CN109777954B - Method for extracting ions in mineral liquid - Google Patents
Method for extracting ions in mineral liquid Download PDFInfo
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- CN109777954B CN109777954B CN201910187879.8A CN201910187879A CN109777954B CN 109777954 B CN109777954 B CN 109777954B CN 201910187879 A CN201910187879 A CN 201910187879A CN 109777954 B CN109777954 B CN 109777954B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for extracting ions in mineral liquid. The extraction method comprises the following steps: 1) carrying out sodium soap on the P204 organic phase, adding nickel sulfate to carry out nickel soap reaction until nickel ions replace sodium ions in the organic phase to obtain a nickel-P204 organic phase; 2) adding mineral liquid into the nickel-P204 organic phase, wherein the ratio of O to A is 1: 2-4: 1, and fully reacting to obtain a first extraction phase and a first raffinate; 3) adding 0.1-2N sulfuric acid into the first extraction phase, and fully reacting to obtain a second raffinate and a second extraction phase; 4) adding 0.01-2N hydrochloric acid into the second extraction phase, and fully reacting to obtain a third raffinate and a third extraction phase; the mineral liquid at least contains iron, nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5. The extraction method can effectively separate copper, nickel, cobalt, manganese and zinc, and the recovery rate is over 90 percent.
Description
Technical Field
The invention relates to the technical field of separation and extraction in hydrometallurgy, and particularly relates to a method for extracting ions in mineral liquid.
Background
The laterite-nickel ore contains abundant metal resources, the laterite-nickel ore generally contains nickel, cobalt, iron, manganese, zinc, copper, calcium, magnesium and other elements, the content of Ni is 0.8-3.0%, and the content of Co is 0.02-0.3%.
In the prior art, effective elements in the alloy are usually extracted by wet smelting, wherein only Ni and Co in the alloy are extracted by the wet smelting, and the rest part of the alloy, which accounts for nearly 97 percent of the total weight, contains high-content Fe (accounting for 10-45 percent of the total weight) and a small amount of Cr and is completely discarded as solid waste. At present, impurities such as calcium and magnesium can be removed by a chemical method, and nickel and cobalt can be separated from other impurity elements (iron, manganese, zinc and copper) by using an extracting agent such as P204 and P507. However, it is known that the solution obtained by acid leaching laterite-nickel ore or other nickel-cobalt raw materials or other substances obtained from the solution contains high-content impurities such as manganese, magnesium, zinc, calcium and the like, and each impurity can be more difficult to be effectively separated by using the prior art; meanwhile, the impurities are easy to form interference phases under a P204 and P507 system, so that the extraction of nickel and cobalt is greatly reduced, and the waste of resources is caused.
Disclosure of Invention
The first purpose of the invention is to provide a method for extracting ions in mineral liquid. The extraction method can effectively extract certain ions in the mineral liquid, and the recovery rate of the ions can reach more than 95%.
The extraction method comprises the following steps:
1) carrying out sodium soap on the P204 organic phase, adding a nickel sulfate solution to carry out nickel soap reaction until nickel ions replace sodium ions in the P204 organic phase to obtain a nickel-P204 organic phase;
2) adding the mineral liquid into the nickel-P204 organic phase, wherein the ratio of O to A is 1: 2-4: 1, fully mixing, and standing to obtain a first extract phase and a first raffinate;
3) adding 0.1-2N sulfuric acid into the first extraction phase, fully reacting, and standing to obtain a second raffinate and a second extraction phase;
4) adding 0.01-2N hydrochloric acid into the second extraction phase, fully reacting, and standing to obtain a third raffinate and a third extraction phase;
the mineral liquid at least contains iron, nickel, cobalt, manganese, magnesium, copper, zinc and calcium ions; the pH value of the mineral liquid is 4-5.
In step 3) and step 4), the reaction is preferably carried out for at least 5 min.
Wherein, in the step 3), the concentration of the sulfuric acid is preferably 1-2N. In the step 4), the concentration of the hydrochloric acid is preferably 1-2N.
Among them, the P204 organic phase used when the sodium soap is carried out in step 1) is preferably an organic phase obtained by mixing a blank P204 organic phase and mineral spirit in a volume ratio of 1: 3. Among them, the saponification rate of the sodium soap in step 1) is preferably not higher than 50%. Wherein P204 is diisooctyl phosphate.
The first extraction phase mainly comprises a P204 organic phase loaded with iron, calcium, copper, zinc and manganese ions, and the first raffinate comprises nickel, cobalt and magnesium ions. And step 3) is a nickel washing step, so that the subsequent extraction effect can be effectively further improved, the second extraction phase mainly comprises a P204 organic phase loaded with iron, calcium, copper, zinc and manganese ions, and the second raffinate comprises nickel, cobalt and magnesium ions. In the actual process, the first raffinate and the second raffinate are mixed for subsequent treatment. Wherein, preferably, the second raffinate and the mineral liquid are added into the step 2) together, and are fully mixed with the nickel-P204 organic phase when the ratio is 1: 2-4: 1.
Through the treatment, the zinc and the manganese can be completely transferred into the third extraction phase, namely the third extraction phase contains zinc-P204, manganese-P204 and blank-P204; the copper ions can be completely separated into the third raffinate, and the copper ions and the calcium ions can be effectively separated from a plurality of ions without influencing the subsequent separation of other ions. The recovery rate of copper ions is as high as 95%. Wherein the third raffinate contains calcium ions and copper ions. Iron powder can be added into the third raffinate, and the iron powder can be completely replaced to obtain the precipitated copper and the solution containing calcium ions. In a practical process, the solution of calcium ions can be directly fed into water for treatment.
The mineral liquid in the invention can be a solution prepared by dissolving MHP prepared from laterite-nickel ore in acid.
In a preferred embodiment of the invention, the concentration of iron in the mineral liquid is less than 100mg/L, the concentration of nickel is 80000-110000 mg/L, the concentration of cobalt is 2000-10000 mg/L, the concentration of manganese is 2000-20000 mg/L, the concentration of magnesium is 1000-15000 mg/L, the concentration of copper is 10-1000 mg/L, the concentration of zinc is 100-10000 mg/L, and the concentration of calcium is 10-2000 mg/L.
