CN103898327B - A kind of manganese cobalt nickel waste residue extracts the method for nickel - Google Patents
A kind of manganese cobalt nickel waste residue extracts the method for nickel Download PDFInfo
- Publication number
- CN103898327B CN103898327B CN201410032075.8A CN201410032075A CN103898327B CN 103898327 B CN103898327 B CN 103898327B CN 201410032075 A CN201410032075 A CN 201410032075A CN 103898327 B CN103898327 B CN 103898327B
- Authority
- CN
- China
- Prior art keywords
- nickel
- solution
- cobalt
- cobalt nickel
- manganese
- 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.)
- Active
Links
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a kind of method extracting nickel in manganese cobalt nickel waste residue, in turn includes the following steps: a) is added water by the solid-to-liquid ratio of 1:2��5 by manganese cobalt nickel slag and sizes mixing, under agitation heats bubbling, obtain cobalt nickel foam slag and ferromanganese sediment; B) described cobalt nickel foam slag is heated pickling and obtain cobalt nickel filter cake after filtration; C) cobalt nickel solution is obtained after adopting vitriol oil slaking to leach described cobalt nickel filter cake; D) described cobalt nickel solution is carried out removal of impurities, remove copper, iron, calcium, magnesium, manganese and zinc impurity, make impurity mass concentration in solution all drop to below 0.01g/L; E) P507 extraction agent extracting and separating is adopted to go out nickel sulfate solution and cobalt load organic phases the cobalt nickel solution after described removal of impurities; F) described nickel solution is carried out crystallisation by cooling, reclaim(ed) sulfuric acid nickel product. The working condition that the inventive method uses is relatively simple, it is possible to efficiently divide into groups, and the rate of recovery height of nickel.
Description
Technical field
The present invention relates to the extracting method of a heavy metal species, in particular to a kind of method extracting nickel in manganese cobalt nickel waste residue.
Background technology
The important nonferrous metal resource of Gu Nieshi China shortage, south China, especially mostly containing cobalt nickel in the manganese ore in Guangxi.
Adopting the method for hydrometallurgy to produce electrolytic metal Mn, electrolytic manganese dioxide, during the products such as manganous sulfate, the cobalt nickel in manganese ore, will enter into the infusion solution of the first step together with manganese. in the leaching process of manganese ore, when control leaching terminal is pH5��5.4, it is possible to the impurity elements such as the Fe of the overwhelming majority are removed, but Co, Ni still all stay in the solution, it is necessary to reclaimed. deep purifying Co from the leach liquor of manganese ore at present, the method of the impurity elements such as Ni adopts a kind of sequestrant being SDD, it can and Co, many metal element chelates such as Ni, can by the Co in solution, Ni is except to < 0.1ppm, Fe=0.5ppm, but the main body in purification slag or ferromanganese, Co, Ni content is still lower, Ni:1��3%, Co��1wt%, cobalt nickel only has about the 10% of ferromanganese, but the cobalt nickel ore deposit relative to nature, it has been richer cobalt nickel ore deposit, especially China lacks cobalt nickel resources very much, so reclaiming the cobalt nickel that this kind is enriched, it is significant. at present, for the method mainly fire method and wet method of the extraction of manganese cobalt nickel waste residue, owing to fire method needs pyroprocessing waste residue, it is necessary to a large amount of heat, objective condition more complicated, therefore to carry cobalt nickel in widespread attention for wet method. wet method is carried cobalt nickel and be it is generally acknowledged that adopting alkali lye to leach can obtain high leaching yield, but mostly need the pre-treatment such as reduction and high-temperature pressurizing equipment, using acidleach to go out comparable being easier to and obtain higher leaching yield, but selectivity is poor, in waste residue, solvability composition is more is unfavorable for subsequent disposal.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method extracting nickel in manganese cobalt nickel waste residue, working condition is relatively simple, can efficiently divide into groups, and the rate of recovery height of nickel, it is possible to solve in electrolytic manganese production process in the waste residue produced and fail to utilize the problem being caused resource waste and pollution environment containing valency elemental nickel cobalt.
