CN114314698A - Method for producing nickel protoxide by preparing low-sulfur nickel chloride through extraction method - Google Patents
Method for producing nickel protoxide by preparing low-sulfur nickel chloride through extraction method Download PDFInfo
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Abstract
The invention relates to a method for producing nickel protoxide by preparing low-sulfur nickel chloride through an extraction method, which takes a crude nickel sulfate solution as a raw material, and the crude nickel sulfate solution is used as a raw material solution for spray pyrolysis after P204 extraction, impurity removal and purification. The technology of preparing nickel-containing solution into nickel carbonate and directly producing nickel protoxide is replaced. The method reduces the risk of introducing impurities such as sulfur, calcium, magnesium, sodium and the like into the product in the nickel carbonate synthesis process, shortens the process flow, reduces the generation of wastewater, reduces the production cost and improves the operating environment. The invention shortens the process flow, reduces the generation of wastewater, reduces the production cost, improves the product quality, improves the operation environment and has good economic value.
Description
Technical Field
The invention relates to the technical field of wet and pyrometallurgy of nonferrous metals, in particular to a method for producing nickel protoxide by preparing low-sulfur nickel chloride through an extraction method.
Background
Nickel protoxide (NiO), dark green or grayish green powder, is an important inorganic fine chemical, and is mainly used for preparing alloys, storage batteries, glass, enamel, ceramics, catalysts for electronic components, and the like. The preparation method of nickel protoxide mainly includes two methods, one is to prepare high-quality nickel carbonate and calcine the nickel carbonate into nickel protoxide powder, then to wash sulfur, dry and screen, the other is to prepare high-quality nickel chloride solution by dissolving high-purity nickel with refined hydrochloric acid, then to prepare nickel protoxide solution by spray pyrolysis method, then to wash, screen and dry. The two processes have respective characteristics, but have the common characteristic of high production cost. The calcination method of nickel carbonate, preparing high-quality nickel carbonate needs high-quality nickel sulfate or nickel chloride solution at first, add high-purity sodium carbonate and synthesize nickel carbonate, the nickel carbonate synthesized must be washed many times and can guarantee sodium, sulphur, etc. reach standard, the preparation method is complicated, and produce a large amount of waste water, is unfavorable for environmental protection. The high-purity nickel is prepared by generally using nickel hydroxide or nickel sulfide as a raw material through multi-process impurity removal and electrolysis, the generation cost is high, the cost of refining hydrochloric acid is high to ensure low sulfur content, and the cost is greatly increased by preparing a nickel chloride solution through the solution, so that the production cost of the nickel protoxide is high at present. And the whole process flow is long and the process is complex.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention takes the crude nickel sulfate solution as the raw material, directly prepares the high-purity low-sulfur nickel chloride solution after removing impurities by an extraction method, and achieves the purposes of shortening the preparation process flow of the nickel protoxide and reducing the production cost when being used for preparing the nickel protoxide by spray roasting.
