CN111410217A - Method for removing nickel and cobalt in magnesium sulfate solution by adopting extraction separation method - Google Patents
Method for removing nickel and cobalt in magnesium sulfate solution by adopting extraction separation method Download PDFInfo
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- CN111410217A CN111410217A CN202010278614.1A CN202010278614A CN111410217A CN 111410217 A CN111410217 A CN 111410217A CN 202010278614 A CN202010278614 A CN 202010278614A CN 111410217 A CN111410217 A CN 111410217A
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 186
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 93
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 93
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 71
- 239000010941 cobalt Substances 0.000 title claims abstract description 69
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 69
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000605 extraction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000926 separation method Methods 0.000 title claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011777 magnesium Substances 0.000 claims abstract description 59
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 59
- 239000000344 soap Substances 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical group CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003350 kerosene Substances 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims description 89
- 239000000243 solution Substances 0.000 claims description 53
- 239000012071 phase Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008346 aqueous phase Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000007127 saponification reaction Methods 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method, which belongs to the field of inorganic salt, and is characterized in that magnesium soap is carried out on an organic solvent by using magnesium sulfate solution or light magnesium oxide, then cobalt and nickel in the magnesium sulfate solution are extracted and separated by using the organic solvent after the magnesium soap, the magnesium sulfate solution is extracted by using the organic solvent, other impurities in the magnesium sulfate solution can not be brought, a condition is created for preparing a qualified magnesium sulfate product in the subsequent production by using a raffinate magnesium sulfate solution, the organic solvent is prepared by uniformly mixing 20-30% of an extracting agent and 70-80% of sulfonated kerosene according to volume percentage, the extracting agent is neodecanoic acid, the content of cobalt and nickel in the magnesium sulfate solution can be reduced to be less than 0.002 g/L, the obtained magnesium sulfate solution meets the quality requirement of producing an industrial-grade magnesium sulfate product, and no other three wastes are generated in the whole process.
Description
Technical Field
The invention belongs to the field of inorganic salt, and particularly relates to a method for removing nickel and cobalt in a magnesium sulfate solution by adopting an extraction separation method.
Background
In the process of producing battery-grade nickel sulfate by taking a nickel wet-process smelting intermediate product as a raw material, a certain amount of magnesium sulfate solution (waste liquid) containing cobalt and nickel with high content can be produced, and for the method for separating nickel and cobalt from the magnesium sulfate waste liquid produced by producing nickel sulfate by using the nickel wet-process intermediate product, most companies adopt a precipitation method to precipitate nickel and cobalt in magnesium sulfate by using excessive alkali, a large amount of alkali can be wasted in the process, magnesium is co-precipitated by using the alkali, a large amount of slag is produced while the alkali is wasted, and resource waste and environmental pollution are caused.
Disclosure of Invention
The invention aims to provide a method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method, which has simple production process and strong operability, recycles cobalt and nickel resources with higher utilization value while recycling magnesium sulfate waste liquid, and does not generate other three wastes in the whole process except that a small amount of sodium sulfate waste liquid is generated and is required to be sent to a sodium sulfate recycling post to produce anhydrous sodium sulfate.
