1 of middle cobalt ~ 0.25%, then stop reacting, carries out solid-liquor separation by filter press, leached Solution.
Further, it in leaching step, is additionally added in steam to the mixed liquor.
Further, the extraction steps for copper removal specifically includes：By the infusion solution of acquisition with containing percent by volume it is dense The sulfonated kerosene that the N902 extractants and concentration of volume percent that degree is 25%-30% are 75%-70% is by hybrid extraction, clarification point From rear, the first load organic phases are obtained；It is stripped to obtain sulfuric acid with the first load organic phases of sulfuric acid pair containing 180~220g/L Copper solution and extraction copper removal extraction raffinate.
Further, the abstraction impurity removal step specifically includes：The P204 that concentration of volume percent is 15%-20% will be contained The sodium hydroxide or quality that the sulfonated kerosene that extractant and concentration of volume percent are 85%-80% is 8%-10% with mass percent The ammonium hydroxide that percent concentration is 6-12% carries out saponification, then carries out hybrid extraction removal of impurities with extraction copper removal extraction raffinate.
Further, the purification step specifically includes：By after abstraction impurity removal solution and contain percent by volume The P507 extractants and concentration of volume percent of a concentration of 20%-25% is the sulfonated kerosene of 75%-80% and passes through quality percentage Organic phase after the ammonium hydroxide saponification that the sodium hydroxide or mass percent concentration that specific concentration is 8%-10% are 6-12% carries out mixing extraction Take, respectively obtain the second load organic phases and extraction extraction raffinate, then with the second load organic phases of hydrochloric acid pair containing 2-2.5mol/L into Row back extraction obtains cobalt chloride solution；Cobalt chloride is obtained by evaporative crystallization.
Further, the inorganic acid is sulfuric acid or hydrochloric acid.
The present invention has the advantages that：The present invention mixes the ore pulp that heterogenite is worn into and cobalt sulfide slag, reaches To the purpose for being uniformly mixed and preventing generation sulfur dioxide gas spilling pollution environment；Make full use of oxidized metal object in heterogenite Play the role of oxidation → restore and be reduced → oxidation chemistry reaction in acid condition with metal sulphide in cobalt sulfide slag, subtracts The consumption for having lacked reducing agent and oxidant reduces production cost, while effectively preventing and generating sulfur dioxide gas spilling dirt The accident for contaminating environment occurs；The farthest valuable metal in selective solvent extraction of heterogenite with and cobalt sulfide slag；Solves production The cobalt sulfide slag that cobalt, nickel, Xin Deng enterprises generate in purification process is not suitable for the problem individually handled, avoids the wave of resource Take, realizes resource comprehensive and recycle.Also, extract technology is simple, and cost is relatively low, rationally easy.
Description of the drawings
Fig. 1 is the flow chart of the method for heterogenite leaching cobalt of the present invention.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase It mutually combines, invention is further described in detail in the following with reference to the drawings and specific embodiments.
As shown in Figure 1, the present invention provides a kind of method of heterogenite leaching cobalt, include the following steps：
1）Ore grinding：By heterogenite material and water by solid：Liquid=1：3 volume ratio is mixed into ball mill and carries out wet milling, Ore pulp is worn into, the requirement of granularity -80 ~ -100 mesh, 80 ~ 90% percent of pass ore pulps is met；
2）Mixing：By cobalt sulfide slag and ore pulp by weight 3:Mixing 1h is carried out in 1 ~ 2 input stirred tank, is mixed Liquid is mixed the principle not chemically reacted using under conditions of no acid, is reached and is uniformly mixed and prevents to generate The purpose that sulfur dioxide gas overflows；