The present invention solves the problems of the technologies described above the technical scheme adopted to be to provide a kind of method extracting nickel in manganese cobalt nickel waste residue, in turn include the following steps: a) manganese cobalt nickel slag is added water by the solid-to-liquid ratio of 1:2��5 and size mixing, under agitation heat bubbling, obtain cobalt nickel foam slag and ferromanganese sediment; B) described cobalt nickel foam slag is heated pickling and obtain cobalt nickel filter cake after filtration; C) cobalt nickel solution is obtained after adopting vitriol oil slaking to leach described cobalt nickel filter cake; D) described cobalt nickel solution is carried out removal of impurities, remove copper, iron, calcium, magnesium, manganese and zinc impurity, make impurity mass concentration in solution all drop to below 0.01g/L; E) P507 extraction agent extracting and separating is adopted to go out nickel sulfate solution and cobalt load organic phases the cobalt nickel solution after described removal of impurities; F) described nickel solution is carried out crystallisation by cooling, reclaim(ed) sulfuric acid nickel product.
Extracting the method for nickel in above-mentioned manganese cobalt nickel waste residue, wherein, described step b) detailed process is as follows: described cobalt nickel foam slag is heated to 80��85 DEG C, with 0.5��2mol/LH2SO4Washing, control PH value in 1.5��2.5 scopes, when PH value reach 2.5 no longer raise at 10��15min time, be washing terminal, after filtration, obtain cobalt nickel filter cake.
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, described step c) detailed process is as follows: by cobalt nickel filter cake (dry base weight): the vitriol oil (volume)=1:0.5��1.5 add vitriol oil slaking, control temperature 150��180 DEG C, 1��2.5 hour time, and then add the water of cobalt nickel filter cake weight 2��3 times, leach 1 hours, obtain cobalt nickel solution.
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, described steps d) removal of impurities comprise the steps: d1) described cobalt nickel solution adopts yellow sodium ferrum vanadium process deironing; D2) described cobalt nickel solution adds NaF and removes calcium or/and magnesium; D3) described cobalt nickel solution adds P204 extraction agent and removes copper, iron, manganese further or/and zinc impurity.
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, described steps d 1) in the processing condition of cobalt nickel solution yellow sodium ferrum vanadium process deironing be: control cobalt nickel solution temperature 92 DEG C, time 4-6h, pH value of solution=2.0 before deironing, pH value of solution=2.5��3.0 after deironing, iron ion mass concentration < 100mg/L, n (NaClO after deironing3)/n(Fe2+)=0.5,n(Na2CO3)/n(Fe2+)=2.0��
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, described steps d 2) in described cobalt nickel solution add NaF remove calcium and magnesium time, cobalt nickel solution PH value controls 5��5.5, and temperature of reaction controls at 95��100 DEG C.
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, the volume fraction of described P204 extraction agent is 15%, comparing Vo: Va is 1: 2, first described P204 extraction agent NaOH solution is carried out saponification before extraction, extraction carries out at 20 DEG C, and aqueous phase solution PH value controls about 3, and the volume ratio of organic phase and aqueous phase is 1: 1.
Above-mentioned manganese cobalt nickel waste residue extracts the method for nickel, wherein, by the saponification deg of 75%, organic phase P204 is carried out saponification by the NaOH solution of 500g/L.
Extracting the method for nickel in above-mentioned manganese cobalt nickel waste residue, wherein, to the organic phase washed with water after extraction, washings and raffinate return in the lump for the P507 extracting and separating nickel sulfate solution in step e) and cobalt load organic phases.
Extracting the method for nickel in above-mentioned manganese cobalt nickel waste residue, wherein, the volume fraction of described P507 extraction agent is 25%, and comparing Vo: Va is 1: 1, and described P507 NaOH solution, about 4, is first carried out saponification before extraction by control solution PH value, and saponification degree is 65%.