In a preferred embodiment of the present invention, the extraction method further includes:
adding 2-6N hydrochloric acid into the third extraction phase, fully reacting, and standing to obtain a fourth raffinate and a fourth extraction phase;
and adding 6-12N hydrochloric acid into the fourth extraction phase, fully reacting, and standing to obtain a fifth raffinate and a fifth extraction phase.
Wherein the concentration of the hydrochloric acid added to the third extraction phase is more preferably 5N. The concentration of the hydrochloric acid added to the third extraction phase is more preferably 12N.
In the above reaction, it is preferable that the reaction is carried out sufficiently for at least 5 min.
Through the steps, the third extraction phase containing the P204 organic phase loaded with zinc and manganese and the blank P204 organic phase can be converted into the fourth extraction phase containing iron-P204 and the blank-P204 and the fourth extraction liquid containing zinc ions and manganese ions. And then the fourth extraction phase is converted into a fifth extraction phase only containing blank, and the obtained fifth extraction phase is washed by water to obtain a dioctyl phosphate organic phase without impurities and an inorganic phase containing iron ions. The iron ions can be separated into the inorganic phase through the steps, and simultaneously, a blank P204 organic phase can be obtained. The blank P204 organic phase can be reused.
In a preferred embodiment of the present invention, in order to further separate effective ions, the extraction method further comprises:
carrying out sodium soap on the P507 organic phase, adding nickel sulfate to carry out nickel soap reaction until nickel ions replace sodium ions in the P507 organic phase to obtain a nickel-P507 organic phase;
and adding the nickel-P507 organic phase into the first raffinate, wherein the ratio of O to A is 1: 2-4: 1, fully mixing, and standing to obtain a sixth extract phase and a sixth raffinate.
The P507 organic phase used is preferably an organic phase obtained by mixing the blank P507 organic phase and solvent oil in a volume ratio of 1: 3. Among them, the saponification rate of the sodium soap is preferably not higher than 50%. Wherein P507 is 2-ethylhexyl phosphate mono-2-ethylhexyl ester.
Wherein, the first raffinate mainly contains nickel, cobalt and magnesium ions. The sixth extraction phase mainly contains a P507 organic phase loaded with cobalt and magnesium and a P507 organic phase loaded with a small amount of nickel. The sixth raffinate contains nickel sulfate. The nickel sulfate in the sixth raffinate may be recovered using means commonly used in the art.
In order to further improve the recovery rate of nickel, the extraction method further comprises the following steps:
and adding 0.1-2N sulfuric acid into the sixth extraction phase, fully reacting, and standing to obtain a seventh raffinate and a seventh extraction phase.
Wherein the concentration of the sulfuric acid added to the sixth extraction phase is more preferably 1N.
Wherein, the seventh extraction phase mainly comprises a P507 organic phase loaded with cobalt and magnesium and a blank P507 organic phase.
Preferably, the seventh raffinate is added into the first raffinate, and the subsequent steps are continued, so that the seventh raffinate can be recycled, and the recovery rate is increased. Namely, mixing the first raffinate and the seventh raffinate, adding the nickel-P507 organic phase into the mixture, fully mixing the mixture and standing the mixture to obtain a sixth extract phase and a sixth raffinate, wherein the ratio of O to A is 1: 2-4: 1.
And (4) deoiling, filtering, demagnetizing and crystallizing the sixth raffinate to obtain nickel sulfate crystals. The recovery rate of nickel is as high as 98%, and the purity of the obtained nickel sulfate can be as high as 98%. In the actual production process, the obtained nickel sulfate can be directly added into a finished product barrel and enters a crystal workshop.
In a preferred embodiment of the present invention, in order to further separate effective ions, the extraction method further comprises:
and adding 2-4N sulfuric acid into the seventh extraction phase, fully reacting, and standing to obtain an eighth raffinate and an eighth extraction phase.
Wherein the concentration of the sulfuric acid added to the seventh extraction phase is more preferably 3N.
After the above treatment, the eighth raffinate contains a small amount of nickel sulfate, a small amount of cobalt sulfate and a large amount of magnesium sulfate. Wherein the concentration of nickel and cobalt ions in the raffinate is less than 100 mg/L. The nickel and cobalt sulfate may be removed using methods commonly used in the art to obtain a solution of magnesium sulfate. Specifically, the magnesium sulfate solution can be subjected to primary nickel-cobalt precipitation to obtain the magnesium sulfate solution, and the magnesium sulfate solution is directly subjected to water treatment in an actual process. The eighth raffinate phase contains a cobalt-loaded P507 organic phase.
And adding 4-7N sulfuric acid into the eighth extraction phase, fully reacting, and standing to obtain a ninth raffinate and a ninth extraction phase.
And the ninth raffinate is cobalt sulfate solution, and is subjected to oil removal, filtration, magnetic separation removal, concentration and crystallization to obtain cobalt sulfate crystals. The recovery rate of cobalt is as high as 97%, and the purity of the obtained cobalt sulfate can be as high as 98%. In the actual production process, the obtained cobalt sulfate can be directly added into a finished product barrel and enters a crystal workshop. Wherein the concentration of the sulfuric acid added to the eighth extraction phase is more preferably 5N.
And preferably, 6-12N concentrated hydrochloric acid is added into the obtained iron-loaded organic phase P507 contained in the ninth extraction phase, and the ninth extraction phase is fully reacted and then stands to obtain a tenth raffinate and a tenth extraction phase.
Washing the obtained tenth extraction phase with water to obtain a blank organic phase P507 and an inorganic phase containing iron ions. The blank organic phase P507 can be reused.
In order to further extract zinc ions and manganese ions, in a preferred embodiment of the present invention, the following steps may be included:
and (3) carrying out sodium soap treatment on the P204 organic phase, controlling the saponification rate to be not higher than 65%, adding the fourth raffinate into the P204 organic phase after the reaction is completed, fully mixing the fourth raffinate with the O: A ratio of 1: 1-3: 1, and standing the mixture to obtain an eleventh extract phase and an eleventh raffinate.