3）It leaches：Inorganic acid is added to the stirred tank equipped with mixed liquor by the flow of 100-120L/min by diversion pipe In, it is 75~130r/min to be kept stirring speed, and initial acidity is 150 ~ 180g/L, while preferably being improved by the way that steam is added Reaction temperature and the activity for increasing metal ion, keep reaction more abundant；Carry out aoxidizing under conditions of controlling 50 ~ 90 DEG C of temperature → 7 ~ 12h of reduction reaction, after so that cobalt and other metals is entered solution with ionic condition, sample detection analysis, when solution terminal acidity When mass percentage content≤0.1 of cobalt in pH=3~4 and slag ~ 0.25%, then stop reacting, main chemical reactions formula：
MeS+H2SO4=MeSO4+H2S ↑,（1）
Me2O3+3H2S=2MeS+3H2O+S↓；（2）
Solid-liquor separation is carried out by filter press, leached mud is sent after washing to Bricks and Tiles Plant's building material product, infusion solution It is handled into next procedure；
4）Extract copper removal：The infusion solution obtained after press filtration and the 260# kerosene containing 30% N902 extractants and 70% After hybrid extraction, clarified separation, the first obtained load organic phases are loaded with the sulfuric acid pair first containing 180~220g/L Organic phase, which is stripped to obtain the high copper-bath of purity and is sent directly into electrolysis copper process, to be electrolysed, while being obtained extraction and being removed Copper extraction raffinate, main chemical reactions formula：
Extract reaction equation：2RH+Cu2+ = CuR2+2H+,（3）
It is stripped reaction equation：CuR2+H2SO4=CuSO4+2RH （4）
It indicates；RH indicates N902, CuR2Indicate the complex compound that extractant is formed with copper；
5）Abstraction impurity removal：By be 15% containing concentration of volume percent P204 extractants and concentration of volume percent be 85% 260# kerosene and mass percent concentration be 10% sodium hydroxide solution carry out saponification, then mixed with extraction copper removal extraction raffinate Extraction is closed, according to each foreign metal（Fe3+、Mn2+）Deng with Ni2+、Co2+Extraction yield and stoste pH value and extraction order not Together, foreign metal is made to enter organic phase respectively, Ni2+、Co2+Metal ion stays in water phase, and metal impurities are removed to reach Purpose, main chemical reactions formula（HX indicates extractant）：
Saponification formula：HX+NaOH=NaX+H2O, （5）
Extract reaction equation：NaX+CoSO4=CoX2+Na2SO4,（6）
It is stripped reaction equation：CoX2+HCl=CoCl2+2HX；（7）
6）Purification：Solution after P204 extracting impurities extracts with containing concentration of volume percent for 20%~25% P507 The hydrogen-oxygen for taking the sulfonated kerosene that agent and concentration of volume percent are 80%~75% and being 8%~10% by mass percent concentration Change sodium or mass percent concentration and pass through hybrid extraction for the organic phase after 6-12% ammonium hydroxide saponification, respectively obtaining the second load has Machine phase and extraction extraction raffinate, then be stripped to obtain the high chlorine of purity with the second load organic phases of hydrochloric acid pair containing 2~2.5mol/L Change cobalt liquor and input next procedure, cobalt chloride product, main chemical reactions formula are obtained by evaporative crystallization：P507 is extracted（HX Indicate extractant）,
Soda soap：HX+NaOH=NaX+H2O,（8）
Extraction：NiX2+Co2+=CoX2+Ni2+,（9）
Back extraction：CoX2+2HCI=CoCl2+2HX （10）.
The present invention mixes the ore pulp that heterogenite is worn into and cobalt sulfide slag, reaches and is uniformly mixed and prevents to generate dioxy Change the purpose of sulphur gas overflowing pollution environment；Make full use of in heterogenite in oxidized metal object and cobalt sulfide slag metal sulphide in acid Property under the conditions of play the role of oxidation → restore and be reduced → oxidation chemistry reaction, reduce disappearing for reducing agent and oxidant Consumption reduces production cost, while the accident for generating sulfur dioxide gas spilling pollution environment effectively being prevented to occur；Maximum journey Valuable metal in degree ground selective solvent extraction of heterogenite with and cobalt sulfide slag, the leaching rate of wherein cobalt reach 99%；Solves production The cobalt sulfide slag that cobalt, nickel, Xin Deng enterprises generate in purification process is suitble to the problem individually handled, avoids the waste of resource, Resource comprehensive is realized to recycle.Extract technology is simple, and cost is relatively low, rationally easy.
The specific implementation process further illustrated the present invention below by way of several embodiments.