The present invention contrasts prior art following useful effect: the method extracting nickel in manganese cobalt nickel waste residue provided by the invention, extracts several big step of cobalt nickel through efficiently grouping, pickling ferromanganese, vitriol oil slaking leaching, deep purifying removal of impurities, extraction; Having following advantage compared to existing technology: 1, adopt vitriol oil slaking lixiviation process to extract cobalt nickel, working condition is relatively simple, and test reagent very generally also easily realizes in the industrial production; 2, efficiently divide into groups, chemical reagent consumption is few: the foamy slag owing to separating only accounts for about 1/3rd of manganese cobalt nickel slag total amount, and Co, Ni of more than 95% are in this foamy slag, only need a small amount of strong acid to leach Co, the Ni in this foamy slag, a lot of chemical reagent material can be saved like this; 3. retrieving cobalt nickel rate height: the present invention adopts grouping acidleach, obtains the solution of high Co, Ni low Mn, Fe, leaches, than overall, the solution obtaining high Mn, Fe low Co, Ni, and the former retrieving cobalt nickel rate is higher than the latter; 4. in manganese cobalt nickel slag, cobalt nickel manganese is all recycled: during pickling cobalt nickel slag, diluted acid only dissolves ferromanganese, oligodynamical nickel, but not dissolved cobalt, ensures that cobalt is not suffered a loss, and micro-Ni loses, and washes out manganese and iron further. Cobalt nickel is recycled in foamy slag, and ferromanganese mainly concentrates in sediment, and the manganese in sediment is easy to leach with dilute sulphuric acid, and iron leaching more difficult than manganese, so manganese also can be recycled.
Accompanying drawing explanation
Fig. 1 is the process flow sheet extracting nickel in the manganese cobalt nickel waste residue in the embodiment of the present invention;
Fig. 2 is the relation schematic diagram of the reaction times used in the embodiment of the present invention in NaF removal of impurities process, NaF consumption and pH value of solution;
Fig. 3 is the relation schematic diagram using nickel, cobalt rate of loss and pH value of solution in NaF removal of impurities process in the embodiment of the present invention;
Fig. 4 is the relation schematic diagram used in the embodiment of the present invention in NaF removal of impurities process between Sodium Fluoride consumption and calcium magnesium decontamination effect improving;
Fig. 5 is the relation schematic diagram adopting nickel cobalt percentage extraction and pH in P507 extraction separation process in the embodiment of the present invention;
Fig. 6 adopts the impact that in P507 extraction separation process, nickel cobalt is extracted by P507 saponification degree in the embodiment of the present invention;
Fig. 7 be the embodiment of the present invention adopts nickel cobalt percentage extraction in P507 extraction separation process with compared with the relation schematic diagram of V0:Va.
Embodiment
Fig. 1 is the process flow sheet extracting nickel in the manganese cobalt nickel waste residue in the embodiment of the present invention.
Refer to Fig. 1, manganese cobalt nickel waste residue provided by the invention extracts the method for nickel, comprises the steps:
Step S1, adds water manganese cobalt nickel slag by the solid-to-liquid ratio of 1:2��5 and sizes mixing, under agitation heat bubbling, obtain cobalt nickel foam slag and ferromanganese sediment; Test-results after the grouping of manganese cobalt nickel slag bubbling sees the following form:
Different from the bonding force of the cobalt each element of nickel ferromanganese according to SDD, adopt the method for efficient grouping, the cobalt nickel by more than 95% is enriched in the cobalt nickel group accounting for weight ratio about 15%, and the ferromanganese of the overwhelming majority is then stayed in the ferromanganese group accounting for weight ratio about 85%.
Step S2: described cobalt nickel foam slag is heated pickling and obtains cobalt nickel filter cake after filtration; Detailed process is as follows: described cobalt nickel foam slag is heated to 80��85 DEG C, with 0.5��2mol/LH2SO4Washing, control PH value in 1.5��2.5 scopes, when PH value reach 2.5 no longer raise at 10��15min time, be washing terminal, after filtration, obtain cobalt nickel filter cake. Cobalt nickel foam slag acid washing test result is as follows:
Therefore, by pickling, reducing further the ferromanganese in cobalt nickel group and enriched in cobalt nickel, at this moment, the content of cobalt and nickel in cobalt nickel slag has been more than 10 times of ferromanganese, and the quantity of slag only the former manganese cobalt quantity of slag about 10%.
Step S3: obtain cobalt nickel solution after adopting vitriol oil slaking to leach described cobalt nickel filter cake; Detailed process is as follows: by cobalt nickel filter cake (dry base weight): the vitriol oil (volume)=1:0.5��1.5 add vitriol oil slaking, control temperature 150��180 DEG C, 1��2.5 hour time, and then add the water of cobalt nickel filter cake weight 2��3 times, leach 1 hours, make Co, Ni, Cu, Zn etc. are transferred in solution, obtain cobalt nickel solution.