Among them, the P204 organic phase used in the case of performing the sodium soap is preferably an organic phase obtained by mixing the blank P204 organic phase and the mineral spirit in a volume ratio of 1: 3.
The eleventh extraction phase contains a P204 organic phase loaded with manganese and zinc and a small amount of a P204 organic phase loaded with sodium, and in order to further improve the recovery purity of manganese and zinc ions, 0.1N-2N sulfuric acid can be added into the eleventh extraction phase, and the twelfth extraction phase and the twelfth raffinate are obtained after full reaction and standing. Wherein the concentration of the sulfuric acid added to the eleventh extraction phase is more preferably 0.8 to 1N.
In this case, the twelfth extraction phase contains only the manganese-and zinc-loaded P204 organic phase. The manganese and zinc in the twelfth extract phase can be separately recovered using methods commonly used in the art.
In a preferred embodiment of the invention, 2 to 4N sulfuric acid may be added to the twelfth extract phase, and after sufficient reaction, the mixture is allowed to stand to obtain a thirteenth extract phase and a thirteenth raffinate; and (4) removing oil, filtering, removing magnetic particles and concentrating and crystallizing the thirteenth raffinate to obtain manganese sulfate crystals. The purity of the manganese sulfate crystal obtained by the method is up to more than 98%, wherein the recovery rate of manganese ions is up to 95%. In the actual production process, the obtained manganese sulfate can be directly added into a finished product barrel and enters a crystal workshop.
In the above step, the thirteenth extract phase contains a P204 organic phase loaded with zinc, 4 to 7N sulfuric acid may be added thereto, and after sufficient reaction, the thirteenth extract phase and the fourteenth raffinate are obtained by standing. At the moment, the fourteenth raffinate is manganese sulfate solution, and is subjected to oil removal, filtration, magnetic separation removal, concentration and crystallization to obtain zinc sulfate crystals. The zinc sulfate crystal obtained by the step is up to more than 98%, and the recovery rate of zinc ions is up to 95%. In the actual production process, the obtained zinc sulfate can be directly added into a finished product barrel and enters a crystal workshop.
The obtained fourteenth extraction phase can be processed to obtain a blank organic phase P204 without impurities, preferably, concentrated hydrochloric acid is added into the fourteenth extraction phase, and the mixture is allowed to stand after reacting for at least 5min to obtain a fifteenth raffinate and a fifteenth extraction phase; washing the fifteenth extraction phase with water to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions. The blank organic phase P204 can be reused.
The extraction method can effectively separate copper, calcium and other ions, more preferably nickel, cobalt, manganese and zinc ions, and the recovery rate of the copper, nickel, cobalt, manganese and zinc ions is more than 90%, preferably more than 95%. The method provided by the invention can directly obtain nickel sulfate, cobalt sulfate, manganese sulfate and zinc sulfate with the purity of more than 95 percent, can realize the conversion from laterite-nickel ore directly to nickel sulfate, cobalt sulfate, manganese sulfate and zinc sulfate, and has important application in practical production. Compared with the prior art, the method greatly simplifies the steps, effectively saves resources and reduces the cost on the basis of ensuring the purity and the recovery rate.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available.
Example 1
The embodiment provides an extraction method of mineral liquid containing various ions, which comprises the following steps:
1) MHP prepared from laterite-nickel ore is dissolved in sulfuric acid to obtain a raw material solution, namely a mineral solution, wherein the mineral solution contains nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5; the MHP can be prepared by leaching laterite-nickel ore as a raw material through one or more of normal pressure, high pressure and oxygen pressure; the iron content in the mineral liquid is less than 100mg/L, nickel content is 90g/L, cobalt content is 6g/L, manganese content is 16g/L, magnesium content is 7g/L, copper content is 0.2g/L, zinc content is 2g/L, and calcium content is 0.2 g/L.
2) Ni-P204 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic phase (the volume ratio of P204 to the solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding a nickel sulfate solution into the mixture to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, adding a mineral liquid into the mixture after the reaction is completed, and controlling the ratio of O: mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a first extraction phase and a first raffinate; the first raffinate was directly subjected to the following step 7) Ni-P507 extraction.
3) P204 nickel washing: adding 1N sulfuric acid into the first extraction phase in the step 2), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a second raffinate and a second extraction phase; mixing the second raffinate with the mineral liquid in the step 2) for circular extraction.
4) P204 back extraction 1), namely adding 1N hydrochloric acid into the second extraction phase obtained in the step 3), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a third raffinate and a third extraction phase; and adding iron powder into the third raffinate, and performing iron powder replacement to obtain precipitated copper and a solution containing calcium ions, wherein the recovery rate of copper is within 95 percent, the purity is within 80 percent, and the solution containing the calcium ions is directly subjected to water treatment.
5) P204 back extraction 2: adding 5N hydrochloric acid into the third extraction phase obtained in the step 4), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourth raffinate and a fourth extraction phase;
6) p204, iron reversal: adding 12N concentrated hydrochloric acid into the fourth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifth extraction phase and a fifth raffinate, washing the fifth extraction phase with water, and clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions; wherein, the blank organic phase P204 can be reused.
7) Ni-P507 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P507 blank organic phase (the volume ratio of P507: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding nickel sulfate into the blank organic phase to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, and after the reaction is completed, adding a first raffinate obtained in the step 2), and controlling the ratio of O: and (3) mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a sixth extraction phase and a sixth raffinate.
8) P507, nickel washing: adding 1N sulfuric acid into the sixth extraction phase in the step 7), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining seventh raffinate and a seventh extraction phase. Mixing the seventh raffinate with the first raffinate in the step 7), adding the mixture into the system, and performing circulating extraction.
9) And (3) removing oil from the sixth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain nickel sulfate crystals, wherein the yield is within 98 percent, and the purity is up to more than 98 percent.
