CN112458281A - Method for preparing nickel salt by using nickel-magnesium-containing waste liquid - Google Patents
Method for preparing nickel salt by using nickel-magnesium-containing waste liquid Download PDFInfo
- Publication number
- CN112458281A CN112458281A CN202011333083.8A CN202011333083A CN112458281A CN 112458281 A CN112458281 A CN 112458281A CN 202011333083 A CN202011333083 A CN 202011333083A CN 112458281 A CN112458281 A CN 112458281A
- Authority
- CN
- China
- Prior art keywords
- organic phase
- nickel
- magnesium
- solution
- waste liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to a method for preparing nickel salt by using nickel-magnesium containing waste liquid, which comprises the following steps: (1) preparing an organic phase with a certain concentration by using an extracting agent and a diluting agent; (2) saponifying the organic phase by using liquid alkali to obtain a saponified organic phase; (3) extracting the saponified organic phase obtained in the step (2) with a nickel-magnesium containing solution to obtain a loaded organic phase and an extraction water phase; (4) and (4) washing and back-extracting the loaded organic phase to obtain a regenerated organic phase and a high-purity nickel solution. The extractant in the step (1) is a carboxylic acid extractant BC194, and the carboxylic acid extractant BC194 has good selectivity on ions, high nickel-magnesium separation coefficient, low water solubility and environmental friendliness. The method adopted by the invention can effectively separate nickel and magnesium in the nickel and magnesium containing waste liquid, and has the advantages of short flow, low acid consumption, small pollution and high economic benefit.
Description
Technical Field
The invention belongs to the field of non-ferrous metal hydrometallurgy and resource recovery, and particularly relates to a method for preparing nickel salt by using waste liquid containing nickel and magnesium.
Background
The nickel resource mainly exists in the laterite-nickel ore and the nickel sulfide ore, wherein the laterite-nickel ore accounts for about 55%, the extraction process of high-purity nickel metal in the prior art is inevitably influenced by magnesium ions, and no matter the laterite-nickel ore or the nickel sulfide ore or the nickel metal recovery process in a battery, a brand new process is developed to ensure that the nickel and the magnesium can be separated efficiently in one step, so that the economic benefit can be obviously improved, the production cost is reduced, and the resource waste and the environmental pollution are reduced.
The existing hydrometallurgy technology can realize effective separation of nickel and magnesium, but the separation process usually needs to extract magnesium first and enrich nickel, so that the purpose of obtaining pure nickel liquid is achieved, and the process has high acid-base consumption and long flow, and is not more and more in line with the requirements of industry development.
CN102814058B discloses a method for separating, enriching and purifying nickel and magnesium by using an adsorption material experiment, wherein a solution to be treated containing nickel ions and magnesium ions is adjusted to pH 1.0-5.5 to obtain an acid leaching solution, the acid leaching solution is contacted and mixed with an adsorbed heavy metal adsorption material, the heavy metal adsorption material can adsorb the nickel ions in the acid leaching solution, the magnesium ions are remained in the acid leaching solution, and the heavy metal adsorption material is washed by 5-30% sulfuric acid solution to carry out desorption operation to obtain a nickel-containing desorption solution and an analyzed heavy metal adsorption material. And (3) carrying out electrodeposition operation by using the nickel-containing desorption solution to obtain nickel metal or nickel metal powder, wherein the desorbed heavy metal adsorption material can be recycled. The method has the advantages of convenience in operation and simplicity in equipment, but the production process of the heavy metal adsorption material is complex, the capacity and the adsorption efficiency of the heavy metal adsorption material are reduced after the heavy metal adsorption material is used for multiple times, the heavy metal adsorption material is easily affected by insoluble substances and impurities in a system, and the heavy metal adsorption material needs to be replaced and needs to be further treated after being replaced.
