CN110777269B - Method for extracting calcium without saponification - Google Patents
Method for extracting calcium without saponification Download PDFInfo
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- CN110777269B CN110777269B CN201911049436.9A CN201911049436A CN110777269B CN 110777269 B CN110777269 B CN 110777269B CN 201911049436 A CN201911049436 A CN 201911049436A CN 110777269 B CN110777269 B CN 110777269B
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
Abstract
The invention belongs to the field of wet metallurgy, and discloses a method for extracting calcium without saponification, which comprises the following steps: (1) adjusting the pH of the calcium-containing aqueous phase to 3.0-5.5; (2) preparing di (2-ethylhexyl) phosphate, tributyl phosphate and a diluent into an organic phase, mixing the organic phase and a calcium-containing water phase according to the volume ratio of 1:0.5-4, extracting, and separating the water phase to obtain the calcium-containing organic phase. The combined extractant has high extraction rate of calcium and good selectivity, and the single-stage extraction rate can reach more than 90%; after 4-stage countercurrent extraction, the calcium content in the water phase can be reduced to below 1mg/L from 600mg/L, and the extraction rate can reach 99.8%.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to a method for extracting calcium without saponification.
Background
In hydrometallurgical leaching of metal minerals with acidic solutions, the calcium is usually present as Ca2+Enter solution with valuable metals, Ca2+The presence of (a) can seriously affect the quality of the product. Contains a large amount of Ca2+Of (2)The production water is easy to generate precipitates such as calcium carbonate, calcium sulfate and the like in the heating, cooling and conveying processes, and the precipitates are attached to the wall of the equipment to deposit and scale, so that the flow velocity of fluid in the pipe is reduced, the equipment is corroded, and the productivity is reduced.
Removal of Ca, commonly used in industry2+The method comprises chemical precipitation, adsorption, membrane separation, ion exchange, extraction, etc. Wherein, the precipitation method has the problems of incomplete calcium removal, complex operation, easy metal adsorption of the precipitate, environmental pollution caused by stacking filter residues and the like; the adsorption method has the advantages of strong selectivity, simple operation and the like, but has the problem of insufficient adsorption capacity, and the research on how to regenerate the adsorbent is less; removal of Ca by membrane separation2+The method has the advantages of simple operation, high efficiency, energy conservation, no phase change and good selectivity, but the surface of the membrane is easy to be polluted, so that the separation effect is reduced, the membrane needs to be cleaned regularly, certain maintenance cost is increased, the heat resistance, the drug resistance, the solvent resistance and the acid and alkali resistance of the membrane are limited, and the application range of the membrane is limited; the extraction method can be operated continuously, has the advantages of large treatment capacity, strong selectivity, high extraction rate, renewable and recyclable extracting agent and the like, and becomes a main method for removing calcium in industrial production at home and abroad.
Many studies on the removal of calcium by solvent extraction have been reported: in the process for preparing high-purity strontium carbonate, the influence of factors such as extraction equilibrium time, diluent, equilibrium pH value, temperature, water phase calcium ion concentration, extractant concentration and the like on the calcium extraction rate is examined by adopting D2EHPA (di- (2-hexyl) phosphoric acid) as an extractant and sulfonated kerosene as a diluent, and in a solution obtained by leaching crude strontium carbonate with hydrochloric acid and removing barium and iron impurities, the primary extraction rate of a D2 EHPA-sulfonated kerosene system on calcium is 46.11 percent and the saturated extraction rate is 83 percent, but the method has the defects of low extraction rate and unsuitability for precise extraction; lei Ching et al studied the extraction and removal of low-concentration calcium (Ca) from pickle liquor containing high-concentration nickel-cobalt alloy slag2+Concentration 16.3mg/L), the influence factor of calcium ion removal was examined, 10% P204+ 90% 260# kerosene was used as the organic phase, and saponification was carried out with NaOH at a saponification rate of 35%, Ca was used under conditions of aqueous phase pH 5.0, Vo: Va (volume ratio of organic phase to calcium-containing aqueous phase) 1:2, extraction time 3min, and temperature 25 ℃2+The single-stage extraction rate of (3) is 80%, and Ca is obtained by 3-stage countercurrent extraction2+The concentration is reduced to below 1mg/L, and the Ca of feed liquid required by producing high-quality cobalt sulfate and nickel sulfate products is achieved2+However, the addition of NaOH for saponification will generate sodium ions to affect the quality of the product. And the saponification process is easy to bring adverse factors such as environmental pollution, cost increase, impurity increase and the like.
Therefore, the extraction method which does not need saponification, has high calcium extraction efficiency, low extraction rate of other metals, low cost of the extractant and low energy consumption needs to be developed.