Described cobalt nickel filter cake is carried out vitriol oil slaking leaching, now soaks slag yield��30%, that is, leach the quantity of slag only former manganese cobalt slag about 3%, and to leach slag containing cobalt nickel be 0.02��0.05%. So it is very micro-by the cobalt nickel leaching slag loss.
Step S4: described cobalt nickel solution is carried out removal of impurities, removes the impurity such as copper, iron, calcium, magnesium, manganese and zinc, makes impurity mass concentration in solution all drop to below 0.01g/L; Removal of impurities in this step mainly comprises the steps:
S401: described cobalt nickel solution is adopted yellow sodium ferrum vanadium process deironing; The processing condition of yellow sodium ferrum vanadium process deironing are: control cobalt nickel solution temperature 92 DEG C, time 4-6h, pH value of solution=2.0 before deironing, pH value of solution=2.5��3.0 after deironing, iron ion mass concentration < 100mg/L, n (NaClO after deironing3)/n(Fe2+)=0.5,n(Na2CO3)/n(Fe2+)=2.0��
Sodium jarosite [Na2Fe6 (SO4) 4 (OH) 12] is yolk yellow crystal, is a kind of filterableness, good compound vitriol of detergency. When iron ion in solution exists at comparatively high temps (being greater than 90 DEG C), enough sodium ions and sulfate ion, a certain amount of crystal seed exists, pH is suitable, namely generate sodium jarosite. The reaction generating sodium jarosite is very complicated, is mainly reflected as:
3Fe2(SO4)4+Na2SO4+12H2O=Na2Fe6(SO4)4(OH)12��+6H2SO4
Na reaction have sulfuric acid generate, so need to be adopted2CO3Neutralization, to control the Optimal pH that sodium jarosite generates. Through test, the optimum process condition of yellow modumite method deironing is: temperature 92 DEG C, time 5h, pH value of solution=2.0 before deironing, pH value of solution=2.5��3.0 after deironing, iron ion mass concentration < 100mg/L, n (NaClO after deironing3)/n(Fe2+)=0.5,n(Na2CO3)/n(Fe2+)=2.0. Deironing is forward and backward, and in solution, each mass of ion concentration sees the following form.
It may be seen that yellow modumite method can effectively remove the iron ion in solution, iron clearance reaches 99%, and the rate of loss of valuable metal cobalt, nickel extremely low (being all less than 1%).
Step S402: adding NaF at described cobalt nickel solution and remove calcium and magnesium, cobalt nickel solution PH value controls 5��5.5, and temperature of reaction controls at 95��100 DEG C, and in the present embodiment, the consumption of NaF is 3g. The principle of Sodium Fluoride removal calcium, magnesium is very simple. Ca in Sodium Fluoride and solution2+And Mg2+There is chemical reaction, generate difficult molten Calcium Fluoride (Fluorspan), magnesium fluoride precipitation. Reaction formula is as follows:
2NaF+Ca2+=CaF2��+2Na+,
2NaF+Mg2+=MgF2��+2Na+��
1, the impact of pH value
PH value of solution affects the main factor that Sodium Fluoride removes calcium, magnesium. Test shows, when pH value of solution, < when 5.0, reducing with pH, Sodium Fluoride consumption sharply increases, and the reaction times obviously extends. Particularly when in solution, calcium-magnesium content sum is more than 0.1%, Sodium Fluoride consumption increases several times, even tens times; Reaction times is then increased to more than 9h (see Fig. 2) by original 20min. Meanwhile, pH value of solution is again the important factor in order that single nickel salt, rose vitriol are converted into precipitation of hydroxide, when pH value of solution is more than 6.0, there will be suspended particle in system, and the nickel in calcium magnesium slag after filtering, cobalt contents also can rapid rise (see Fig. 3). According to Fig. 2��3, comprehensive each influence factor, with NaF except pH when Ca, Mg is relatively more reasonable to control between 5��5.5.
2, the impact of temperature
Temperature of reaction on calcium magnesium purification and Calcium Fluoride (Fluorspan), magnesium fluoride slag strainability have bigger impact. Temperature raises the dissolving being conducive to solid Sodium Fluoride, accelerate speed of reaction, Reaction time shorten also improves the press filtration performance of Calcium Fluoride (Fluorspan), magnesium fluoride slag, but temperature is too high, energy consumption increases, simultaneous reactions process causes single nickel salt crystalline deposit owing to steam output is big and has unnecessary Sodium Fluoride to precipitate out, thus cause insolubles content in single nickel salt product to exceed standard. Temperature is too low, and Calcium Fluoride (Fluorspan), magnesium fluoride are easily cementing, and its absorbed Ni, cobalt ability increase rapidly, and difficulty in filtration also increases sharply. Test shows, it is relatively more reasonable that temperature of reaction controls between 95��100 DEG C.