In order to achieve the aim, the method for producing nickel protoxide by preparing low-sulfur nickel chloride through the extraction method is characterized by comprising the following steps of,
a, removing calcium and magnesium from the crude nickel sulfate solution to obtain a nickel sulfate solution with the calcium and magnesium content concentration less than or equal to 0.002 g/L;
b. mixing a diluent and a P204 extracting agent in a volume ratio of 3:1 to prepare an extraction organic phase, uniformly stirring, and analyzing the hydrogen ion concentration to be 0.65-0.75 mol/L;
c. saponifying the extracted organic phase; adding 25-30% NaOH solution into the prepared extraction organic phase, and reacting for 5min to ensure that the hydrogen ions in the saponified organic phase are 0.05-0.15 mol/L;
d. and (c) carrying out 9-11 grade countercurrent extraction reaction on the nickel sulfate solution subjected to calcium and magnesium removal in the step a and the organic phase subjected to soap in the step c, wherein the reaction temperature is maintained at 45-55 ℃, and the organic phase is a solution of 4-6: 1, extracting nickel in the solution into an organic phase, and leaving high-concentration sodium sulfate in raffinate to be used as wastewater for centralized treatment;
e. loading nickel-containing P204 into an organic phase; carrying out 8-10 grade countercurrent sulfur and sodium washing by using dilute hydrochloric acid with the concentration of 1.0-1.5mol/L at normal temperature, wherein the organic phases are solution 10-12: 1, enabling redundant sodium and sulfate radicals in an organic phase to enter a washing liquid, transferring nickel which is about 10-15% of the loaded organic phase into the washing liquid in the process, outputting the nickel in a form of nickel chloride solution, merging the nickel into an extraction feeding stage, and washing to obtain a washed P204 loaded organic phase;
f. and (3) carrying out back extraction on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10-12mol/L, wherein the organic phase comprises a solution of 10-12: 1, producing nickel in an organic phase in a nickel chloride form to obtain a low-sulfur high-purity nickel chloride solution, wherein the nickel chloride solution is used as a raw material solution for spray pyrolysis;
g. regenerating the back-extracted P204 organic phase by using hydrochloric acid with the concentration of 4-6mol/L, wherein the ratio of hydrochloric acid to hydrochloric acid is 6-8:1, and the regenerated organic phase is recycled;
h. preparing crude nickel protoxide by spray pyrolysis: the prepared low-sulfur high-purity nickel chloride solution is conveyed to preconcentration for concentration, when the specific gravity of the solution reaches 1.45-1.55, the solution is sprayed into a pyrolysis furnace through a collision head of the pyrolysis furnace under high pressure, the pyrolysis temperature of the pyrolysis furnace is 650-750 ℃, the sprayed solution is instantly dehydrated, the solution is thermally decomposed to generate crude nickelous oxide powder, the nickelous oxide powder is settled at the bottom of the furnace under the action of gravity, negative pressure is formed through a centrifugal fan, and the crude nickelous oxide powder is pumped into a storage bin;
i. washing the crude nickel protoxide: in order to avoid that the quality of nickelous oxide is influenced by an unreacted nickel chloride solution in the spraying process, slurrying and washing crude nickelous oxide obtained by spray pyrolysis, slurrying and washing pure water and the crude nickelous oxide according to the mass ratio of 7-10:1, injecting the pure water in the washing process, screening the nickelous oxide by a 40-mesh screen separator, adding the screened nickelous oxide into a slurrying reaction kettle, stirring and washing for 1-1.5h, wherein the washing water temperature is 70-90 ℃;
j. centrifuging and drying the slurry: injecting the washed nickel protoxide slurry into an intermittent centrifuge for centrifugal dehydration, wherein the dehydrated material contains 10-15% of water, then conveying the material to drying for drying, and conveying the dried material to a storage bin sequentially by cyclone dust collection;
k. mixing materials, screening and packaging to obtain a nickel protoxide product: and opening a storage bin for stirring, uniformly mixing the materials, screening the materials by a screening machine with standard requirements, and packaging to obtain a qualified nickel protoxide product.
In the technical scheme of the method for producing nickel protoxide by preparing low-sulfur nickel chloride through the extraction method, the further preferable technical scheme is characterized in that:
1. after the step b is uniformly stirred, the concentration of analyzed hydrogen ions is 0.72 mol/L;
2. the reaction temperature of the step d is maintained at 50 ℃, and the organic phase: 1;
3. and e, performing 9-stage countercurrent sulfur and sodium washing by using dilute hydrochloric acid with the concentration of 1.0mol/L at normal temperature, wherein the organic phases are solution 11: 1;
4. the pyrolysis temperature of the pyrolysis furnace in the step h is 700 ℃;
5. the washing time in the step i is 1h, and the washing water temperature is 80 ℃;
6. and (5) the dehydrated material in the step i contains 12.8% of water.