Disclosure of Invention
The invention aims to provide a method for extracting calcium without saponification, which has the advantages of high calcium extraction efficiency, low extraction rate of other metals, low extractant cost and low energy consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH of the calcium-containing aqueous phase to 3.0-5.5;
(2) preparing di (2-ethylhexyl) phosphate, tributyl phosphate and a diluent into an organic phase, mixing the organic phase and a calcium-containing aqueous phase according to the volume ratio of 1:0.5-4, extracting, and separating the aqueous phase to obtain the calcium-containing organic phase.
Preferably, the organic phase in the step (2) is composed of the following components in percentage by mass: 10-25% of an extracting agent, 10-25% of a synergistic agent and 50-80% of a diluent.
Preferably, the extractant is di (2-ethylhexyl) phosphate (P204).
Preferably, the synergist is tributyl phosphate (TBP).
Preferably, the diluent is sulfonated kerosene.
Preferably, the calcium-containing aqueous phase in the step (1) is selected from a nickel-cobalt-manganese ternary solution or calcium-containing wastewater.
More preferably, the calcium-containing aqueous phase of step (1) further comprises Ni2+、Co2+、Mn2+、Cd2+、Mg2+、Zn2+、F-、SO4 2-And Li+One or more ions of (a).
Preferably, the Ca of said calcium-containing aqueous phase of step (1)2+The concentration of (A) is 20-700 mg/L.
Preferably, the volume ratio of the organic phase to the aqueous phase in the step (2) is 1: 1-2.
Preferably, the rotation speed of the oscillation in the step (2) is 150-.
Preferably, the temperature of the extraction in the step (2) is 10-50 ℃, and the extraction time is 1-10 min.
Preferably, the extraction in the step (2) is single-stage extraction or multi-stage countercurrent extraction.
The invention has the advantages that:
1) the combined extractant has high extraction rate of calcium and good selectivity, and the single-stage extraction rate can reach more than 90%; after 4-stage countercurrent extraction, the calcium content in the water phase can be reduced to below 1mg/L from 600mg/L, and the extraction rate can reach 99.8%;
2) the combined extractant has extremely low extraction rate on other metals, particularly on main metals, and greatly reduces the loss of valuable main metals;
3) the combined extractant does not need to be saponified, so that on one hand, energy can be saved; on one hand, the entrainment of the saponifier sodium hydroxide in the organic phase can be eliminated, the pollution of sodium to the product is avoided, and the product purity is improved; on the other hand, the trouble that a large amount of sodium salt generated in the subsequent process blocks the pipeline and influences the production can be avoided.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below with reference to the examples to further illustrate the features and advantages of the invention, and any changes or modifications that do not depart from the gist of the invention will be understood by those skilled in the art to which the invention pertains, the scope of which is defined by the scope of the appended claims.
Example 1
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 3.1;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, oscillating at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 45s, and separating out a water phase to obtain the organic phase containing calcium ions.
The detection results of the contents of calcium and other metals in the raffinate are shown in table 1, the extraction rate of calcium is 85.8%, the extraction rates of main metals of nickel, cobalt and manganese are 7.5%, 0.01% and 5.6%, and the extraction rate of magnesium is 4.3%, and the combined extractant has extremely high selectivity on calcium.
TABLE 1 iron-removed Ni-Co-Mn leachate before and after extraction of each metal content
Example 2
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing an organic phase from 10% of P204 (di (2-ethylhexyl) phosphate), 10% of TBP (tributyl phosphate) and 80% of sulfonated kerosene by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution in a separating funnel, oscillating at the rotation speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for 36s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution after iron and aluminum removal are shown in table 2, and the detection result of the calcium content in the raffinate is shown in table 2.
Example 3
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 15% of P204 (di (2-ethylhexyl) phosphate), 10% of TBP (tributyl phosphate) and 75% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 38s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution after iron and aluminum removal are shown in table 2, and the detection result of the calcium content in the raffinate is shown in table 2.
Example 4
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 10% of TBP (tributyl phosphate) and 70% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, oscillating at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 38s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution after iron and aluminum removal are shown in table 2, and the detection result of the calcium content in the raffinate is shown in table 2.
TABLE 2 metals content before and after extraction of Ni, Co and Mn leaching solution after removal of Fe and Al
Example 5
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 34s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution without iron, aluminum and copper are shown in table 3, and the detection result of the calcium content in the raffinate is shown in table 3.
Example 6
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 15% of TBP (tributyl phosphate) and 65% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 35s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution without iron, aluminum and copper are shown in table 3, and the detection result of the calcium content in the raffinate is shown in table 3.
Example 7
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 38s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution without iron, aluminum and copper are shown in table 3, and the detection result of the calcium content in the raffinate is shown in table 3.
Example 8
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
preparing an organic phase from 20% by mass of P204 (di (2-ethylhexyl) phosphate), 25% of TBP (tributyl phosphate) and 55% of sulfonated kerosene, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leachate into a separating funnel, oscillating at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 43s, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution without iron, aluminum and copper are shown in table 3, and the detection result of the calcium content in the raffinate is shown in table 3.