CN101824550B discloses a high-purity nickel extraction purification process, which comprises adding an oxidant, namely hydrogen peroxide, into a nickel sulfate solution, reacting completely, adding sodium carbonate to generate a complex, precipitating to remove iron, removing metals such as Co, Mn, Ca, Zn and the like by using P204 countercurrent extraction, then using P507 to extract magnesium in the solution, performing back extraction on the residual organic phase anode solution or dilute sulfuric acid to obtain electronic-grade nickel sulfate from a water phase. The set of purification process firstly adopts P507 to extract magnesium from the solution containing nickel and magnesium ions after Co, Mn, Ca, Zn and Fe are removed, and then electronic-grade nickel sulfate is obtained after enrichment and back extraction, wherein the nickel and magnesium separation needs two steps, a large amount of acid and alkali is consumed, and the economic benefit is low.
Therefore, it is a key point of research in the field to develop a nickel-magnesium separation system that can extract nickel preferentially before extracting calcium and magnesium ions, reduce the cost of extracting calcium and magnesium, reduce the consumption of acid and alkali, and improve the separation efficiency and recovery rate of nickel and magnesium.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for preparing nickel salt by using waste liquid containing nickel and magnesium, the carboxylic acid extractant BC194 adopted by the invention can extract nickel before extracting calcium and magnesium ions, the nickel and magnesium separation effect is good, so that the purpose of purifying nickel in one step is achieved, and the carboxylic acid extractant BC194 has low water solubility, is environment-friendly, has less loss in the actual use process and high stability; the back extraction rate is high, the organic phase after back extraction can be recycled, the operation cost is low, and the economic benefit is high.
The specific technical scheme of the invention is as follows:
a method for preparing nickel salt by using waste liquid containing nickel and magnesium comprises the following steps:
(1) preparing an organic phase with corresponding concentration by using an extracting agent and a diluting agent;
(2) saponifying the organic phase prepared in the step (1) by using liquid alkali to obtain a saponified organic phase;
(3) extracting the saponified organic phase obtained in the step (2) relative to the nickel-magnesium-containing waste liquid, standing and layering to obtain a loaded organic phase and an extracted water phase;
(4) and (4) carrying out washing and back extraction operations on the loaded organic phase obtained in the step (3) to obtain a nickel enriched solution.
Wherein the extractant in the step (1) is a carboxylic acid extractant BC 194; the structural formula of the carboxylic acid extractant BC194 is shown as the formula I:
compared with the prior art, the method provided by the invention can realize the effects of one-step extraction and high-purity nickel obtaining, reduces the cost of magnesium extraction in the prior art, reduces the acid-base consumption, and simultaneously has good separation effect on Ni and Mg by the carboxylic acid extractant, the extraction rate of Ni is more than 99.0 percent, and the sulfuric acid back extraction rate is more than 99.5 percent.
As a preferable technical scheme of the invention, the volume fraction of the extracting agent in the organic phase in the step (1) is 5-30%.
Preferably, the volume fraction of the extractant in the organic phase is 5 to 30%, for example, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 21%, 23%, 25%, 27%, or 30%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the diluent of the extractant in the step (1) is any one or a combination of at least two of Escaid110, sulfonated kerosene, toluene, hexane, heptane, dodecane or kerosene;
preferably, the diluent is Escaid110 and/or dodecane.
As a preferred technical scheme of the invention, the liquid alkali used in the saponification in the step (2) comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water.
Preferably, the concentration of the liquid alkali is 6 to 14mol/L, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
As a preferable technical scheme of the invention, the volume ratio of the saponified organic phase in the step (3) to the waste liquid containing nickel and magnesium is 1 (0.1-10).
Preferably, the volume ratio of the saponified organic phase to the waste liquid containing nickel and magnesium is 1 (0.1-10), and may be, for example, 1:0.1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1:10, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferable technical scheme, the volume ratio of the saponified organic phase to the nickel-magnesium-containing waste liquid in the step (3) is 1 (0.1-10), and the overlarge volume ratio causes the volume proportion of the nickel-magnesium-containing waste liquid to be too low, so that magnesium-containing extract liquid is entrained or extracted by magnesium ions, and the purity of the nickel-containing solution in the later period is influenced; too small a volume ratio results in insufficient extraction capacity for extracting the organic phase, resulting in inefficient extraction of nickel ions and difficulty in uniform mixing.