The extraction mechanism of the invention is as follows:
Mg2++F-→MgF2↓
Ca2++F-→CaF2↓
RH+NaOH→NaR+H2o (formula, RH represents P204)
NaR +Ni2+→NiR+Na+
NaR +HCl→NiCl2+ RH
NiCl2 +O2→NiO+ Cl2
Compared with the prior art, the invention has the following beneficial effects: the method takes crude nickel sulfate solution as a raw material, and the crude nickel sulfate solution is extracted, decontaminated and purified by P204 to be used as a raw material solution for spray pyrolysis. The technology of preparing nickel-containing solution into nickel carbonate and directly producing nickel protoxide is replaced. The method reduces the risk of introducing impurities such as sulfur, calcium, magnesium, sodium and the like into the product in the nickel carbonate synthesis process, shortens the process flow, reduces the generation of wastewater, reduces the production cost and improves the operating environment. The invention shortens the process flow, reduces the generation of wastewater, reduces the production cost, improves the product quality, improves the operation environment and has good economic value.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1, a method for producing nickel protoxide by preparing low-sulfur nickel chloride through an extraction method, comprising the following steps: a, removing calcium and magnesium from the crude nickel sulfate solution to obtain a nickel sulfate solution with the calcium and magnesium content concentration less than or equal to 0.002 g/L; b. mixing a diluent and a P204 extracting agent in a volume ratio of 3:1 to prepare an extraction organic phase, uniformly stirring, and analyzing the hydrogen ion concentration to be 0.65-0.75 mol/L; c. saponifying the extracted organic phase; adding 25-30% NaOH solution into the prepared extraction organic phase, and reacting for 5min to ensure that the hydrogen ions in the saponified organic phase are 0.05-0.15 mol/L; d. and (c) carrying out 9-11 grade countercurrent extraction reaction on the nickel sulfate solution subjected to calcium and magnesium removal in the step a and the organic phase subjected to soap in the step c, wherein the reaction temperature is maintained at 45-55 ℃, and the organic phase is a solution of 4-6: 1, extracting nickel in the solution into an organic phase, and leaving high-concentration sodium sulfate in raffinate to be used as wastewater for centralized treatment; e. loading nickel-containing P204 into an organic phase; carrying out 8-10 grade countercurrent sulfur and sodium washing by using dilute hydrochloric acid with the concentration of 1.0-1.5mol/L at normal temperature, wherein the organic phases are solution 10-12: 1, enabling redundant sodium and sulfate radicals in an organic phase to enter a washing liquid, transferring nickel which is about 10-15% of the loaded organic phase into the washing liquid in the process, outputting the nickel in a form of nickel chloride solution, merging the nickel into an extraction feeding stage, and washing to obtain a washed P204 loaded organic phase; f. and (3) carrying out back extraction on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10-12mol/L, wherein the organic phase comprises a solution of 10-12: 1, producing nickel in an organic phase in a nickel chloride form to obtain a low-sulfur high-purity nickel chloride solution, wherein the nickel chloride solution is used as a raw material solution for spray pyrolysis; g. regenerating the back-extracted P204 organic phase by using hydrochloric acid with the concentration of 4-6mol/L, wherein the ratio of hydrochloric acid to hydrochloric acid is 6-8:1, and the regenerated organic phase is recycled; h. preparing crude nickel protoxide by spray pyrolysis: the prepared low-sulfur high-purity nickel chloride solution is conveyed to preconcentration for concentration, when the specific gravity of the solution reaches 1.45-1.55, the solution is sprayed into a pyrolysis furnace through a collision head of the