3, the impact of NaF consumption
Sodium Fluoride is the reactive material participating in removal of impurities directly, and from reaction kinetics angle, the concentration of reactant and the size of surface-area all may affect the speed of reaction of heterogeneous reaction; Chemically balancing angle, the ratio of reactant consumption can affect equilibrium conversion. Therefore, if Sodium Fluoride consumption is not enough, then impurity cannot Ex-all; But if Sodium Fluoride consumption is too much, causes again waste, but also the calcium magnesium quantity of slag can be made to increase, nickel, cobalt number of dropouts strengthen. Fig. 4 is the relation schematic diagram between Sodium Fluoride consumption and calcium magnesium purification rate, and as seen from Figure 4, in the present embodiment, Sodium Fluoride consumption reaches more than 95% at about 3.0g, calcium, magnesium purification rate.
Step S403: described cobalt nickel solution adds P204 extraction agent and removes copper, iron, manganese further or/and impurity such as zinc. Containing cobalt nickel solution after aforesaid method removal of impurities, wherein also containing impurity such as the iron of trace and zinc, copper, manganese, calcium, it is necessary to purify further. The present embodiment adopts P204 solvent extration deep impurity-removing matter. P204 is a kind of acidic phosphorus extractant, and the process of its extracting metals ion belongs to base exchange process. P204 extracts the order of each metal ion species in an acidic solution: Fe3+>Zn2+>Cu2+>Fe2+>Mn2+>Co2+>Ni2+>Mg2+>Ca2+, control suitable acidity condition, Fe can be made3+��Zn2+��Cu2+��Mn2+��Ca2+Enter organic phase Deng impurity, thus realize removal of impurities. For maintaining the pH of extraction process, need before extraction first by P204 NaOH saponification. Extraction carries out at 20 DEG C, and the volume fraction that the volume ratio of organic phase and aqueous phase is 1: 1, P204 extraction agent is 15%, and comparing Vo: Va is 1: 2.
1, P2O4 volume fraction is on the impact of abstraction impurity removal effect
Following table be in organic phase P2O4 volume fraction on the impact of abstraction impurity removal effect
As can be seen from the above table, when in organic phase, �� (P204) is 20%, the effect of extracting of the impurity such as Cu, Mn is better, but the extraction of cobalt, nickel is also increased. Test determines that the volume fraction of P204 is 15%.
2, the impact of removal of impurities is compared
With 15%P2042 kerosin, at room temperature extracting, compare (Vo: Va, throughput ratio) more big, impurity-eliminating effect is more good, but also corresponding increase and the increase of organic phase consumption of the extraction quantity of cobalt, nickel. Find out from following table, select Vo: Va to be 1: 2 proper.
3, aqueous pH values is on the impact of removal of impurities
Following table is for comparing 1: 2, under extraction agent volume fraction 15% condition, aqueous phase solution pH value is on the impact of removal of impurities. It may be seen that the pH of the effect of extracting of impurity and solution is closely related. When pH is higher, the extraction quantity of metal ion is relatively big, but the extraction quantity of cobalt, nickel also increases, so, pH is about 3.0 comparatively suitable.
In test, by the saponification deg of 75%, organic phase is carried out saponification by the NaOH solution of 500g/L. In order to improve nickel, the cobalt rate of recovery, reducing loss, to the organic phase washed with water after extraction, washings and raffinate return in the lump for the P507 extraction of nickel in step S5, cobalt.
Step S5: adopt P507 extraction agent extracting and separating to go out nickel sulfate solution and cobalt load organic phases the cobalt nickel solution after described removal of impurities; P507 is a kind of acidic organophosphorus extractant, and some metal ion is had good extraction ability. The extraction order of each metal ion species is by P507: Fe3+>Zn2+>Cu2+��Mn2+��Ca2+>Co2+>Mg2+>Ni2+, therefore can realize effective separation of Ni, Co under certain pH value. The same with P204, P507 also needs saponification in advance before use. With P507 extracting and separating nickel cobalt, its volume fraction is generally 25%, in addition, and paper examines material liquid pH value, saponification degree and compare the impact of nickel cobalt percentage extraction. Comparing of the extraction agent of P507 described in the present embodiment Vo: Va is 1: 1, and described P507 NaOH solution, about 4, is first carried out saponification before extraction by control solution PH value, and saponification degree is 65%.