Preferably, the waste liquid containing nickel and magnesium in the step (3) is a chloride system nickel and magnesium waste liquid or a sulfate system nickel and magnesium waste liquid;
preferably, the nickel-magnesium ratio in the nickel-magnesium containing waste liquid in the step (3) is 1 (0.5-20), and may be, for example, 1:0.5, 1:1, 1:1.5, 1:2, 1:3, 1:5, 1:8, 1:10, 1:12, 1:14, 1:15, 1:16, 1:18, 1:19, or 1:20, but is not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical scheme of the invention, the extraction in the step (3) is multi-stage countercurrent extraction.
Preferably, the extraction stages of the multistage countercurrent extraction are 2 to 20 stages, such as 2, 3, 4, 5, 8, 10, 12, 14, 15, 17, 18, 19 or 20 stages, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the extraction stirring speed in step (3) is 100-250 rpm/min, such as 100rpm/min, 120rpm/min, 140rpm/min, 150rpm/min, 180rpm/min, 200rpm/min, 220rpm/min, 230rpm/min, 240rpm/min or 250rpm/min, but not limited to the enumerated values, and other non-enumerated values in this range are also applicable.
Preferably, the stirring and mixing time in step (3) is 3 to 30min, for example, 3min, 5min, 8min, 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the standing and layering time in step (3) is 2-30 min, such as 2min, 5min, 10min, 15min, 20min, 25min, 27min, 28min, 29min or 30min, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the pH of the aqueous raffinate phase in step (3) is 3.0 to 6.5, and may be, for example, 3.0, 3.8, 4.0, 4.4, 4.7, 5.0, 6.1, 6.2, 6.3, 6.4 or 6.5, but is not limited to the values recited, and other values not recited in this range are equally applicable.
As a preferred technical scheme, the pH value of the raffinate water phase is 3.0-6.5, the pH value is too small, and the nickel extraction rate is low; the pH value is too large, magnesium extracted by an organic phase is increased, and the washing cost is increased.
As a preferable technical scheme of the invention, the loaded organic phase in the step (4) is subjected to multi-stage countercurrent washing to obtain a washed organic phase.
Preferably, the number of the multistage countercurrent washing stages in the step (4) is 2 to 20, such as 2, 5, 8, 10, 15, 17, 18, 19 or 20, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the washing in step (4) is performed with an acid solution.
Preferably, the washing acid solution is one or at least two of inorganic acid, acidified water and/or nickel sulfate solution.
Preferably, the pH of the washing acid solution is 0.1 to 4, and may be, for example, 0.1, 0.2, 0.5, 0.6, 0.8, 1, 2, 3, or 4, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the concentration of the nickel sulfate solution is 0.5-20 g/L, for example, 0.5g/L, 1g/L, 3g/L, 5g/L, 10g/L, 12g/L, 13g/L, 15g/L, 18g/L, 19g/L or 20g/L, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the volume ratio of the washing liquid to the loaded organic phase in the step (4) is 1 (5-10), and may be, for example, 1:5, 1:7, 1:8, 1:9 or 1:10, but not limited to the values listed, and other values not listed in the range are also applicable.
As the preferable technical scheme of the invention, the washed organic phase is subjected to acid liquor back extraction to obtain a nickel enriched solution, and the nickel enriched solution is evaporated and crystallized to obtain nickel salt;
preferably, the stripping stage number is 1 to 6 stages, for example, 1 stage, 2 stages, 3 stages, 4 stages, 5 stages or 6 stages, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preference is given toThe acid solution used for the back extraction is H+The sulfuric acid or hydrochloric acid solution having a concentration of 3 to 6mol/L may be, for example, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L or 6mol/L, but is not limited to the values listed above, and other values not listed within the range are also applicable.