Embodiment 1：
1）Ball milling：By heterogenite material and a certain proportion of water（Heterogenite material and water volume ratio 1：3）After mixing, by automatic Dispenser enters ball mill and carries out wet milling, wears into the requirement that pulp granularity reaches -100 mesh, 80% percent of pass ore pulp；
2）Mixing：By ore pulp by ore slurry pump and cobalt sulfide slag according to 3:It is mixed in 1 weight ratio input stirred tank After 1h, two kinds of former cobalt material is made to be uniformly mixed；
3）It leaches：The concentrated sulfuric acid is added to the stirring equipped with mixed liquor by the flow of 100~120L/min by diversion pipe In slot, it is 75 ~ 100r/min, a concentration of 180/L of the initial concentrated sulfuric acid to be kept stirring speed, and steam is added to improve reaction temperature Degree carries out aoxidizing → 8 ~ 10h of reduction reaction, makes cobalt and other metals with ionic condition under conditions of controlling 80 ~ 90 DEG C of temperature Into after solution, sample detection analysis, when the mass percentage content of cobalt in terminal pH value of solution=3~4 and slag≤0.1%, then Stop reaction；Solid-liquor separation is carried out by filter press, after washing, leached mud is sent after washing to Bricks and Tiles Plant's system leached mud Building material product obtains infusion solution and enters next procedure, and after measured, infusion solution contains：Co30.2g/L、Cu32.5g/L、 Ni1.4g/L、Fe4g/L、Ca2.1g/L、Mg5.6g/L；
4）Extract copper removal：The infusion solution obtained after press filtration is entered by infusion pump and contains concentration of volume percent The sulfonated kerosene that N902 extractants and concentration of volume percent for 30% are 70% is after hybrid extraction, clarified separation, respectively The first load organic phases and extraction extraction raffinate are obtained, then are stripped with the first load organic phases of sulfuric acid pair containing 180~220g/L It is molten to obtain the copper sulphate containing Co0.5g/L, Cu45.9g/L, Ni0.003g/L, Fe0.05g/L, Ca0.005g/L, Mg0.008g/L Liquid is directly inputted to electrowinning process and is electrolysed, while obtaining extraction copper removal extraction raffinate, and after measured, which contains： Co28.5g/L、Cu0.05g/L、Ni0.1.2g/L、Fe3.8g/L、Ca1.8g/L、Mg4.6g/L；
5）Abstraction impurity removal：Copper removal extraction raffinate will be extracted to enter containing the P204 extractants that concentration of volume percent is 15% concentration And concentration of volume percent be 85% sulfonated kerosene and after the sodium hydroxide solution soap that mass percent concentration is 10% Organic phase carry out hybrid extraction, remove foreign metal Fe3+、Mn2+Plasma obtains raffinate, and after measured, raffinate contains： Co27.6g/L、Ni0.72g/L；
6）Purification：By the raffinate after abstraction impurity removal enter containing concentration of volume percent be 20% P507 extractants and Sulfonated kerosene that concentration of volume percent is 80% and organic after the sodium hydroxide saponification that mass percent concentration is 8% Hybrid extraction, clarification are mutually carried out, obtained load organic phases carry out the second load organic phases of hydrochloric acid pair containing 2.5mol/L anti- Extraction obtains cobalt chloride solution input next procedure and contains in cobalt chloride solution after measured：Co130g/L、Cu0.005g/L、 Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, Mg0.003g/L, cobalt chloride solution obtain cobalt chloride by evaporative crystallization Product, extraction extraction raffinate enter nickel purification process.
Embodiment 2：
1）Ball milling：By heterogenite material and a certain proportion of water（Heterogenite material and water volume ratio 1：3）After mixing, by automatic Dispenser enters ball mill and carries out wet milling, wears into the requirement that pulp granularity reaches -100 mesh, 80% percent of pass ore pulp；
2）Mixing：By ore pulp by ore slurry pump and cobalt sulfide slag according to 3:It is mixed in 1 weight ratio input stirred tank After 1h, two kinds of former cobalt material is made to be uniformly mixed；
3）It leaches：Hydrochloric acid is added to the stirred tank equipped with mixed liquor by the flow of 100-120L/min by diversion pipe In, it is 75~110r/min, a concentration of 165g/L of initial hydrochloric acid to be kept stirring speed, under conditions of 50-75 DEG C of temperature into Row oxidation → 8 ~ 10h of reduction reaction, after so that cobalt and other metals is entered solution with ionic condition, terminal is worked as in sample detection analysis Mass percentage content≤0.2% of cobalt in solution PH=3~4 and slag then stops reacting, and solid-liquor separation is carried out by filter press, Leached mud send the infusion solution obtained to Bricks and Tiles Plant's building material product to enter next procedure after washing, leaches after measured molten Contain in liquid：Co29.4g/L、Cu30.5g/L、Ni1.2g/L、Fe3.8g/L、Ca1.9g/L、Mg4.6g/L；