pyrolysis furnace under high pressure, the pyrolysis temperature of the pyrolysis furnace is 650-750 ℃, the sprayed solution is instantly dehydrated, the solution is thermally decomposed to generate crude nickelous oxide powder, the nickelous oxide powder is settled at the bottom of the furnace under the action of gravity, negative pressure is formed through a centrifugal fan, and the crude nickelous oxide powder is pumped into a storage bin; i. washing the crude nickel protoxide: in order to avoid that the quality of nickelous oxide is influenced by an unreacted nickel chloride solution in the spraying process, slurrying and washing crude nickelous oxide obtained by spray pyrolysis, slurrying and washing pure water and the crude nickelous oxide according to the mass ratio of 7-10:1, injecting the pure water in the washing process, screening the nickelous oxide by a 40-mesh screen separator, adding the screened nickelous oxide into a slurrying reaction kettle, stirring and washing for 1-1.5h, wherein the washing water temperature is 70-90 ℃; j. centrifuging and drying the slurry: injecting the washed nickel protoxide slurry into an intermittent centrifuge for centrifugal dehydration, wherein the dehydrated material contains 10-15% of water, then conveying the material to drying for drying, and conveying the dried material to a storage bin sequentially by cyclone dust collection; k. mixing materials, screening and packaging to obtain a nickel protoxide product: and opening a storage bin for stirring, uniformly mixing the materials, screening the materials by a screening machine with standard requirements, and packaging to obtain a qualified nickel protoxide product. The crude nickel sulfate solution comprises the following components: ni 25 g/L-45%, Co 0.01 g/L-0.005 g/L, Ca 0.01 g/L-0.5 g/L, Cd 0.001 g/L-0.003 g/L, Mg 0.5 g/L-2.5 g/L. The preparation method of calcium and magnesium removal comprises the following steps: and injecting the solution into a calcium and magnesium removing reaction kettle, starting stirring, heating to 70-80 ℃, analyzing the calcium and magnesium content in the solution, adding sodium fluoride according to 8-10 times of the total amount of calcium and magnesium, generating insoluble calcium magnesium fluoride and calcium fluoride, and performing filter pressing to obtain a nickel sulfate solution with the calcium and magnesium content concentration of less than or equal to 0.002 g/L.
Example 2, in the method for producing nickel protoxide by using low-sulfur nickel chloride through the extraction method described in example 1, the hydrogen ion concentration analyzed after the step b is uniformly stirred is 0.72 mol/L.
Example 3, in the method for producing nickel protoxide by using low-sulfur nickel chloride through extraction according to example 1 or 2, the reaction temperature of the step d is maintained at 50 ℃, and the ratio of organic phase to solution 5: 1.
example 4, in the method for producing nickel protoxide by using low-sulfur nickel chloride through extraction method according to any one of examples 1 to 3, step e is implemented by 9-stage countercurrent sulfur and sodium washing with dilute hydrochloric acid with concentration of 1.0mol/L at normal temperature, and the organic phase is as follows, namely solution 11: 1.
example 5. in the method for producing nickel protoxide by using low-sulfur nickel chloride through the extraction method according to any one of examples 1 to 4, the pyrolysis temperature of the pyrolysis furnace in the step h is 700 ℃.
Example 6. in the method for producing nickel protoxide by using low-sulfur nickel chloride through extraction according to any one of examples 1 to 5, the washing time in the step i is 1h, and the washing water temperature is 80 ℃.
Example 7. in the process for producing nickel protoxide by low sulfur nickel chloride through extraction according to any one of examples 1 to 6, the dehydrated material in step i contains 12.8% of water.