Preferably, the volume ratio of the stripping solution to the washing organic phase is 1:5 to 20, and may be, for example, 1:5, 1:8, 1:10, 1:13, 1:15, 1:17, 1:18, 1:19 or 1:20, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the crystallization is MVR evaporation;
preferably, a regenerated organic phase is also obtained after the stripping operation.
Preferably, the regenerated organic phase is returned to the saponification step for recycling.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) preparing an extracting agent and a diluent into an organic phase with the concentration of 5-30%, wherein the extracting agent is a carboxylic acid extracting agent BC194, and the structural formula of the carboxylic acid extracting agent BC194 is as shown in formula I:
(2) saponifying the organic phase prepared in the step (1) by using 6-14 mol/L liquid alkali to obtain a saponified organic phase;
(3) extracting the saponified organic phase obtained in the step (2) relative to the nickel-magnesium-containing waste liquid, mixing and stirring the extracted organic phase and the nickel-magnesium-containing waste liquid according to a volume ratio of 1 (0.1-10), then performing multistage countercurrent extraction, wherein the stirring speed is 100-250 rpm/min, the stirring time is 3-30 min, the extraction stage number is 2-20, and after extraction, contacting and layering for 2-50 min to obtain a loaded organic phase and an extracted water phase with a pH value of 3.0-6.5;
(4) carrying out 2-20-stage multistage countercurrent washing on the loaded organic phase in the step (3) by using a washing solution with a pH value of 0.1-4, wherein the volume ratio of the washing solution to the loaded organic phase is 1 (5-10); then adopt againH+And (3) carrying out 1-6-stage back extraction on the washed organic phase by using a back extraction solution with the concentration of 3-6 mol/L, wherein the volume ratio of the back extraction solution to the washed organic phase is 1 (5-20), obtaining a nickel enrichment solution and a regenerated organic phase after the back extraction, evaporating and concentrating the obtained nickel enrichment solution to obtain nickel salt, and returning the regenerated organic phase to the saponification process for recycling.
In the present invention, the reaction equation of the relevant process is as follows:
saponification of carboxylic acid extractant: HA (org) + NaOH → NaA (org) + H2O
Extracting with carboxylic acid extractant: 2NaA (org) + MSO4→MA2(org)+Na2SO4
Sulfuric acid back extraction: MA (MA)2(org)+H2SO4→2HA(org)+MSO4
Wherein: m is Ni2+A metal.
According to the nickel salt preparation method provided by the invention, firstly, saponification treatment is carried out on an organic phase containing carboxylic acid compounds with a specific structure to obtain a saponified organic phase, then the saponified organic phase is used for extracting nickel ions in a nickel-magnesium containing waste liquid, magnesium is remained in an extracted water phase, and finally the organic phase loaded with nickel is subjected to back extraction to obtain a regenerated organic phase and a nickel enriched solution.
Drawings
FIG. 1 is a schematic view of a recovery flow in example 1 of the present invention.
FIG. 2 is a graph of the E-pH of the novel carboxylic acid extractant BC194 used in the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
preparation example 1
A novel carboxylic acid extractant BC194 has the following structure:
the preparation method comprises the following steps:
into a 500mL round bottom flask was added 20g (0.12mol) of dipicolinic acid, and 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, and the reaction was confirmed by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 25g (0.25mol) of triethylamine were added to the flask, and 24.6g (0.12mol) of p-octylaniline was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid at pH 1, then 1 time with water, drying over sodium sulfate and spin-drying the solvent, the desired product 32.1g was obtained in about 75% yield.