10) P507 back extraction 1), namely adding 3N sulfuric acid into the seventh extraction phase obtained in the step 8), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain an eighth raffinate and an eighth extraction phase; and carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution, and directly carrying out water treatment.
11) P507 back extraction 2: adding 5N sulfuric acid into the eighth extraction phase obtained in the step 10), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a ninth raffinate and a ninth extraction phase.
12) P507 reverse iron: adding 12N concentrated hydrochloric acid into the ninth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a tenth extraction phase and a tenth raffinate, washing the tenth extraction phase with water, and clarifying to obtain a blank organic phase P507 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P507 can be recycled;
13) deoiling and filtering the ninth raffinate obtained in the step 11), evaporating, concentrating and crystallizing the solution after the magnetic separation is removed to obtain cobalt sulfate crystals, wherein the recovery rate is up to 97%, and the purity is up to more than 98%.
14) Mn-P204 sodium soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic substance (the volume ratio of P204: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 65%, adding the fourth raffinate obtained in the step 5) after the reaction is completed, and controlling the ratio of O: and (3) mixing A to 2:1, reacting and mixing for about 5 minutes, standing and clarifying for about 8 minutes to obtain an eleventh extract phase and an eleventh raffinate.
15) P204 sodium washing: adding 1N sulfuric acid into the eleventh extraction phase in the step 14), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a twelfth raffinate and a twelfth extraction phase; the twelfth raffinate directly enters the Mn-P204 extraction.
16) P204 back extraction 1), namely adding 3N sulfuric acid into the twelfth extraction phase obtained in the step 15), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a thirteenth raffinate and a thirteenth extraction phase; and (3) removing oil from the thirteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation removal to obtain manganese sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
17) P204 back extraction 2: adding 5N sulfuric acid into the thirteenth extraction phase obtained in the step 16), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourteenth raffinate and a fourteenth extraction phase; and (3) removing oil from the fourteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain zinc sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
18) P204, iron reversal: adding 12N concentrated hydrochloric acid into the fourteenth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifteenth extraction phase and a fifteenth raffinate, washing the fifteenth extraction phase with water, clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P204 can be recycled.
Example 2
The embodiment provides an extraction method of mineral liquid containing various ions, which comprises the following steps:
1) MHP prepared from laterite-nickel ore is dissolved in sulfuric acid to obtain a raw material solution, namely a mineral solution, wherein the mineral solution contains nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5; the MHP can be prepared by leaching laterite-nickel ore as a raw material through one or more of normal pressure, high pressure and oxygen pressure; the iron content in the mineral liquid is less than 100mg/L, the nickel content is 80g/L, the cobalt content is 2g/L, the manganese content is 2g/L, the magnesium content is 1g/L, the copper content is 0.01g/L, the zinc content is 0.1g/L and the calcium content is 0.01 g/L.
2) Ni-P204 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic phase (the volume ratio of P204 to the solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding a nickel sulfate solution into the mixture to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, adding a mineral liquid into the mixture after the reaction is completed, and controlling the ratio of O: mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a first extraction phase and a first raffinate; the first raffinate was directly subjected to the following step 7) Ni-P507 extraction.
3) P204 nickel washing: adding 0.2N sulfuric acid into the first extraction phase in the step 2), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a second raffinate and a second extraction phase; mixing the second raffinate with the mineral liquid in the step 2) for circular extraction.
4) P204 back extraction 1, adding 0.5N hydrochloric acid into the second extraction phase obtained in the step 3), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a third raffinate and a third extraction phase; and adding iron powder into the third raffinate, and performing iron powder replacement to obtain precipitated copper and a solution containing calcium ions, wherein the recovery rate of copper is within 95 percent, the purity is within 80 percent, and the solution containing the calcium ions is directly subjected to water treatment.
5) P204 back extraction 2: adding 2N hydrochloric acid into the third extraction phase obtained in the step 4), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourth raffinate and a fourth extraction phase;
6) p204, iron reversal: adding 6N hydrochloric acid into the fourth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifth extraction phase and a fifth raffinate, washing the fifth extraction phase with water, and clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions; wherein, the blank organic phase P204 can be reused.
7) Ni-P507 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P507 blank organic phase (the volume ratio of P507: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding nickel sulfate into the blank organic phase to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, and after the reaction is completed, adding a first raffinate obtained in the step 2), and controlling the ratio of O: and (3) mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a sixth extraction phase and a sixth raffinate.
8) P507, nickel washing: adding 0.1N sulfuric acid into the sixth extraction phase in the step 7), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining seventh raffinate and a seventh extraction phase. Mixing the seventh raffinate with the first raffinate in the step 7), adding the mixture into the system, and performing circulating extraction.
9) And (3) deoiling and filtering the sixth raffinate, and evaporating, concentrating and crystallizing the solution after magnetic separation to obtain nickel sulfate crystals, wherein the yield is within 98 percent, and the purity is up to more than 98 percent.
10) P507 back extraction 1), namely adding 2N sulfuric acid into the seventh extraction phase obtained in the step 8), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain an eighth raffinate and an eighth extraction phase; and carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution, and directly carrying out water treatment.
11) P507 back extraction 2: adding 4N sulfuric acid into the eighth extraction phase obtained in the step 10), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a ninth raffinate and a ninth extraction phase.
12) P507 reverse iron: adding 6N concentrated hydrochloric acid into the ninth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a tenth extraction phase and a tenth raffinate, washing the tenth extraction phase with water, and clarifying to obtain a blank organic phase P507 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P507 can be recycled;
13) deoiling and filtering the ninth raffinate obtained in the step 11), evaporating, concentrating and crystallizing the solution after the magnetic separation is removed to obtain cobalt sulfate crystals, wherein the recovery rate is up to 97%, and the purity is up to more than 98%.
14) Mn-P204 sodium soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic substance (the volume ratio of P204: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 65%, adding the fourth raffinate obtained in the step 5) after the reaction is completed, and controlling the ratio of O: and (3) mixing A to 1:1, reacting and mixing for about 5 minutes, standing and clarifying for about 8 minutes to obtain an eleventh extract phase and an eleventh raffinate.