Example 8 a crude nickel sulfate solution having the following composition (Ni: 32g/L, Co: 0.008g/L, Ca:0.08g/L, Cd 0.001.001 g/L, Mg: 1.5 g/L), was heated to 70 ℃ and reacted by adding sodium fluoride, after the reaction, Ni =31.3g/L, Co =0.008g/L, Cd =0.001g/L Ca =0.001g/L, Mg =0.0023g/L, in a ratio of 3:1, the concentration of hydrogen ions analyzed by the extractant prepared is 0.72 mol/L; adding 30% NaOH solution to react for 5min, and analyzing the hydrogen ions in the organic phase to be 0.1mol/L after the soap is analyzed; then, carrying out 9-stage countercurrent extraction reaction on the nickel sulfate solution without calcium and magnesium and the organic phase after the soap, wherein the reaction temperature is maintained at 45 ℃, and the flow ratio (organic phase: solution) is 4.5: 1, carrying out 8-stage countercurrent sulfur and sodium washing on the washing section by using dilute hydrochloric acid with the concentration of 1.0mol/L at normal temperature, wherein the flow ratio (organic phase: solution) is 10: and 1, a stripping section performs stripping on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10mol/L (S =0.01 g/L), wherein the flow ratio (organic phase: solution) is 10:1, obtaining a nickel chloride strip liquor, wherein the strip liquor comprises the following components (Ni: 133g/L, Co: 0.006g/L, Ca:0.0016g/L, Cd 0.0008.0008 g/L, Mg: 0.008g/L, S:0.021 g/L), and regenerating a P204 organic phase by hydrochloric acid with the concentration of 4-mol/L in a rising section, wherein the regenerated organic phase is recycled compared with 6: 1.
Conveying the prepared nickel chloride solution to preconcentration by a pump for concentration, and spraying the solution into a pyrolysis furnace through the collision of the solution through the pyrolysis furnace at high pressure when the specific gravity of the solution reaches 1.45, wherein the pyrolysis temperature of the pyrolysis furnace is 651 ℃; pure water and crude nickel protoxide are slurried and washed according to the mass ratio (water: materials) of 7-1, the washing water temperature is 70 ℃, and the nickel protoxide is sieved by a 40-mesh sieve before being added. After the addition, the mixture was stirred for 1 hour and then sent to a centrifuge for centrifugation, and the moisture content of the centrifuged wet material was 12.8%. The centrifuged material was then dried in a dryer, mixed with agitation after entering the blender, sieved through a 100 mesh sieve and packaged, and analyzed for nickel protoxide product composition as follows (Ni =77.81, Co =0.0240.15 Cu =0.0048, Fe =0.015, Zn =0.0003, Ca =0.0094, Mg =0.0076, Na =0.031, Cd =0.0001, S =0.018, hydrochloric acid insoluble = 0.10)
Example 9 a crude nickel sulfate solution having the composition (Ni: 26g/L, Co: 0.002g/L, Ca:0.1g/L, Cd 0.0008.0008 g/L, Mg: 0.6 g/L) was heated to 80 ℃ and reacted by adding sodium fluoride, after which Ni =25.6g/L, Co =0.0023g/L, Cd =0.00078g/L Ca =0.0012g/L, Mg =0.0021g/L, as follows: 1, the concentration of hydrogen ions analyzed by the extractant prepared is 0.68 mol/L; adding 25% NaOH solution to react for 5min, and analyzing the hydrogen ions in the organic phase to be 0.06mol/L after the soap is analyzed; then, carrying out 10-grade countercurrent extraction reaction on the nickel sulfate solution without calcium and magnesium and the organic phase after the soap, wherein the reaction temperature is maintained at 50 ℃, and the flow ratio (organic phase: solution) is 5: 1, carrying out 9-stage countercurrent sulfur and sodium washing on the washing section by using dilute hydrochloric acid with the concentration of 1.2mol/L at normal temperature, wherein the flow ratio (organic phase: solution) is 11: and 1, a stripping section performs stripping on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 11mol/L (S =0.012 g/L), and the flow ratio (organic phase: solution) is 11: 1, obtaining a nickel chloride strip liquor, wherein the strip liquor comprises the following components (Ni: 136g/L, Co: 0.0052g/L, Ca:0.0016g/L, Cd 0.00065.00065 g/L, Mg: 0.0048g/L, S:0.023 g/L), and the P204 organic phase is regenerated by hydrochloric acid with the concentration of 5mol/L in a rising section, and the regenerated organic phase is recycled compared with 7: 1.