Characterization data:13C NMR(101MHz,CDCl3)δ168.1(s),142.3(s),139.2(s),135.1(s),127.7(s),125.6(s),128.3(m),121.6(m),51.6(m),32.5–31.1(m),29.7(m),27.4(m),24.7(m),14.3(d,J＝5.9Hz)；1H NMR(400MHz,CDCl3)δ9.86(1H)，8.81(1H)，8.75(1H)，8.52(1H),7.58(2H),7.15(1H)，2.52(2H),1.56(2H),1.27(10H),0.86(3H)；MS:354.2
example 1
A method for preparing nickel salt by using waste liquid containing nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid extractant BC194 obtained in preparation example 1 in a diluent Escaid110 to enable the volume fraction of the BC194 in the Escaid110 to be 25%, adding a NaOH solution with the concentration of 10mol/L, and mixing to obtain a saponified organic phase with the saponification degree of 30%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the nickel-magnesium containing waste liquid as an aqueous phase system (2.3 g/L of nickel, 19g/L of magnesium and 3.20 of pH value specifically from waste water after nickel extraction from a nickel intermediate product leaching solution), respectively flowing the nickel-magnesium containing waste liquid and the saponified organic phase obtained in the step (1) from two ends of an extractor (the flow ratio of the saponified organic phase to the nickel-magnesium containing waste liquid is 1:4), carrying out multi-stage countercurrent extraction, mixing and keeping the mixing at a stirring speed of 250rpm/min for 15min and at a temperature of 20 ℃, wherein the extraction stages are 8 stages, and standing for phase separation for 10min to obtain a nickel ion loaded organic phase and a magnesium ion containing outlet aqueous phase (namely a raffinate aqueous phase) with a pH value of 6;
(3) and (3) carrying out 12-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using a sulfuric acid solution with a pH value of 1, and then carrying out back extraction by using sulfuric acid with a concentration of 2mol/L, wherein the number of the back extraction stages is 5, the flow ratio of the washing sulfuric acid solution to the loaded organic phase is 1:5, and the flow ratio of the 2mol/L back extraction sulfuric acid to the loaded organic phase is 1:15, so as to obtain a nickel ion enriched solution and a regenerated organic phase.
Example 2
A method for preparing nickel salt by using waste liquid containing nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid extractant BC194 obtained in the preparation example 1 into Escaid110, wherein the volume fraction of the BC194 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponification extractant with a saponification degree of 20%, wherein the saponification extractant is used as an organic phase system;
(2) taking the nickel-magnesium-containing waste liquid as an aqueous phase system (2.30 g/L of nickel, 19g/L of magnesium and 3.20 of pH value, specifically derived from waste water after nickel extraction of nickel intermediate product leachate), respectively flowing the nickel-magnesium-containing waste liquid and the saponification extracting agent in the step (1) from two ends of an extractor (the volume ratio of the saponification extracting agent to the nickel-magnesium-containing waste liquid is 1:5), carrying out multi-stage countercurrent extraction, mixing and keeping the mixing at a stirring speed of 200rpm/min for 10min and at a temperature of 25 ℃, wherein the extraction stages are 6 stages, standing for 20min, and layering to obtain a nickel ion-loaded organic phase and a magnesium ion-containing raffinate aqueous phase with a pH value of 6.5;
(3) carrying out 8-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using sulfuric acid with the pH value of 0.5, and then carrying out back extraction by using sulfuric acid with the concentration of 2.5mol/L, wherein the back extraction frequency is 2 times; the volume ratio of the washing sulfuric acid to the loaded organic phase is 1:8, and the volume ratio of the 2.5mol/L stripping sulfuric acid to the loaded organic phase is 1:16, so that a nickel ion enriched solution and a regenerated organic phase are obtained.
Example 3
A method for preparing nickel salt by using waste liquid containing nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid extractant BC194 obtained in the preparation example 1 in dodecane, wherein the volume fraction of the BC194 in the dodecane is 20%, adding an ammonia water solution with the concentration of 11mol/L, and mixing to obtain a saponified organic phase with the saponification degree of 20%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the nickel-magnesium containing waste liquid as a water phase system (2.30 g/L of nickel, 19g/L of magnesium and 3.20 of pH value, specifically derived from waste water after nickel extraction of nickel intermediate product leachate), respectively flowing into the two ends of the extractor with the saponified organic phase in the step (1) (the volume ratio of the saponified organic phase to the nickel-magnesium containing waste liquid is 1:4.5), mixing and keeping the stirring speed at 180rpm/min, the mixing time at 5min and the temperature at 25 ℃, carrying out multi-stage countercurrent fractional extraction, wherein the extraction stages are 6 stages, clarifying and layering for 10min, and obtaining a nickel ion loaded organic phase and a magnesium ion containing raffinate water phase with the pH value of 5.5;
(3) carrying out 8-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using sulfuric acid with the pH value of 1.0, and then carrying out back extraction by using sulfuric acid with the concentration of 2.5mol/L for 4 times; the flow ratio of the washing sulfuric acid to the loaded organic phase is 1:10, and the flow ratio of the 2.5mol/L stripping sulfuric acid to the loaded organic phase is 1:10, so that a nickel ion enriched solution and a regenerated organic phase are obtained.