TABLE 3 content of metals before and after extraction of Ni, Co and Mn leaching solution without Fe, Al and Cu
Example 9
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the calcium-containing wastewater to 5.0;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing for layering for 56s, and separating out a water phase to obtain the organic phase containing calcium ions.
The calcium-containing wastewater components are shown in table 4, and the detection result of the calcium content in the raffinate is shown in table 4;
TABLE 4 content of metals before and after extraction of certain calcium-containing wastewater
Example 10
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, shaking at the rotating speed of 300rpm, performing four-stage countercurrent extraction at the temperature of 25 ℃, and separating out a water phase to obtain the organic phase containing calcium ions.
The components of the nickel-cobalt-manganese leaching solution after iron, aluminum and copper removal are shown in table 5, and the calcium content in the organic phase after the raffinate and the four-stage countercurrent extraction is shown in table 5.
TABLE 5 four-stage countercurrent extraction data for a certain Ni-Co-Mn leach solution
Example 11
A method for extracting calcium without saponification comprises the following steps:
(1) adjusting the pH value of the nickel-cobalt-manganese leaching solution to 5.5;
(2) preparing 20% of P204 (di (2-ethylhexyl) phosphate), 20% of TBP (tributyl phosphate) and 60% of sulfonated kerosene into an organic phase by mass percent, placing 100mL of the organic phase and 100mL of nickel-cobalt-manganese leaching solution into a separating funnel, oscillating at the rotating speed of 300rpm, extracting at the temperature of 25 ℃ for 8min, standing and layering for 43s, and separating out a water phase to obtain the organic phase containing calcium ions.
The results of the measurements of calcium and other metals in the raffinate are shown in table 6.
Comparative example 1
The difference from example 11 is that the organic phase is formulated with 20% by mass of P204 (di (2-ethylhexyl) phosphate) and 80% by mass of sulfonated kerosene.
The results of the measurements of calcium and other metals in the raffinate are shown in table 6.
Comparative example 2
The difference from example 11 is that the organic phase is prepared from TBP (tributyl phosphate) and sulfonated kerosene in the mass percentages of 20% and 80%.
The results of the measurements of calcium and other metals in the raffinate are shown in table 6.
The detection results of calcium and other metals in the raffinate are shown in table 6, and the extraction rate of calcium by the combined extractant is 90.8%, the extraction rate of Ca by P204 (di (2-ethylhexyl) phosphate) is 38.6%, and the extraction rate of Ca by TBP (tributyl phosphate) is 41.5%.
TABLE 2 comparison of P204 and TBP Combined extractants with P204 or TBP extraction rates alone
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications and simplifications that do not depart from the spirit and principle of the present invention should be construed as equivalent replacements and equivalents thereof, which are included in the protection scope of the present invention.
Claims (8)
1. The method for extracting calcium without saponification is characterized by comprising the following steps of:
(1) adjusting the pH of the calcium-containing aqueous phase to 3.0-5.5;
(2) preparing di (2-ethylhexyl) phosphate, tributyl phosphate and a diluent into an organic phase, mixing the organic phase and a calcium-containing water phase according to the volume ratio of 1:0.5-4, extracting, and separating the water phase to obtain the calcium-containing organic phase; the calcium-containing aqueous phase of step (1) further comprises Ni2+、Co2+、Mn2+、Cd2+、Mg2+、Zn2+、F-、SO4 2-And Li+One or more ions of (a); the calcium-containing water phase in the step (1) is selected from nickel-cobalt-manganese leaching solution; ca of the calcium-containing aqueous phase of step (1)2+The concentration of (b) is 20-700 mg/L.
2. The method for extracting calcium without saponification of claim 1, wherein the organic phase in step (2) consists of the following components in percentage by mass: 10-25% of an extracting agent, 10-25% of a synergistic agent and 50-80% of a diluent.
3. The method for non-saponification calcium extraction according to claim 2, characterized in that the extractant is di (2-ethylhexyl) phosphate.
4. The method for soap-free extraction of calcium as claimed in claim 2, wherein the synergist is tributyl phosphate.
5. The method for non-saponification calcium extraction according to claim 2, wherein the diluent is sulfonated kerosene.
6. The method for extracting calcium without saponification of claim 1, wherein the temperature of the extraction in the step (2) is 10-50 ℃, and the extraction time is 1-10 min.
7. The method for extracting calcium without saponification according to claim 1, wherein the extraction in step (2) is single-stage extraction or multi-stage countercurrent extraction.
8. The method for extracting calcium without saponification as claimed in claim 1, wherein the shaking rotation speed in step (2) is 150-300rpm for 1-10 min.
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| CN106756011A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | The method that saponification directly extracts calcium is exempted from a kind of synergic solvent extraction from solution |
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