15) P204 sodium washing: adding 0.1N sulfuric acid into the eleventh extraction phase in the step 14), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a twelfth raffinate and a twelfth extraction phase; the twelfth raffinate directly enters the Mn-P204 extraction.
16) P204 back extraction 1), namely adding 2N sulfuric acid into the twelfth extraction phase obtained in the step 15), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a thirteenth raffinate and a thirteenth extraction phase; and (3) removing oil from the thirteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation removal to obtain manganese sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
17) P204 back extraction 2: adding 4N sulfuric acid into the thirteenth extraction phase obtained in the step 16), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourteenth raffinate and a fourteenth extraction phase; and (3) removing oil from the fourteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain zinc sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
18) P204, iron reversal: adding 6N concentrated hydrochloric acid into the fourteenth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifteenth extraction phase and a fifteenth raffinate, washing the fifteenth extraction phase with water, clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P204 can be recycled.
Example 3
The embodiment provides an extraction method of mineral liquid containing various ions, which comprises the following steps:
1) MHP prepared from laterite-nickel ore is dissolved in sulfuric acid to obtain a raw material solution, namely a mineral solution, wherein the mineral solution contains nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5; the MHP can be prepared by leaching laterite-nickel ore as a raw material through one or more of normal pressure, high pressure and oxygen pressure; the iron content in the mineral liquid is less than 100mg/L, the nickel content is 110g/L, the cobalt content is 10g/L, the manganese content is 20g/L, the magnesium content is 15g/L, the copper content is 1g/L, the zinc content is 10g/L, and the calcium content is 2 g/L.
2) Ni-P204 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic phase (the volume ratio of P204 to the solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding a nickel sulfate solution into the mixture to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, adding a mineral liquid into the mixture after the reaction is completed, and controlling the ratio of O: mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a first extraction phase and a first raffinate; the first raffinate was directly subjected to the following step 7) Ni-P507 extraction.
3) P204 nickel washing: adding 2N sulfuric acid into the first extraction phase in the step 2), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a second raffinate and a second extraction phase; mixing the second raffinate with the mineral liquid in the step 2) for circular extraction.
4) P204 back extraction 1, adding 2N hydrochloric acid into the second extraction phase obtained in the step 3), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a third raffinate and a third extraction phase; and adding iron powder into the third raffinate, and performing iron powder replacement to obtain precipitated copper and a solution containing calcium ions, wherein the recovery rate of copper is within 95 percent, the purity is within 80 percent, and the solution containing the calcium ions is directly subjected to water treatment.
5) P204 back extraction 2: adding 6N hydrochloric acid into the third extraction phase obtained in the step 4), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourth raffinate and a fourth extraction phase;
6) p204, iron reversal: adding 12N hydrochloric acid into the fourth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifth extraction phase and a fifth raffinate, washing the fifth extraction phase with water, and clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions; wherein, the blank organic phase P204 can be reused.
7) Ni-P507 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P507 blank organic phase (the volume ratio of P507: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding nickel sulfate into the blank organic phase to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, and after the reaction is completed, adding a first raffinate obtained in the step 2), and controlling the ratio of O: and mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a sixth extraction phase and a sixth raffinate.
8) P507, nickel washing: adding 2N sulfuric acid into the sixth extraction phase in the step 7), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining seventh raffinate and a seventh extraction phase. Mixing the seventh raffinate with the first raffinate in the step 7), adding the mixture into the system, and performing circulating extraction.
9) And (3) removing oil from the sixth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain nickel sulfate crystals, wherein the yield is within 98 percent, and the purity is up to more than 98 percent.
10) P507 back extraction 1), namely adding 4N sulfuric acid into the seventh extraction phase obtained in the step 8), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain an eighth raffinate and an eighth extraction phase; and carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution, and directly carrying out water treatment.
11) P507 back extraction 2: adding 7N sulfuric acid into the eighth extraction phase obtained in the step 10), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a ninth raffinate and a ninth extraction phase.
12) P507 reverse iron: adding 12N concentrated hydrochloric acid into the ninth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a tenth extraction phase and a tenth raffinate, washing the tenth extraction phase with water, and clarifying to obtain a blank organic phase P507 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P507 can be recycled;
13) deoiling and filtering the ninth raffinate obtained in the step 11), evaporating, concentrating and crystallizing the solution after the magnetic separation is removed to obtain cobalt sulfate crystals, wherein the recovery rate is up to 97%, and the purity is up to more than 98%.
14) Mn-P204 sodium soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic substance (the volume ratio of P204: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 65%, adding the fourth raffinate obtained in the step 5) after the reaction is completed, and controlling the ratio of O: and (3) mixing the A with the A: 1 for about 5 minutes, standing and clarifying for about 8 minutes to obtain an eleventh extract phase and an eleventh raffinate.
15) P204 sodium washing: adding 2N sulfuric acid into the eleventh extraction phase in the step 14), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a twelfth raffinate and a twelfth extraction phase; the twelfth raffinate directly enters the Mn-P204 extraction.
16) P204 back extraction 1), namely adding 4N sulfuric acid into the twelfth extraction phase obtained in the step 15), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a thirteenth raffinate and a thirteenth extraction phase; and (3) removing oil from the thirteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation removal to obtain manganese sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
17) P204 back extraction 2: adding 7N sulfuric acid into the thirteenth extraction phase obtained in the step 16), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourteenth raffinate and a fourteenth extraction phase; and (3) removing oil from the fourteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain zinc sulfate crystals, wherein the recovery rate is up to 95%, and the purity is up to more than 98%.
18) P204, iron reversal: adding 12N concentrated hydrochloric acid into the fourteenth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifteenth extraction phase and a fifteenth raffinate, washing the fifteenth extraction phase with water, clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P204 can be recycled.