In order to achieve the purpose, the invention adopts the following scheme: a method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method is characterized by comprising the following steps:
step one, early preparation:
uniformly mixing 20-30% of an extracting agent and 70-80% of sulfonated kerosene according to the volume percentage, configuring an organic phase, and pumping the configured organic phase into an extraction box; the extractant is neodecanoic acid;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.5-4.0, the cobalt content is 4.7 g/L-5.8 g/L, the magnesium content is 26 g/L-29 g/L, and the nickel content is 0.8 g/L-1.5 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with the prepared organic phase to prepare magnesium soap; the saponification rate is controlled to be 45-55%, the reaction temperature is 30-40 ℃, and the ratio of the organic phase to the water phase is controlled to be 1: (5-6), controlling the rotating speed of the stirring paddle to be 200-300 revolutions per minute, and reacting for 2-3 minutes to perform five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in the water phase in the step one by using the magnesium soap organic phase obtained by saponification in the step two, wherein the extraction section adopts an organic phase to water phase ratio of 1 (2.8-3.5), the reaction temperature is 35-40 ℃, the reaction time is 2-3 minutes, six-stage countercurrent magnesium soap is carried out, raffinate magnesium sulfate solution is used for producing magnesium sulfate products, the nickel content in the raffinate magnesium sulfate solution is less than 0.002 g/L, the cobalt content is less than 0.002 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters the step five;
step four, preparing sulfuric acid with the concentration of 1.5-2.0M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 1.5-2.0M, and controlling the ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 35-40 ℃, the mixing reaction is carried out for 3-4 minutes, the pH of the water phase after the back extraction is controlled to be 4.8-5.8, and the organic phase after the back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
Wherein the magnesium sulfate waste liquid is generated in the process of preparing nickel sulfate or cobalt sulfate.
The method for removing nickel and cobalt in the magnesium sulfate solution by adopting the extraction separation method is characterized by also comprising the following steps: in the third step, after the extraction is finished, the raffinate magnesium sulfate solution enters an evaporation and crystallization process to prepare magnesium sulfate.
The invention has the advantages that the cobalt and nickel content in the magnesium sulfate solution can be reduced to less than 0.002 g/L, and the obtained magnesium sulfate solution meets the quality requirement of producing industrial-grade magnesium sulfate products.
Drawings
The invention is further described with reference to the following figures and detailed description:
FIG. 1 is a flow chart of a method for removing nickel and cobalt from a magnesium sulfate solution by an extraction separation method in the embodiment of the invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further illustrated below in connection with specific examples, which will be understood by those skilled in the art. The following detailed description is illustrative and not restrictive, and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
As shown in fig. 1, a method for removing nickel and cobalt from magnesium sulfate solution by using an extraction separation method is characterized in that an organic solvent is subjected to magnesium soap by using magnesium sulfate solution (or light magnesium oxide), then the magnesium soap is used for extracting and separating the cobalt and the nickel in the magnesium sulfate solution by using the organic solvent, the magnesium sulfate solution is extracted by using the organic solvent, other impurities in the magnesium sulfate solution cannot be brought, and conditions are created for preparing qualified magnesium sulfate products in subsequent production by using the raffinate magnesium sulfate solution; according to volume percentage, the organic solvent is prepared by evenly mixing 20 to 30 percent of extractant and 70 to 80 percent of sulfonated kerosene; the extractant is neodecanoic acid;
the method comprises the following specific steps:
step one, early preparation:
the organic phase was configured: uniformly mixing 20-30% of an extracting agent and 70-80% of sulfonated kerosene according to volume percentage to prepare an organic phase, wherein the extracting agent is neodecanoic acid, and pumping the prepared organic phase into an extraction box;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.5-4.0, the cobalt content is 4.7 g/L-5.8 g/L, the magnesium content is 26 g/L-29 g/L, and the nickel content is 0.8 g/L-1.5 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with the organic phase prepared in the step one to prepare the magnesium soap, wherein the saponification rate is controlled to be 45-55%, the reaction temperature is 30-40 ℃, and the ratio of the organic phase to the water phase is controlled to be 1: (5-6), controlling the rotating speed of the stirring paddle to be 200-300 revolutions per minute, and reacting for 2-3 minutes to perform five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in an aqueous phase (magnesium sulfate waste liquid) by using a saponified magnesium soap organic phase (organic solvent), so that the cobalt and nickel in the aqueous phase are transferred into the organic phase, magnesium in the organic phase enters the aqueous phase, and the magnesium, the cobalt and the nickel are completely separated, wherein the extraction section adopts the organic phase to aqueous phase ratio of 1 (2.8-3.5), the reaction temperature is 35-40 ℃, the reaction time is 2-3 minutes, six-stage countercurrent magnesium soap is carried out, a raffinate magnesium sulfate solution is used for producing a magnesium sulfate product, the nickel content in the raffinate magnesium sulfate solution is less than 0.002 g/L, the cobalt content is less than 0.002 g/L, namely qualified magnesium sulfate before evaporation, and the cobalt and nickel loaded organic phase enters step five;
step four, preparing sulfuric acid with the concentration of 1.5-2.0M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 1.5-2.0M, and controlling the ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 35-40 ℃, the mixing reaction is carried out for 3-4 minutes, the pH of the water phase after back extraction is controlled to be 4.8-5.8, and the organic phase after back extraction is returned to the saponification section for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
In the third step, after extraction is finished, raffinate magnesium sulfate solution enters an evaporation crystallization process to prepare magnesium sulfate, and an organic phase is recycled after acid washing;
example 1
A method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method comprises the following steps:
step one, early preparation:
the organic phase was configured: uniformly mixing 20% of an extracting agent and 80% of sulfonated kerosene according to the volume percentage, configuring an organic phase, wherein the extracting agent is neodecanoic acid, and pumping the configured organic phase into an extraction box;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.83, the cobalt content is 5.29 g/L, the iron content is 0.0001 g/L, the calcium content is 0.001 g/L, the magnesium content is 28.7 g/L, the nickel content is 1.1 g/L, and the sodium content is 0.0005 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with a prepared organic phase to prepare the magnesium soap, wherein the saponification rate is controlled to be 45%, the reaction temperature is 30 ℃, and the ratio of the organic phase to the aqueous phase is 1: 5, controlling the rotating speed of a stirring paddle at 300 revolutions per minute, and reacting for 3 minutes to carry out five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in an aqueous phase (magnesium sulfate waste liquid) by using a saponified magnesium soap organic phase (organic solvent), so that the cobalt and nickel in the aqueous phase are transferred into the organic phase, magnesium in the organic phase enters the aqueous phase, and the magnesium, the cobalt and the nickel are completely separated, wherein the extraction section adopts the organic phase-aqueous phase ratio of 1: 2.8, the reaction temperature is 35 ℃, the reaction time is 3 minutes, six-stage countercurrent magnesium soap is carried out, a magnesium sulfate product is produced by using a raffinate magnesium sulfate solution, the cobalt content in the raffinate magnesium sulfate solution is 0.0018 g/L, the iron content is 0.0001 g/L, the calcium content is 0.0003 g/L, the magnesium content is 27.2 g/L, the nickel content is 0.001 g/L, the sodium content is 0.001 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters step five;
step four, preparing sulfuric acid with the concentration of 1.5M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 1.5M, and controlling the phase ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 40 ℃, the mixture reaction is carried out for 3 minutes, the pH of the water phase after the back extraction is controlled to be 5.2, and the organic phase after the back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
Example 2
A method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method comprises the following steps:
step one, early preparation