1, pH value of solution is on the impact of nickel, cobalt extraction
Under room temperature, P507 volume fraction is 25%, and saponification degree is 65%, Vo: Va is 1: 1, uses NiCO3Powder adjusts solution ph, and vibration 1min, the impact of Ni, Co percentage extraction is referred to Fig. 5 by pH value of solution.
As seen from Figure 5, as pH=4.0, nickel is minimum to the amount of organic phase by common extraction, and the separating factor of cobalt and nickel is maximum, is 302.
2, the impact that nickel cobalt is extracted by P507 saponification degree
Work as Co2+After being extracted by P507, aqueous phase pH reduces. Reduce the impact on metal ion percentage extraction for reducing aqueous phase pH, first by part extraction agent NaOH solution saponification, and then need to extract. Under room temperature, pH value of solution=4.0, Vo: Va=1: 1, �� (P507)=25%, extraction vibration 1min, refers to Fig. 6, and result shows, extraction agent saponification degree is in 30%��70% scope, nickel percentage extraction is without considerable change, and all below 6.5%, and cobalt percentage extraction is all more than 60%; When saponification degree is 65%, cobalt percentage extraction is greater than 90%.
3, Vo: Va on the impact of nickel cobalt extracting and separating
Under room temperature, fixing material liquid pH=4.0, �� (P507)=25%, organic phase saponification degree 65%, changes Vo: Va, and vibration 1min, test-results please participate in Fig. 7.
It may be seen that compare more big, the percentage extraction of cobalt is more high, and the percentage extraction of nickel does not have considerable change. In order to reduce extraction progression, simplification of flowsheet, choosing Vo: Va is 1: 1.
Step S6: described nickel solution is carried out crystallisation by cooling, reclaim(ed) sulfuric acid nickel product.
The sulfuric acid of the organic phase 5.0mol/L of load cobalt is stripped, obtains the cobalt sulfate solution (stripping rate 99.5%) of 72g/L; By concentrated for nickel sulfate solution heating, then crystallisation by cooling at 30 DEG C, obtains with NiSO4��7H2O be main, containing part Ni2SO4��6H2The crystal single nickel salt product of O.
Although the present invention discloses as above with better embodiment; so itself and be not used to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little amendment and perfect, therefore protection scope of the present invention is when with being as the criterion that claim book defines.
Claims (5)
1. a manganese cobalt nickel waste residue extracts the method for nickel, it is characterised in that in turn include the following steps:
A) manganese cobalt nickel slag is added water by the solid-to-liquid ratio of 1:2��5 size mixing, under agitation heat bubbling, obtain cobalt nickel foam slag and ferromanganese sediment;
B) described cobalt nickel foam slag is heated pickling and obtain cobalt nickel filter cake after filtration;
C) cobalt nickel solution is obtained after adopting vitriol oil slaking to leach described cobalt nickel filter cake;
D) described cobalt nickel solution is carried out removal of impurities, remove copper, iron, calcium, magnesium, manganese and zinc impurity, make impurity mass concentration in solution all drop to below 0.01g/L; Described removal of impurities comprises the steps: d1) the employing yellow sodium ferrum vanadium process deironing of described cobalt nickel solution, control cobalt nickel solution temperature 92 DEG C, time 4-6h, pH value of solution=2.0 before deironing, pH value of solution=2.5��3.0 after deironing, iron ion mass concentration < 100mg/L, n (NaClO after deironing3)/n(Fe2+)=0.5, n (Na2CO3)/n(Fe2+)=2.0; D2) described cobalt nickel solution adds NaF removing calcium or/and magnesium, and cobalt nickel solution PH value controls 5��5.5, and temperature of reaction controls at 95��100 DEG C; D3) described cobalt nickel solution adds P204 extraction agent and removes copper, iron, manganese further or/and zinc impurity; The volume fraction of described P204 extraction agent is 15%, and comparing Vo: Va is 1: 2, first described P204 extraction agent NaOH solution is carried out saponification before extraction, and extraction carries out at 20 DEG C, and aqueous phase solution PH value controls about 3;
E) P507 extraction agent extracting and separating is adopted to go out nickel sulfate solution and cobalt load organic phases the cobalt nickel solution after described removal of impurities; To the organic phase washed with water after extraction, washings returns in the lump with raffinate and is separated nickel sulfate solution and cobalt load organic phases with P507 cycling extraction;
F) described nickel sulfate solution is carried out crystallisation by cooling, reclaim(ed) sulfuric acid nickel product: stripped by the sulfuric acid of the organic phase 5.0mol/L of load cobalt, obtain the cobalt sulfate solution of 72g/L; By concentrated for nickel sulfate solution heating, then crystallisation by cooling at 30 DEG C, obtains containing NiSO4��7H2O and Ni2SO4��6H2The crystal single nickel salt product of O.