Comparative example 1
The comparative example provides a method for extracting mineral liquid containing various ions, comprising the following steps:
1) MHP prepared from laterite-nickel ore is dissolved in sulfuric acid to obtain a raw material solution, namely a mineral solution, wherein the mineral solution contains nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5; the MHP can be prepared by leaching laterite-nickel ore as a raw material through one or more of normal pressure, high pressure and oxygen pressure; the iron content in the mineral liquid is less than 100mg/L, nickel content is 90g/L, cobalt content is 6g/L, manganese content is 16g/L, magnesium content is 7g/L, copper content is 0.2g/L, zinc content is 2g/L, and calcium content is 0.2 g/L.
2) Ni-P204 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic phase (the volume ratio of P204 to the solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding a nickel sulfate solution into the mixture to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, adding a mineral liquid into the mixture after the reaction is completed, and controlling the ratio of O: mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a first extraction phase and a first raffinate; the first raffinate was directly subjected to the following step 7) Ni-P507 extraction.
3) P204 nickel washing: adding 0.08N sulfuric acid into the first extraction phase in the step 2), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a second raffinate and a second extraction phase; mixing the second raffinate with the mineral liquid in the step 2) for circular extraction.
4) P204 back extraction 1), namely adding 1N hydrochloric acid into the second extraction phase obtained in the step 3), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a third raffinate and a third extraction phase; and adding iron powder into the third raffinate, and performing iron powder replacement to obtain precipitated copper and a solution containing calcium ions, wherein the recovery rate of copper is 85%, the purity of copper is 80%, and the solution containing the calcium ions is directly subjected to water treatment.
5) P204 back extraction 2: adding 0.8N hydrochloric acid into the third extraction phase obtained in the step 4), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourth raffinate and a fourth extraction phase;
6) p204, iron reversal: adding 12N concentrated hydrochloric acid into the fourth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifth extraction phase and a fifth raffinate, washing the fifth extraction phase with water, and clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions; wherein, the blank organic phase P204 can be reused.
7) Ni-P507 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P507 blank organic phase (the volume ratio of P507: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding nickel sulfate into the blank organic phase to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, and after the reaction is completed, adding a first raffinate obtained in the step 2), and controlling the ratio of O: and (3) mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a sixth extraction phase and a sixth raffinate.
8) P507, nickel washing: adding 0.08N sulfuric acid into the sixth extraction phase in the step 7), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining seventh raffinate and seventh extraction phase. Mixing the seventh raffinate with the first raffinate in the step 7), adding the mixture into the system, and performing circulating extraction.
9) And (3) removing oil from the sixth raffinate, filtering, and evaporating, concentrating and crystallizing the solution after magnetic separation to obtain nickel sulfate crystals, wherein the yield is less than 90% and the purity is 85%.
10) P507 back extraction 1), namely adding 0.08N sulfuric acid into the seventh extraction phase obtained in the step 8), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain an eighth raffinate and an eighth extraction phase; and carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution, and directly carrying out water treatment.
11) P507 back extraction 2: adding 0.8N sulfuric acid into the eighth extraction phase obtained in the step 10), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a ninth raffinate and a ninth extraction phase.
12) P507 reverse iron: adding 12N concentrated hydrochloric acid into the ninth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a tenth extraction phase and a tenth raffinate, washing the tenth extraction phase with water, and clarifying to obtain a blank organic phase P507 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P507 can be recycled;
13) deoiling and filtering the ninth raffinate obtained in the step 11), and evaporating, concentrating and crystallizing the solution after the magnetic separation is removed to obtain cobalt sulfate crystals, wherein the recovery rate is 85% and the purity is 85%.
14) Mn-P204 sodium soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic substance (the volume ratio of P204: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 65%, adding the fourth raffinate obtained in the step 5) after the reaction is completed, and controlling the ratio of O: and (3) mixing A to 1:2, reacting and mixing for about 5 minutes, standing and clarifying for about 8 minutes to obtain an eleventh extract phase and an eleventh raffinate.
15) P204 sodium washing: adding 0.08N sulfuric acid into the eleventh extraction phase in the step 14), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining twelfth raffinate and twelfth extraction phase; the twelfth raffinate directly enters the Mn-P204 extraction.
16) P204 back extraction 1), namely adding 0.08N sulfuric acid into the twelfth extraction phase obtained in the step 15), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain thirteenth raffinate and a thirteenth extraction phase; and (3) removing oil from the thirteenth raffinate, filtering, and evaporating, concentrating and crystallizing the solution subjected to magnetic separation removal to obtain manganese sulfate crystals, wherein the recovery rate is 75% and the purity is 80%.
17) P204 back extraction 2: adding 0.8N sulfuric acid into the thirteenth extraction phase obtained in the step 16), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourteenth raffinate and a fourteenth extraction phase; and (3) removing oil from the fourteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain zinc sulfate crystals, wherein the recovery rate is 65% and the purity is 80%.
18) P204, iron reversal: adding 12N concentrated hydrochloric acid into the fourteenth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifteenth extraction phase and a fifteenth raffinate, washing the fifteenth extraction phase with water, clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P204 can be recycled.
Comparative example 2
The comparative example provides a method for extracting mineral liquid containing various ions, comprising the following steps:
1) MHP prepared from laterite-nickel ore is dissolved in sulfuric acid to obtain a raw material solution, namely a mineral solution, wherein the mineral solution contains nickel, cobalt, manganese, magnesium, copper, zinc and calcium; the pH value of the mineral liquid is 4-5; the MHP can be prepared by leaching laterite-nickel ore as a raw material through one or more of normal pressure, high pressure and oxygen pressure; the iron content in the mineral liquid is less than 100mg/L, nickel content is 90g/L, cobalt content is 6g/L, manganese content is 16g/L, magnesium content is 7g/L, copper content is 0.2g/L, zinc content is 2g/L, and calcium content is 0.2 g/L.
2) Ni-P204 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic phase (the volume ratio of P204 to the solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding a nickel sulfate solution into the mixture to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, adding a mineral liquid into the mixture after the reaction is completed, and controlling the ratio of O: mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a first extraction phase and a first raffinate; the first raffinate was directly subjected to the following step 7) Ni-P507 extraction.