Conveying the prepared nickel chloride solution to preconcentration by a pump for concentration, and spraying the solution into a pyrolysis furnace through a collision head of the pyrolysis furnace under high pressure when the specific gravity of the solution reaches 1.51, wherein the pyrolysis temperature of the pyrolysis furnace is 680 ℃; pure water and crude nickel protoxide are slurried and washed according to a mass ratio (water: material) of 8:1, the washing water temperature is 75 ℃, and the nickel protoxide is sieved by a 40-mesh sieve before being added. After the addition, the mixture was stirred for 1 hour and then sent to a centrifuge for centrifugation, and the moisture content of the centrifuged wet material was 10.4%. The centrifuged material was then dried in a dryer, mixed with stirring after entering the blender, sieved through a 100 mesh sieve and packaged, and analyzed for nickel protoxide product composition as follows (Ni =77.64, Co =0.024, Cu =0.0032, Fe =0.023, Zn =0.0001, Ca =0.0074, Mg =0.0086, Na =0.033, Cd =0.0001, S =0.021, hydrochloric acid insoluble = 0.10)
Example 10 a crude nickel sulfate solution having the following composition (Ni: 32g/L, Co: 0.008g/L, Ca:0.08g/L, Cd 0.001.001 g/L, Mg: 1.5 g/L), was heated to 70 ℃ and reacted by adding sodium fluoride, after the reaction, Ni =31.3g/L, Co =0.008g/L, Cd =0.001g/L Ca =0.001g/L, Mg =0.0023g/L, in a ratio of 3:1, the concentration of hydrogen ions analyzed by the extractant prepared is 0.72 mol/L; adding 30% NaOH solution to react for 5min, and analyzing the hydrogen ions in the organic phase to be 0.1mol/L after the soap is analyzed; then, carrying out 9-stage countercurrent extraction reaction on the nickel sulfate solution without calcium and magnesium and the organic phase after the soap, wherein the reaction temperature is maintained at 45 ℃, and the flow ratio (organic phase: solution) is 4.5: 1, carrying out 8-stage countercurrent sulfur and sodium washing on the washing section by using dilute hydrochloric acid with the concentration of 1.0mol/L at normal temperature, wherein the flow ratio (organic phase: solution) is 10: and 1, a stripping section performs stripping on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10mol/L (S =0.01 g/L), wherein the flow ratio (organic phase: solution) is 10:1, obtaining a nickel chloride strip liquor, wherein the strip liquor comprises the following components (Ni: 133g/L, Co: 0.006g/L, Ca:0.0016g/L, Cd 0.0008.0008 g/L, Mg: 0.008g/L, S:0.021 g/L), and regenerating a P204 organic phase by hydrochloric acid with the concentration of 4-mol/L in a rising section, wherein the regenerated organic phase is recycled compared with 6: 1.
Conveying the prepared nickel chloride solution to preconcentration by a pump for concentration, and spraying the solution into a pyrolysis furnace through the collision of the solution through the pyrolysis furnace at high pressure when the specific gravity of the solution reaches 1.45, wherein the pyrolysis temperature of the pyrolysis furnace is 651 ℃; pure water and crude nickel protoxide are slurried and washed according to the mass ratio (water: materials) of 7-1, the washing water temperature is 70 ℃, and the nickel protoxide is sieved by a 40-mesh sieve before being added. After the addition, the mixture was stirred for 1 hour and then sent to a centrifuge for centrifugation, and the moisture content of the centrifuged wet material was 12.8%. The centrifuged material was then dried in a dryer, mixed with agitation after entering the blender, sieved through a 100 mesh sieve and packaged, and analyzed for nickel protoxide product composition as follows (Ni =77.81, Co =0.0240.15 Cu =0.0048, Fe =0.015, Zn =0.0003, Ca =0.0094, Mg =0.0076, Na =0.031, Cd =0.0001, S =0.018, hydrochloric acid insoluble = 0.10)