Example 4
A method for preparing nickel salt by using waste liquid containing nickel and magnesium, which is different from the method of example 1 only in that: the sulfuric acid washing solution in the step (3) was replaced with 5.0g/L of a nickel sulfate solution having a pH of 1.5, and the amounts of other components and experimental conditions were the same as those in example 1.
Comparative example 1
A method for preparing nickel salt by using waste liquid containing nickel and magnesium, which is different from the method of example 1 only in that: the carboxylic acid BC194 in step (1) was replaced by the same amount of extractant P507 (2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), and the amounts of other components and experimental conditions were the same as in example 1.
And (3) performance testing:
the proportion of saponification refers to the alkali metal NH in the extractant+4And/or Na+The ratio of original hydrogen ions, i.e. eta ═ VAlkali×CAlkali)/(VIs provided with×CIs provided with)×100％ (1)
In the formula (1), VAlkaliIs the volume mL of the aqueous solution of the added base, CAlkaliIs the concentration mol/L, V of the alkali in the added alkali water solutionIs provided withVolume of organic phase mL, CIs provided withIs the concentration mol/L of the extractant in the organic phase.
In the examples of the present invention, the content of metal ions in the aqueous phase was measured by inductively coupled plasma emission spectrometry (ICP-OES), and then the content of metal ions in the organic phase was determined by the subtraction method.
The raffinate aqueous phase and the nickel ion-enriched solution obtained in the step (2) of the extraction method described in examples 1 to 4 were tested according to the above test methods, and the results are shown in table 1.
TABLE 1
According to the data in the table 1, the nickel recovery rate of the method for preparing nickel salt by using the waste liquid containing nickel and magnesium is high and reaches over 99 percent, the nickel content in the raffinate is low and is basically lower than 5mg/L, and the direct discharge requirement is met. The obtained product nickel sulfate has high purity, and meets the purity requirement of battery-grade nickel sulfate. The method for preparing nickel salt from the nickel-magnesium containing waste liquid has short process, saves the conventional work of extracting magnesium first, reduces the consumption of acid and alkali, and reduces the nickel recovery cost. The method has the advantages of low metal ion content in the waste liquid, little environmental pollution and low subsequent treatment cost.
The applicant states that the present invention is to illustrate a method for preparing nickel salt by using waste liquid containing nickel and magnesium by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (8)
1. A method for preparing nickel salt by using waste liquid containing nickel and magnesium is characterized by comprising the following steps:
(1) preparing an organic phase with corresponding concentration by using an extracting agent and a diluting agent;
(2) saponifying the organic phase prepared in the step (1) by using liquid alkali to obtain a saponified organic phase;
(3) extracting the saponified organic phase obtained in the step (2) relative to the nickel-magnesium-containing waste liquid, standing and layering to obtain a loaded organic phase and an extracted water phase;
(4) and (4) carrying out washing and back extraction operations on the loaded organic phase obtained in the step (3) to obtain a nickel enriched solution.
Wherein the extractant in the step (1) is a carboxylic acid extractant BC194, and the structural formula of the carboxylic acid extractant BC194 is shown in formula I:
2. the method according to claim 1, wherein the volume fraction of the extractant in the organic phase in the step (1) is 5-30%;
preferably, the diluent of the extractant in the step (1) is any one or a combination of at least two of Escaid110, sulfonated kerosene, toluene, hexane, heptane, dodecane or kerosene;
preferably, the diluent is Escaid110 and/or dodecane.