4）Extract copper removal：The infusion solution obtained after press filtration is entered by infusion pump and contains concentration of volume percent After the sulfonated kerosene that N902 extractants and concentration of volume percent for 30% are 70% carries out hybrid extraction, clarified separation, respectively The first load organic phases and extraction extraction raffinate are obtained, then are stripped with the first load organic phases of sulfuric acid pair containing 180~220g/L It is molten to obtain the copper sulphate containing Co0.5g/L, Cu50.4g/L, Ni0.004g/L, Fe0.06g/L, Ca0.002g/L, Mg0.01g/L Liquid is directly inputted to electrowinning process and is electrolysed, while obtaining containing Co27.2g/L, Cu0.5g/L, Ni0.64g/L, Fe2.8g/ L, the extraction extraction raffinate of Ca1.02g/L, Mg3.06g/L；
5）Abstraction impurity removal：Copper removal extraction raffinate will be extracted to enter the P204 extractants and body that are 15% containing concentration of volume percent Sulfonated kerosene that product percent concentration is 85% and organic phase after the ammonium hydroxide saponification that mass percent concentration is 10% into Row hybrid extraction removes foreign metal Fe3+、Mn2+Plasma, the obtained raffinate containing Co24.2g/L, Ni0.68g/L；
6）Purification：The P507 extractants and body that it is 20% containing concentration of volume percent that raffinate after abstraction impurity removal, which enters, Accumulate the sulfonated kerosene that percent concentration is 80% and the organic phase after the sodium hydroxide saponification that mass percent concentration is 8% Carry out hybrid extraction, clarification, the second obtained load organic phases；It is carried out with the second load organic phases of hydrochloric acid pair containing 2.5mol/L Back extraction obtains the chlorine containing Co135g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, Mg0.003g/L Change cobalt liquor and input next procedure, obtains cobalt chloride product by evaporative crystallization, extraction extraction raffinate enters nickel purification process.
Embodiment 3：
1）Ball milling：By heterogenite material and a certain proportion of water（Heterogenite material and water volume ratio 1：3）After mixing, by automatic Dispenser enters ball mill and carries out wet milling, wears into the requirement that pulp granularity reaches -80 mesh, 95% percent of pass ore pulp；
2）Mixing：By ore pulp by ore slurry pump and cobalt sulfide slag according to 3:It is mixed in 2 weight ratio input stirred tank After 1h, two kinds of former cobalt material is made to be uniformly mixed；
3）It leaches：The concentrated sulfuric acid is added to the stirred tank equipped with mixed liquor by the flow of 100-120L/min by water conservancy diversion In, it is 85~120r/min, a concentration of 150g/L of the initial concentrated sulfuric acid to be kept stirring speed, under conditions of 70-90 DEG C of temperature It carries out aoxidizing → reduction reaction 7-9h, after making cobalt and other metals enter solution with ionic condition, terminal is worked as in sample detection analysis Mass percentage content≤0.25% of cobalt in solution acidity PH=3~4 and slag then stops reacting, and it is solid to carry out liquid by filter press Separation, leached mud send to Bricks and Tiles Plant's building material product after washing, obtain infusion solution and enter next procedure, soak after measured Go out in solution and contains：Co28.6g/L、Cu29.5g/L、Ni1.4g/L、Fe4.0g/L、Ca2.0g/L、Mg4.8g/L；
4）Extract copper removal：The infusion solution obtained after press filtration is entered by infusion pump and contains concentration of volume percent After the sulfonated kerosene that N902 extractants and concentration of volume percent for 30% are 70% carries out hybrid extraction, clarified separation, respectively The first load organic phases and extraction extraction raffinate are obtained, then are stripped with the first load organic phases of sulfuric acid pair containing 180~220g/L It is molten to obtain the copper sulphate containing Co0.45g/L, Cu50.8g/L, Ni0.004g/L, Fe0.05g/L, Ca0.002g/L, Mg0.03g/L Liquid is directly inputted to electrowinning process and is electrolysed, at the same obtain containing Co26.8g/L, Cu0.4g/L, Ni0.74g/L, Fe3.g/L, The extraction extraction raffinate of Ca1.0g/L, Mg3.2g/L；
5）Abstraction impurity removal：Copper removal extraction raffinate will be extracted to enter the P204 extractants and body that are 15% containing concentration of volume percent The product percent concentration sulfonated kerosene that is 85% and organic after the sodium hydroxide saponification that mass percent concentration is 10% Hybrid extraction is mutually carried out, foreign metal Fe is removed3+、Mn2+Plasma, the obtained raffinate containing Co24.5g/L, Ni0.62g/L Liquid；
6）Purification：The P507 that it is 20% containing concentration of volume percent that raffinate after P204 extraction deep impurity-removings, which enters, extracts Take the sulfonated kerosene that agent and concentration of volume percent are 80% and after the sodium hydroxide saponification that mass percent concentration is 8% Organic phase carry out hybrid extraction, clarification, the second obtained load organic phases；Have with the load of hydrochloric acid pair second containing 2.5mol/L Machine be mutually stripped to obtain containing Co128g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, The cobalt chloride solution of Mg0.003g/L inputs next procedure, obtains cobalt chloride product by evaporative crystallization, extraction extraction raffinate enters nickel Purification process.