2. manganese cobalt nickel waste residue according to claim 1 extracts the method for nickel, it is characterised in that, described step b) detailed process is as follows: described cobalt nickel foam slag is heated to 80��85 DEG C, with 0.5��2mol/LH2SO4Washing, control ph in 1.5��2.5 scopes, when pH value reach 2.5 no longer raise at 10��15min time, be washing terminal, after filtration, obtain cobalt nickel filter cake.
3. manganese cobalt nickel waste residue according to claim 1 extracts the method for nickel, it is characterized in that, described step c) detailed process is as follows: by cobalt nickel filter cake in dry base weight: the vitriol oil by volume=1:0.5��1.5 add vitriol oil slaking, control temperature 150��180 DEG C, 1��2.5 hour time, and then add the water of cobalt nickel filter cake weight 2��3 times, leach 1 hours, obtain cobalt nickel solution.
4. manganese cobalt nickel waste residue according to claim 1 extracts the method for nickel, it is characterised in that, by the saponification deg of 75%, organic phase P204 is carried out saponification by the NaOH solution of 500g/L.
5. manganese cobalt nickel waste residue according to claim 1 extracts the method for nickel, it is characterised in that, the volume fraction of described P507 extraction agent is 25%, comparing Vo: Va is 1: 1, described P507 NaOH solution, about 4, is first carried out saponification before extraction by control solution PH value, and saponification degree is 65%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410032075.8A CN103898327B (en) | 2014-01-23 | 2014-01-23 | A kind of manganese cobalt nickel waste residue extracts the method for nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410032075.8A CN103898327B (en) | 2014-01-23 | 2014-01-23 | A kind of manganese cobalt nickel waste residue extracts the method for nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103898327A CN103898327A (en) | 2014-07-02 |
| CN103898327B true CN103898327B (en) | 2016-06-01 |
Family
ID=50989891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410032075.8A Active CN103898327B (en) | 2014-01-23 | 2014-01-23 | A kind of manganese cobalt nickel waste residue extracts the method for nickel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103898327B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629033A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering cobalt and nickel from tungsten waste smelting slag |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108004419B (en) * | 2017-12-05 | 2019-07-09 | 华中科技大学 | A kind of cobalt nickel extraction separating method reducing coextraction |
| CN110699553B (en) * | 2019-11-01 | 2021-02-12 | 广西科技师范学院 | Method for leaching, recovering and separating nickel from manganese-sulfur purification waste residue |
| CN110760680B (en) * | 2019-11-01 | 2021-05-11 | 广西科技师范学院 | Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue |
| CN112522512B (en) * | 2020-11-12 | 2022-09-30 | 四川顺应动力电池材料有限公司 | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| CN113416857A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for selectively extracting cobalt and nickel from nickel sulfide concentrate |
| CN117107071B (en) * | 2023-10-19 | 2024-02-06 | 中国恩菲工程技术有限公司 | Method for treating nickel-cobalt-containing material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073416A1 (en) * | 2004-01-28 | 2005-08-11 | Commonwealth Scientific And Industrial Research Organisation | Solvent extraction process for separating cobalt and/or nickel from impurities in leach solutions. |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN102041381A (en) * | 2011-01-17 | 2011-05-04 | 河南永通镍业有限公司 | Method for recovering nickel, cobalt, iron, manganese and magnesium from oxidized nickel ore |
| CN102234721A (en) * | 2011-06-15 | 2011-11-09 | 金川集团有限公司 | Treatment method of nickel-cobalt material |
-
2014
- 2014-01-23 CN CN201410032075.8A patent/CN103898327B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073416A1 (en) * | 2004-01-28 | 2005-08-11 | Commonwealth Scientific And Industrial Research Organisation | Solvent extraction process for separating cobalt and/or nickel from impurities in leach solutions. |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN102041381A (en) * | 2011-01-17 | 2011-05-04 | 河南永通镍业有限公司 | Method for recovering nickel, cobalt, iron, manganese and magnesium from oxidized nickel ore |