Example 11 a crude nickel sulfate solution having the following composition (Ni: 32g/L, Co: 0.008g/L, Ca:0.08g/L, Cd 0.001.001 g/L, Mg: 1.5 g/L) was heated to 70 ℃ and reacted by adding sodium fluoride, after the reaction, Ni =31.3g/L, Co =0.008g/L, Cd =0.001g/L Ca =0.001g/L, Mg =0.0023g/L, in terms of 3:1, the concentration of hydrogen ions analyzed by the extractant prepared is 0.72 mol/L; adding 30% NaOH solution to react for 5min, and analyzing the hydrogen ions in the organic phase to be 0.1mol/L after the soap is analyzed; then, carrying out 9-stage countercurrent extraction reaction on the nickel sulfate solution without calcium and magnesium and the organic phase after the soap, wherein the reaction temperature is maintained at 45 ℃, and the flow ratio (organic phase: solution) is 4.5: 1, carrying out 8-stage countercurrent sulfur and sodium washing on the washing section by using dilute hydrochloric acid with the concentration of 1.0mol/L at normal temperature, wherein the flow ratio (organic phase: solution) is 10: and 1, a stripping section performs stripping on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10mol/L (S =0.01 g/L), wherein the flow ratio (organic phase: solution) is 10:1, obtaining a nickel chloride strip liquor, wherein the strip liquor comprises the following components (Ni: 133g/L, Co: 0.006g/L, Ca:0.0016g/L, Cd 0.0008.0008 g/L, Mg: 0.008g/L, S:0.021 g/L), and regenerating a P204 organic phase by hydrochloric acid with the concentration of 4-mol/L in a rising section, wherein the regenerated organic phase is recycled compared with 6: 1.
Conveying the prepared nickel chloride solution to preconcentration by a pump for concentration, and spraying the solution into a pyrolysis furnace through the collision of the solution through the pyrolysis furnace at high pressure when the specific gravity of the solution reaches 1.45, wherein the pyrolysis temperature of the pyrolysis furnace is 651 ℃; pure water and crude nickel protoxide are slurried and washed according to the mass ratio (water: materials) of 7-1, the washing water temperature is 70 ℃, and the nickel protoxide is sieved by a 40-mesh sieve before being added. After the addition, the mixture was stirred for 1 hour and then sent to a centrifuge for centrifugation, and the moisture content of the centrifuged wet material was 12.8%. The centrifuged material was then dried in a dryer, mixed with agitation after entering the blender, sieved through a 100 mesh sieve and packaged, and analyzed for nickel protoxide product composition as follows (Ni =77.81, Co =0.0240.15 Cu =0.0048, Fe =0.015, Zn =0.0003, Ca =0.0094, Mg =0.0076, Na =0.031, Cd =0.0001, S =0.018, hydrochloric acid insoluble = 0.10).
The above description is only for the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept thereof within the scope of the present invention.
Claims (7)
1. The method for producing nickel protoxide by preparing low-sulfur nickel chloride through the extraction method is characterized by comprising the following steps of:
a, removing calcium and magnesium from the crude nickel sulfate solution to obtain a nickel sulfate solution with the calcium and magnesium content concentration less than or equal to 0.002 g/L;
b. mixing a diluent and a P204 extracting agent in a volume ratio of 3:1 to prepare an extraction organic phase, uniformly stirring, and analyzing the hydrogen ion concentration to be 0.65-0.75 mol/L;
c. saponifying the extracted organic phase; adding 25-30% NaOH solution into the prepared extraction organic phase, and reacting for 5min to ensure that the hydrogen ions in the saponified organic phase are 0.05-0.15 mol/L;
d. and (c) carrying out 9-11 grade countercurrent extraction reaction on the nickel sulfate solution subjected to calcium and magnesium removal in the step a and the organic phase subjected to soap in the step c, wherein the reaction temperature is maintained at 45-55 ℃, and the organic phase is a solution of 4-6: 1, extracting nickel in the solution into an organic phase, and leaving high-concentration sodium sulfate in raffinate to be used as wastewater for centralized treatment;
e. loading nickel-containing P204 into an organic phase; carrying out 8-10 grade countercurrent sulfur and sodium washing by using dilute hydrochloric acid with the concentration of 1.0-1.5mol/L at normal temperature, wherein the organic phases are solution 10-12: 1, enabling redundant sodium and sulfate radicals in an organic phase to enter a washing liquid, transferring nickel which is about 10-15% of the loaded organic phase into the washing liquid in the process, outputting the nickel in a form of nickel chloride solution, merging the nickel into an extraction feeding stage, and washing to obtain a washed P204 loaded organic phase;