Embodiment 4：
1）Ball milling：By heterogenite material and a certain proportion of water（Heterogenite material and water volume ratio 1：3）After mixing, by automatic Dispenser enters ball mill and carries out wet milling, wears into the requirement that pulp granularity reaches -90 mesh, 90% percent of pass ore pulp；
2）Mixing：By ore pulp by ore slurry pump and cobalt sulfide slag according to 3:It is mixed in 1 weight ratio input stirred tank After 1h, two kinds of former cobalt material is made to be uniformly mixed；
3）It leaches：The concentrated sulfuric acid is added to the stirred tank equipped with mixed liquor by the flow of 100-120L/min by diversion pipe In, it is 90~130r/min, a concentration of 165g/L of the initial concentrated sulfuric acid to be kept stirring speed, and steam is added to improve reaction temperature Degree carries out aoxidizing → reduction reaction 7-12h, makes cobalt and other metals with ionic condition under conditions of controlling 85-90 DEG C of temperature Into after solution, sample detection analysis when mass percentage content≤0.1% of cobalt in terminal solution PH=3~4 and slag, then stops It only reacts, solid-liquor separation is carried out by filter press, leached mud carries out solid-liquor separation, leached mud after washing, by filter press It after washing, send to Bricks and Tiles Plant's building material product, obtains infusion solution and enter next procedure, contain in infusion solution after measured Have：Co30.8g/L、Cu32.9g/L、Ni1.8g/L、Fe3.8g/L、Ca1.8g/L、Mg4.6g/L；
4）Extract copper removal：The infusion solution obtained after press filtration is entered by infusion pump and contains concentration of volume percent The sulfonated kerosene that N902 extractants and concentration of volume percent for 30% are 70% is after hybrid extraction, clarified separation, respectively The first load organic phases and extraction extraction raffinate are obtained, then are stripped with the first load organic phases of sulfuric acid pair containing 180~220g/L Obtain the copper sulphate containing Co0.56g/L, Cu46.9g/L, Ni0.003g/L, Fe0.05g/L, Ca0.005g/L, Mg0.008g/L Solution is directly inputted to electrowinning process and is electrolysed, at the same obtain containing Co29.5g/L, Cu0.04g/L, Ni0.1.0g/L, The extraction copper removal extraction raffinate of Fe3.2g/L, Ca1.2g/L, Mg4.1g/L；
5）Abstraction impurity removal：Copper removal extraction raffinate will be extracted to enter the P204 extractants and body that are 15% containing concentration of volume percent Accumulate the sulfonated kerosene that percent concentration is 85% and having after the sodium hydroxide solution soap that mass percent concentration is 10% Machine mutually carries out hybrid extraction, removes foreign metal Fe3+、Mn2+Plasma, the obtained raffinate containing Co28.6g/L, Ni0.82g/L Liquid；
6）Purification：P204 is extracted to the raffinate after deep impurity-removing and enters the P507 for being 20% containing concentration of volume percent The sodium hydroxide saponification that the sulfonated kerosene and process mass percent concentration that extractant and concentration of volume percent are 80% are 8% Organic phase afterwards carries out hybrid extraction, clarification, and the second obtained load organic phases load the hydrochloric acid pair second containing 2.5mol/L Organic phase be stripped to obtain containing Co135g/L, Cu0.005g/L, Ni0.003g/L, Fe0.005g/L, Ca0.005g/L, The hydrochloric acid solution of Mg0.003g/L inputs next procedure, obtains cobalt chloride product by evaporative crystallization, extraction extraction raffinate enters nickel and carries Pure process.