| CN102234721A (en) * | 2011-06-15 | 2011-11-09 | 金川集团有限公司 | Treatment method of nickel-cobalt material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629033A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering cobalt and nickel from tungsten waste smelting slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103898327A (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103773961B (en) | The method of cobalt and nickel is extracted in a kind of manganese cobalt nickel waste residue | |
| CN103898328B (en) | The method of cobalt is extracted in a kind of manganese cobalt nickel waste residue | |
| CN103898327B (en) | A kind of manganese cobalt nickel waste residue extracts the method for nickel | |
| CN101838736B (en) | Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system | |
| CN102244309B (en) | Method for recovering lithium from lithium power battery of electric automobile | |
| CN102851693B (en) | Technology for recovering production of electrolytic copper and zinc from smelting ash | |
| WO2018076993A1 (en) | Method for preparing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate, and tricobalt tetroxide from battery waste | |
| CN104659438B (en) | A kind of method that utilization refuse battery prepares ternary anode material precursor | |
| CN101974687B (en) | Extraction process for preparing electronic-grade cobalt sulfate from cobalt-containing waste material | |
| CN102140582B (en) | Method for preparing manganese sulfate from leaching slag of electrolytic manganese metal | |
| CN102181666A (en) | Method for treating red soil nickel ore leaching liquid | |
| CN105087935B (en) | The method of copper, indium and gallium is separately recovered in a kind of gallium waste target from copper and indium | |
| CN103290224A (en) | Recovery process for valuable metals in tungsten residues | |
| CN104745823A (en) | Method for recycling lithium from waste lithium ion battery | |
| CN1786225A (en) | Wet treatment method of iron containing nickel sulfide material | |
| CN105296753A (en) | Method for separating cobalt, nickel and magnesium from nickel oxide ore pickle liquor | |
| CN102061382A (en) | Method for recycling zinc from zinc leaching slag cleaning solution | |
| CN103103339B (en) | Method for selectively recovering alum and gallium from alunite concentrate | |
| CN102701263B (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
| CN106086439A (en) | Method for recovering zinc and cobalt from zinc smelting slag | |
| CN101603125B (en) | Method for purification and impurity removal of nickel liquid | |
| CN100564287C (en) | Circuit board plant copper filter mud utilizes and treatment process | |
| CN103966448A (en) | Method for comprehensively recovering zinc from jarosite slag | |
| CN101760650A (en) | Method for leaching vanadium in vanadium-containing stone coal by wet process | |
| CN105483362B (en) | A kind of zinc oxide fumes multi-stage countercurrent continuously rinses the technique and device of dechlorination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Qizhi Inventor after: Shi Lei Inventor after: Zhou Baojin Inventor after: Lin Yan Inventor after: Lu Bin Inventor after: Zeng Dechao Inventor after: Wang Zufang Inventor after: Liang Wenrui Inventor before: Chen Qizhi Inventor before: Shi Lei Inventor before: Lu Bin Inventor before: Zeng Dechao Inventor before: Wang Zufang |
|
| COR | Change of bibliographic data | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Qizhi Inventor after: Shi Lei Inventor after: Lu Bin Inventor after: Zeng Dechao Inventor after: Wang Zufang Inventor before: Chen Qizhi Inventor before: Shi Lei Inventor before: Zhou Baojin Inventor before: Lin Yan Inventor before: Lu Bin Inventor before: Zeng Dechao Inventor before: Wang Zufang Inventor before: Liang Wenrui |
|
| COR | Change of bibliographic data | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 546138 888 Meibin Road, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Huiyuan Manganese Industry Co., Ltd. Address before: 546138 888 Meibin Road, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Non-Ferrous Metals Group Huiyuan Manganese Industry Co., Ltd. |