3) P204 nickel washing: adding 3N sulfuric acid into the first extraction phase in the step 2), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a second raffinate and a second extraction phase; mixing the second raffinate with the mineral liquid in the step 2) for circular extraction.
4) P204 back extraction 1, adding 3N hydrochloric acid into the second extraction phase obtained in the step 3), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a third raffinate and a third extraction phase; and adding iron powder into the third raffinate, and performing iron powder replacement to obtain precipitated copper and a solution containing calcium ions, wherein the recovery rate of copper is 60%, the purity of copper is 80%, and the solution containing the calcium ions is directly subjected to water treatment.
5) P204 back extraction 2: adding 12N hydrochloric acid into the third extraction phase obtained in the step 4), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourth raffinate and a fourth extraction phase;
6) p204, iron reversal: adding 12N concentrated hydrochloric acid into the fourth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifth extraction phase and a fifth raffinate, washing the fifth extraction phase with water, and clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions; wherein, the blank organic phase P204 can be reused.
7) Ni-P507 sodium soap, nickel soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P507 blank organic phase (the volume ratio of P507: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 50%, adding nickel sulfate into the blank organic phase to perform nickel soap reaction until nickel ions replace sodium ions in a saponified organic phase, and after the reaction is completed, adding a first raffinate obtained in the step 2), and controlling the ratio of O: and (3) mixing the organic phase and the pre-extraction solution for about 5 minutes, standing and clarifying for about 8 minutes to obtain a sixth extraction phase and a sixth raffinate.
8) P507, nickel washing: adding 6N sulfuric acid into the sixth extraction phase in the step 7), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining seventh raffinate and a seventh extraction phase. Mixing the seventh raffinate with the first raffinate in the step 7), adding the mixture into the system, and performing circulating extraction.
9) And (3) removing oil and filtering the sixth raffinate, and evaporating, concentrating and crystallizing the solution after removing the magnetic difference to obtain nickel sulfate crystals, wherein the yield is 95% and the purity is 75%.
10) P507 back extraction 1), namely adding 6N sulfuric acid into the seventh extraction phase obtained in the step 8), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain an eighth raffinate and an eighth extraction phase; and carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution, and directly carrying out water treatment.
11) P507 back extraction 2: adding 12N sulfuric acid into the eighth extraction phase obtained in the step 10), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a ninth raffinate and a ninth extraction phase.
12) P507 reverse iron: adding 12N concentrated hydrochloric acid into the ninth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a tenth extraction phase and a tenth raffinate, washing the tenth extraction phase with water, and clarifying to obtain a blank organic phase P507 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P507 can be recycled;
13) deoiling and filtering the ninth raffinate obtained in the step 11), and evaporating, concentrating and crystallizing the solution after the magnetic separation is removed to obtain cobalt sulfate crystals, wherein the recovery rate is 20% and the purity is 85%.
14) Mn-P204 sodium soap + extraction: adding sodium hydroxide with the mass fraction of 32% into a P204 blank organic substance (the volume ratio of P204: solvent oil is 1: 3) to perform sodium soap, controlling the saponification rate within 65%, adding the fourth raffinate obtained in the step 5) after the reaction is completed, and controlling the ratio of O: and (3) mixing A to 4:1, reacting and mixing for about 5 minutes, standing and clarifying for about 8 minutes to obtain an eleventh extract phase and an eleventh raffinate.
15) P204 sodium washing: adding 4N sulfuric acid into the eleventh extraction phase in the step 14), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes, and obtaining a twelfth raffinate and a twelfth extraction phase; the twelfth raffinate directly enters the Mn-P204 extraction.
16) P204 back extraction 1), namely adding 8N sulfuric acid into the twelfth extraction phase obtained in the step 15), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a thirteenth raffinate and a thirteenth extraction phase; and (3) removing oil from the thirteenth raffinate, filtering, and evaporating, concentrating and crystallizing the solution subjected to magnetic separation removal to obtain manganese sulfate crystals, wherein the recovery rate is 70% and the purity is 30%.
17) P204 back extraction 2: adding 12N sulfuric acid into the thirteenth extraction phase obtained in the step 16), reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fourteenth raffinate and a fourteenth extraction phase; and (3) removing oil from the fourteenth raffinate, filtering, evaporating, concentrating and crystallizing the solution after magnetic separation to obtain zinc sulfate crystals, wherein the recovery rate is 10% and the purity is 75%.