The present invention can the effectively Selectively leaching cobalt metal from heterogenite and cobalt sulfide slag, reduce reducing agent and oxidation The consumption of agent avoids sulfur dioxide gas spilling from polluting environmental accident, solves the problems, such as that cobalt sulfide Slag treatment is difficult, realizes Resource comprehensive recycles, and extract technology advantages of simple is easy, and cost is relatively low.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not Therefore it is interpreted as the limitation to the scope of the claims of the present invention, as long as skill obtained in the form of equivalent substitutions or equivalent transformations Art scheme should all be fallen within the scope and spirit of the invention.

Claims (9)

1. a kind of method of heterogenite leaching cobalt, which is characterized in that include the following steps：
Ore grinding step：Heterogenite material is mixed with water and carries out wet milling, obtains ore pulp；
Mixing step, then cobalt sulfide slag and ore pulp are mixed, obtain mixed liquor；
Leaching step：Inorganic acid is added in mixed liquor and is reacted, solid-liquor separation is carried out after the completion of reaction, it is molten to obtain leaching Liquid；
Extract steps for copper removal：Copper extractant is added in infusion solution and carries out extraction copper removal, obtains extraction copper removal extraction raffinate；
Abstraction impurity removal step：Removal of impurities extractant is added in extracting copper removal extraction raffinate and carries out extraction removing impurity；
Purification step：By the purified solution after extracting impurities, cobalt chloride solution is obtained, chlorination is obtained using evaporative crystallization Cobalt.
2. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the ore grinding and mixing step are specific Including：By heterogenite material and water by volume 1：3 mixing carry out wet milling, obtain ore pulp, by cobalt sulfide slag and ore pulp by weight Measure ratio 3:It is stirred mixing 1h in 1~2 input stirred tank, obtains mixed liquor.
3. the method for heterogenite leaching cobalt according to claim 1 or 2, which is characterized in that the pulp granularity is -80 ~-100 mesh, percent of pass 80~90%.
4. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the leaching step specifically includes： Inorganic acid is added into mixed liquor by the flow velocity of 100L~120L/min by diversion pipe, be kept stirring speed be 75~ 130r/min, the inorganic acid are sulfuric acid, a concentration of 150~180g/L of initial sulfuric acid, in the item of 50~90 DEG C of temperature of control Carry out 7~12h of reaction under part, sampling analysis, when mass percentage content≤0.1 of cobalt in pH=3~4 of solution and slag~ When 0.25%, then stop reacting, carries out solid-liquor separation by filter press, obtain infusion solution.
5. the method for heterogenite leaching cobalt according to claim 1 or 4, which is characterized in that in leaching step, be additionally added steaming In vapour to the mixed liquor.
6. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the extraction steps for copper removal is specifically wrapped It includes：The N902 extractants and concentration of volume percent for being 25%~30% by the infusion solution of acquisition and containing concentration of volume percent For 75%~70% sulfonated kerosene after hybrid extraction, clarified separation, obtain the first load organic phases；With containing 180~220g/ The first load organic phases of sulfuric acid pair of L are stripped to obtain copper-bath and extraction copper removal extraction raffinate.
7. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the abstraction impurity removal step is specifically wrapped It includes：The sulfonation for being 85%~80% by the P204 extractants and concentration of volume percent that are 15%~20% containing concentration of volume percent The ammonium hydroxide that the sodium hydroxide or mass percent concentration that kerosene is 8%~10% with mass percent are 6~12% carries out saponification, then Hybrid extraction removal of impurities is carried out with extraction copper removal extraction raffinate.
8. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the purification step specifically includes： By the solution after abstraction impurity removal and the P507 extractants and percent by volume containing concentration of volume percent for 20%~25% The sodium hydroxide or mass percent that a concentration of 75%~80% sulfonated kerosene and process mass percent concentration is 8%~10% Organic phase after a concentration of 6~12% ammonium hydroxide saponification carries out hybrid extraction, respectively obtains more than the second load organic phases and extraction Liquid, then be stripped to obtain cobalt chloride solution with the second load organic phases of hydrochloric acid pair containing 2~2.5mol/L；By evaporative crystallization Obtain cobalt chloride.
9. the method for heterogenite leaching cobalt according to claim 1, which is characterized in that the inorganic acid is sulfuric acid or salt Acid.
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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
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