f. and (3) carrying out back extraction on the washed P204 loaded organic phase by using low-sulfur hydrochloric acid with the concentration of 10-12mol/L, wherein the organic phase comprises a solution of 10-12: 1, producing nickel in an organic phase in a nickel chloride form to obtain a low-sulfur high-purity nickel chloride solution, wherein the nickel chloride solution is used as a raw material solution for spray pyrolysis;
g. regenerating the back-extracted P204 organic phase by using hydrochloric acid with the concentration of 4-6mol/L, wherein the ratio of hydrochloric acid to hydrochloric acid is 6-8:1, and the regenerated organic phase is recycled;
h. preparing crude nickel protoxide by spray pyrolysis: the prepared low-sulfur high-purity nickel chloride solution is conveyed to preconcentration for concentration, when the specific gravity of the solution reaches 1.45-1.55, the solution is sprayed into a pyrolysis furnace through a collision head of the pyrolysis furnace under high pressure, the pyrolysis temperature of the pyrolysis furnace is 650-750 ℃, the sprayed solution is instantly dehydrated, the solution is thermally decomposed to generate crude nickelous oxide powder, the nickelous oxide powder is settled at the bottom of the furnace under the action of gravity, negative pressure is formed through a centrifugal fan, and the crude nickelous oxide powder is pumped into a storage bin;
i. washing the crude nickel protoxide: in order to avoid that the quality of nickelous oxide is influenced by an unreacted nickel chloride solution in the spraying process, slurrying and washing crude nickelous oxide obtained by spray pyrolysis, slurrying and washing pure water and the crude nickelous oxide according to the mass ratio of 7-10:1, injecting the pure water in the washing process, screening the nickelous oxide by a 40-mesh screen separator, adding the screened nickelous oxide into a slurrying reaction kettle, stirring and washing for 1-1.5h, wherein the washing water temperature is 70-90 ℃;
j. centrifuging and drying the slurry: injecting the washed nickel protoxide slurry into an intermittent centrifuge for centrifugal dehydration, wherein the dehydrated material contains 10-15% of water, then conveying the material to drying for drying, and conveying the dried material to a storage bin sequentially by cyclone dust collection;
k. mixing materials, screening and packaging to obtain a nickel protoxide product: and opening a storage bin for stirring, uniformly mixing the materials, screening the materials by a screening machine with standard requirements, and packaging to obtain a qualified nickel protoxide product.
2. The process according to claim 1, wherein the nickel-containing solution is purified by: and b, after the mixture is uniformly stirred, the concentration of the analyzed hydrogen ions is 0.72 mol/L.
3. The process according to claim 1, wherein the nickel-containing solution is purified by: the reaction temperature of the step d is maintained at 50 ℃, and the organic phase: 1.
4. the process according to claim 1, wherein the nickel-containing solution is purified by: and e, performing 9-stage countercurrent sulfur and sodium washing by using dilute hydrochloric acid with the concentration of 1.0mol/L at normal temperature, wherein the organic phases are solution 11: 1.
5. the process according to claim 1, wherein the nickel-containing solution is purified by: the pyrolysis temperature of the pyrolysis furnace in the step h is 700 ℃.
6. The process according to claim 1, wherein the nickel-containing solution is purified by: the washing time in the step i is 1h, and the washing water temperature is 80 ℃.
7. The process according to claim 1, wherein the nickel-containing solution is purified by: and (5) the dehydrated material in the step i contains 12.8% of water.
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