18) P204, iron reversal: adding 12N concentrated hydrochloric acid into the fourteenth extraction phase, reacting for more than 5 minutes, standing and clarifying for more than 8 minutes to obtain a fifteenth extraction phase and a fifteenth raffinate, washing the fifteenth extraction phase with water, clarifying to obtain a blank organic phase P204 without impurities and an inorganic phase containing iron ions, wherein the obtained blank organic phase P204 can be recycled.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A method for extracting ions in mineral liquid is characterized by comprising the following steps:
carrying out sodium soap on the P204 organic phase, adding a nickel sulfate solution to carry out nickel soap reaction until nickel ions replace sodium ions in the organic phase to obtain a nickel-P204 organic phase;
adding the mineral liquid into the nickel-P204 organic phase, wherein the ratio of O to A is 1: 2-4: 1, fully mixing, and standing to obtain a first extract phase and a first raffinate;
adding 0.1-2N sulfuric acid into the first extraction phase, fully reacting, and standing to obtain a second raffinate and a second extraction phase;
adding 0.01-2N hydrochloric acid into the second extraction phase, fully reacting, and standing to obtain a third raffinate and a third extraction phase;
adding 2-6N hydrochloric acid into the third extraction phase, fully reacting, and standing to obtain a fourth raffinate and a fourth extraction phase;
adding 6-12N hydrochloric acid into the fourth extraction phase, reacting for at least 5min, and standing to obtain a fifth raffinate and a fifth extraction phase;
washing the fifth extraction phase with water to obtain a P204 organic phase without impurities and an inorganic phase containing iron ions;
carrying out sodium soap on the P507 organic phase, adding nickel sulfate to carry out nickel soap reaction until nickel ions replace sodium ions in the P507 organic phase to obtain a nickel-P507 organic phase;
adding the nickel-P507 organic phase into the first raffinate, wherein the ratio of O to A is 1: 2-4: 1, fully mixing, and standing to obtain a sixth extract phase and a sixth raffinate;
adding 0.1-2N sulfuric acid into the sixth extraction phase, fully reacting, and standing to obtain a seventh raffinate and a seventh extraction phase; removing oil, filtering, removing magnetic particles, concentrating and crystallizing the sixth raffinate to obtain nickel sulfate crystals; mixing the seventh raffinate with the first raffinate, and adding the nickel-P507 organic phase into the mixture for extraction;
adding 2-4N sulfuric acid into the seventh extraction phase, fully reacting, and standing to obtain an eighth raffinate and an eighth extraction phase; carrying out primary nickel and cobalt precipitation on the eighth raffinate to obtain a magnesium sulfate solution;
adding 4-7N sulfuric acid into the eighth extraction phase, fully reacting, and standing to obtain a ninth raffinate and a ninth extraction phase;
carrying out oil removal, filtration and magnetic separation on the ninth raffinate, and then concentrating and crystallizing to obtain cobalt sulfate crystals;
carrying out sodium soap treatment on an organic phase of an extracting agent P204, controlling the saponification rate to be not higher than 65%, adding the fourth raffinate into the organic phase after the reaction is completed, fully mixing and standing the organic phase with the fourth raffinate, wherein the ratio of O to A is 1: 1-3: 1, and obtaining an eleventh extracted phase and an eleventh raffinate;
adding 0.1-2N sulfuric acid into the eleventh extraction phase, reacting, and standing to obtain a twelfth extraction phase and a twelfth raffinate;
adding 2-4N sulfuric acid into the twelfth extraction phase, reacting, and standing to obtain a thirteenth extraction phase and a thirteenth raffinate; removing oil, filtering, removing magnetism and the like from the thirteenth raffinate, and concentrating and crystallizing to obtain manganese sulfate crystals;
adding 4-7N sulfuric acid into the thirteenth extraction phase, reacting, and standing to obtain a fourteenth extraction phase and a fourteenth raffinate; removing oil, filtering, removing magnetism and performing concentration and crystallization on the fourteenth raffinate to obtain zinc sulfate crystals;
the mineral liquid at least contains iron, nickel, cobalt, manganese, magnesium, copper, zinc and calcium ions; the pH value of the mineral liquid is 4-5;
the mineral liquid is prepared by dissolving MHP prepared from laterite-nickel ore in acid;
the concentration of iron in the mineral liquid is less than 100mg/L, the concentration of nickel is 80000-110000 mg/L, the concentration of cobalt is 2000-10000 mg/L, the concentration of manganese is 2000-20000 mg/L, the concentration of magnesium is 1000-15000 mg/L, the concentration of copper is 10-1000 mg/L, the concentration of zinc is 100-10000 mg/L, and the concentration of calcium is 10-2000 mg/L.
2. The extraction process of claim 1, further comprising adding iron powder to the third raffinate to effect iron powder displacement to completion and obtain precipitated copper.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181666A (en) * | 2011-05-06 | 2011-09-14 | 广西银亿科技矿冶有限公司 | Method for treating red soil nickel ore leaching liquid |
| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
| KR101584120B1 (en) * | 2015-05-22 | 2016-01-13 | 성일하이텍(주) | Manufacturing method of pure nickel sulfate from leaching residue being removed cobalt of lithium secondary battery |
| CN107200364A (en) * | 2017-05-09 | 2017-09-26 | 甘肃有色冶金职业技术学院 | A kind of abstraction impurity removal method to industrial scum sulphuric leachate |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002022896A1 (en) * | 2000-09-15 | 2002-03-21 | Commonwealth Scientific And Industrial Research Organisation | Solvent extraction process for recovering nickel and cobalt from leach solutions |
| CN101532094B (en) * | 2008-03-11 | 2010-07-28 | 江西稀有稀土金属钨业集团有限公司 | Technology for full-process extracting and separating nickel and cobalt from acid material system with high content of calcium and magnesium impurities |
| CN102181665A (en) * | 2011-04-13 | 2011-09-14 | 广西银亿科技矿冶有限公司 | Method for keeping balance of sodium-magnesium-water system in technique for extracting nickel from lateritic nickel ore by wet process |
| CN103484695B (en) * | 2013-08-15 | 2015-04-01 | 中国恩菲工程技术有限公司 | Treatment method for comprehensively recovering valuable elements from laterite-nickel ore |
| CN103468979B (en) * | 2013-08-15 | 2016-02-24 | 中国恩菲工程技术有限公司 | The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag |
| WO2016209178A1 (en) * | 2015-06-22 | 2016-12-29 | Meta Ni̇kel Kobalt Madenci̇li̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ | Recovering scandium and derivatives thereof from a leach solution loaded with metals obtained as a result of leaching lateritic ores comprising nickel, cobalt and scandium, and secondary sources comprising scandium |
| CN108486369A (en) * | 2018-06-15 | 2018-09-04 | 王颖皓 | A kind of processing method of separation and Extraction nickel, cobalt, magnesium, iron in lateritic nickel ore |
-
2019
- 2019-03-13 CN CN201910187879.8A patent/CN109777954B/en active Active
- 2019-04-11 WO PCT/CN2019/082184 patent/WO2020181607A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181666A (en) * | 2011-05-06 | 2011-09-14 | 广西银亿科技矿冶有限公司 | Method for treating red soil nickel ore leaching liquid |
| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
| KR101584120B1 (en) * | 2015-05-22 | 2016-01-13 | 성일하이텍(주) | Manufacturing method of pure nickel sulfate from leaching residue being removed cobalt of lithium secondary battery |
| CN107200364A (en) * | 2017-05-09 | 2017-09-26 | 甘肃有色冶金职业技术学院 | A kind of abstraction impurity removal method to industrial scum sulphuric leachate |
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| WO2020181607A1 (en) | 2020-09-17 |
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