The organic phase was configured: uniformly mixing 30% of an extracting agent and 70% of sulfonated kerosene according to the volume percentage, configuring an organic phase, wherein the extracting agent is neodecanoic acid, and pumping the configured organic phase into an extraction box;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.77, the cobalt content is 5.78 g/L, the iron content is 0.0001 g/L, the calcium content is 0.002 g/L, the magnesium content is 26.93 g/L, the nickel content is 0.87 g/L, and the sodium content is 0.0006 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with an extracting agent to prepare the magnesium soap, wherein the saponification rate is controlled to be 50%, the reaction temperature is 40 ℃, and the phase ratio of an organic phase to a water phase is 1: 6, controlling the rotating speed of a stirring paddle at 300 revolutions per minute, and reacting for 3 minutes to carry out five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in an aqueous phase (magnesium sulfate waste liquid) by using a saponified magnesium soap organic phase (organic solvent), so that the cobalt and nickel in the aqueous phase are transferred into the organic phase, magnesium in the organic phase enters the aqueous phase, and the cobalt and the nickel are completely separated, wherein the extraction section adopts the organic phase-aqueous phase ratio of 1: 3.5, the reaction temperature is 40 ℃, the reaction time is 3 minutes, six-stage countercurrent magnesium soap is carried out, a raffinate magnesium sulfate solution is used for producing a magnesium sulfate product, the cobalt content in the raffinate magnesium sulfate solution is 0.001 g/L, the iron content is 0.0001 g/L, the calcium content is 0.0007 g/L, the magnesium content is 25.12 g/L, the nickel content is 0.0008 g/L, the sodium content is 0.0015 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters step five;
step four, preparing sulfuric acid with the concentration of 2.0M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 2.0M, and controlling the phase ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 35 ℃, the mixture reaction is carried out for 4 minutes, the pH of the water phase after back extraction is controlled to be 5.66, and the organic phase after back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
Example 3
A method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method comprises the following steps:
step one, early preparation:
the organic phase was configured: uniformly mixing 20% of an extracting agent and 80% of sulfonated kerosene according to the volume percentage, configuring an organic phase, wherein the extracting agent is neodecanoic acid, and pumping the configured organic phase into an extraction box;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.61, the cobalt content is 4.73 g/L, the iron content is 0.0002 g/L, the calcium content is 0.0011 g/L, the magnesium content is 26.72 g/L, the nickel content is 0.88 g/L, and the sodium content is 0.0005 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with the organic phase prepared in the step one to prepare the magnesium soap, wherein the saponification rate is controlled to be 55%, the reaction temperature is 35 ℃, and the ratio of the organic phase to the aqueous phase is 1: 5.5, controlling the rotating speed of a stirring paddle at 300 revolutions per minute, controlling the reaction time at 3 minutes, and carrying out five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in an aqueous phase (magnesium sulfate waste liquid) by using a saponified magnesium soap organic phase (organic solvent), so that the cobalt and nickel in the aqueous phase are transferred into the organic phase, magnesium in the organic phase enters the aqueous phase, and the magnesium, the cobalt and the nickel are completely separated, wherein the extraction section adopts the organic phase to aqueous phase ratio of 1: 3, the reaction temperature is 38 ℃, the reaction time is 3 minutes, six-stage countercurrent magnesium soap is carried out, a magnesium sulfate product is produced by using a raffinate magnesium sulfate solution, the cobalt content in the raffinate magnesium sulfate solution is 0.001 g/L, the iron content is 0.0001 g/L, the calcium content is 0.0009 g/L, the magnesium content is 26.34 g/L, the nickel content is 0.0017 g/L, and the sodium content is 0.0009 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters step five;
step four, preparing sulfuric acid with the concentration of 1.7M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 1.7M, and controlling the ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 36 ℃, the mixing reaction is carried out for 3.5 minutes, the pH of the water phase after back extraction is controlled to be 5.36, and the organic phase after back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
Example 4
A method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method comprises the following steps:
step one, early preparation:
the organic phase was configured: uniformly mixing 25% of an extracting agent and 75% of sulfonated kerosene according to the volume percentage, configuring an organic phase, wherein the extracting agent is neodecanoic acid, and pumping the configured organic phase into an extraction box;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.80, the cobalt content is 5.46 g/L, the iron content is 0.0001 g/L, the calcium content is 0.001 g/L, the magnesium content is 28.6 g/L, the nickel content is 1.5 g/L, and the sodium content is 0.0005 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with the magnesium soap prepared in the step one, wherein the saponification rate is controlled to be 47.3%, the reaction temperature is 32 ℃, and the ratio of the organic phase to the water phase is 1: 5.6, controlling the rotating speed of a stirring paddle at 300 revolutions per minute, controlling the reaction time at 3 minutes, and carrying out five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in an aqueous phase (magnesium sulfate waste liquid) by using a saponified magnesium soap organic phase (organic solvent), so that the cobalt and nickel in the aqueous phase are transferred into the organic phase, magnesium in the organic phase enters the aqueous phase, and the cobalt and the nickel are completely separated, wherein the extraction section adopts the organic phase to aqueous phase ratio of 1: 3, the reaction temperature is 39 ℃, the reaction time is 3 minutes, six-stage countercurrent magnesium soap is carried out, a magnesium sulfate product is produced by using a raffinate magnesium sulfate solution, the cobalt content in the raffinate magnesium sulfate solution is 0.00098 g/L, the iron content is 0.0001 g/L, the magnesium content is 28.17 g/L, the nickel content is 0.0008 g/L, the calcium content is 0.001 g/L, and the sodium content is 0.0005 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters step five;
step four, preparing sulfuric acid with the concentration of 2.0M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 2.0M, and controlling the phase ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 35 ℃, the mixture reaction is carried out for 4 minutes, the pH of the water phase after back extraction is controlled to be 5.37, and the organic phase after back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
Claims (3)
1. A method for removing nickel and cobalt in magnesium sulfate solution by adopting an extraction separation method is characterized by comprising the following steps:
step one, early preparation:
uniformly mixing 20-30% of an extracting agent and 70-80% of sulfonated kerosene according to the volume percentage, configuring an organic phase, and pumping the configured organic phase into an extraction box; the extractant is neodecanoic acid;
the water phase is magnesium sulfate waste liquid, and the indexes of the water phase are that the pH value is 3.5-4.0, the cobalt content is 4.7 g/L-5.8 g/L, the magnesium content is 26 g/L-29 g/L, and the nickel content is 0.8 g/L-1.5 g/L;
step two, mixing a sodium hydroxide solution with the organic phase prepared in the step one to perform homogeneous saponification reaction, and then reacting with a magnesium sulfate solution to prepare a magnesium soap; or directly reacting light magnesium oxide with the prepared organic phase to prepare magnesium soap; the saponification rate is controlled to be 45-55%, the reaction temperature is 30-40 ℃, and the ratio of the organic phase to the water phase is controlled to be 1: (5-6), controlling the rotating speed of the stirring paddle to be 200-300 revolutions per minute, and reacting for 2-3 minutes to perform five-stage countercurrent magnesium soap;
step three, extracting cobalt and nickel in the water phase in the step one by using the magnesium soap organic phase obtained by saponification in the step two, wherein the extraction section adopts an organic phase to water phase ratio of 1 (2.8-3.5), the reaction temperature is 35-40 ℃, the reaction time is 2-3 minutes, six-stage countercurrent magnesium soap is carried out, raffinate magnesium sulfate solution is used for producing magnesium sulfate products, the nickel content in the raffinate magnesium sulfate solution is less than 0.002 g/L, the cobalt content is less than 0.002 g/L, namely qualified magnesium sulfate evaporation front liquid, and the cobalt and nickel loaded organic phase enters the step five;
step four, preparing sulfuric acid with the concentration of 1.5-2.0M;
and step five, back-extracting the organic phase loaded with cobalt and nickel by using sulfuric acid with the concentration of 1.5-2.0M, and controlling the ratio of the organic phase to the aqueous phase to be 1: 5, the reaction temperature is 35-40 ℃, the mixing reaction is carried out for 3-4 minutes, the pH of the water phase after the back extraction is controlled to be 4.8-5.8, and the organic phase after the back extraction is returned to the second step for recycling; the cobalt-nickel sulfate mixed solution obtained by back extraction, namely the water phase, is returned to the main production system for use.
2. The process for the removal of nickel and cobalt from magnesium sulfate solutions by extractive separation as claimed in claim 1 wherein: the magnesium sulfate waste liquid is generated in the process of preparing nickel sulfate or cobalt sulfate.
3. The method for removing nickel and cobalt from a magnesium sulfate solution by an extractive separation method according to claim 1, further comprising: in the third step, after the extraction is finished, the raffinate magnesium sulfate solution enters an evaporation and crystallization process to prepare magnesium sulfate.
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