3. The method according to any one of claims 1 to 2, wherein the liquid alkali used in the saponification in the step (2) comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water;
preferably, the concentration of the liquid caustic soda is 6-14 mol/L.
4. The method according to any one of claims 1 to 3, wherein the volume ratio of the saponified organic phase to the waste liquid containing nickel and magnesium in step (3) is 1 (0.1 to 10);
preferably, the waste liquid containing nickel and magnesium in the step (3) is a chloride system nickel and magnesium waste liquid or a sulfate system nickel and magnesium waste liquid;
preferably, the nickel-magnesium ratio in the nickel-magnesium containing waste liquid in the step (3) is 1 (0.5-20).
5. The process of any one of claims 1 to 4, wherein the extraction in step (3) is a multistage countercurrent extraction;
preferably, the extraction stages of the multistage countercurrent extraction are 2-20 stages;
preferably, the extraction stirring speed in the step (3) is 100-250 rpm/min;
preferably, the stirring and mixing time in the step (3) is 3-30 min;
preferably, the standing and layering time in the step (3) is 2-30 min;
preferably, the equilibrium pH value of the raffinate aqueous phase in the step (3) is 3.0-6.5.
6. The method according to any one of claims 1 to 5, wherein the loaded organic phase in step (4) is subjected to multistage countercurrent washing to obtain a washed organic phase;
preferably, the washing grade in the step (4) is 2-20 grades;
preferably, the washing in the step (4) is performed by using an acid solution;
preferably, the washing acid solution is one or at least two of inorganic acid, acidified water and/or nickel sulfate solution;
preferably, the pH value of the washing acid solution is 0.1-4;
preferably, the concentration of the nickel sulfate solution is 0.5-20 g/L;
preferably, the volume ratio of the washing liquid to the loaded organic phase in the step (4) is 1 (5-10).
7. The method according to any one of claims 1 to 6, wherein the washed organic phase is subjected to acid stripping to obtain a nickel-enriched solution, and the nickel-enriched solution is evaporated and crystallized to obtain a nickel salt;
preferably, the back extraction stage number is 1-6;
preferably, the acid solution used for back extraction is H+A sulfuric acid or hydrochloric acid solution with the concentration of 3-6 mol/L;
preferably, the volume ratio of the stripping solution to the washing organic phase is 1 (5-20);
preferably, the crystallization is MVR evaporation;
preferably, a regenerated organic phase is also obtained after the stripping operation;
preferably, the regenerated organic phase is reused as an extractant.
8. The method according to any one of claims 1 to 7, characterized in that it comprises in particular the steps of:
(1) preparing an extracting agent and a diluent into an organic phase with the concentration of 5-30%, wherein the extracting agent is a carboxylic acid extracting agent BC194, and the structural formula of the carboxylic acid extracting agent BC194 is as shown in formula I:
(2) saponifying the organic phase prepared in the step (1) by using 6-14 mol/L liquid alkali to obtain a saponified organic phase;
(3) extracting the saponified organic phase obtained in the step (2) relative to the nickel-magnesium-containing waste liquid, mixing and stirring the extracted organic phase and the nickel-magnesium-containing waste liquid according to a volume ratio of 1 (0.1-10), then performing multistage countercurrent extraction, wherein the stirring speed is 100-250 rpm/min, the stirring time is 3-30 min, the extraction stage number is 2-20, and after extraction, contacting and layering for 2-50 min to obtain a loaded organic phase and an extracted water phase with a pH value of 3.0-6.5;
(4) carrying out 2-20-stage multistage countercurrent washing on the loaded organic phase in the step (3) by using a washing solution with a pH value of 0.1-4, wherein the volume ratio of the washing solution to the loaded organic phase is 1 (5-10); then using H+And (3) carrying out 1-6-stage back extraction on the washed organic phase by using a back extraction solution with the concentration of 3-6 mol/L, wherein the volume ratio of the back extraction solution to the washed organic phase is 1 (5-20), evaporating and crystallizing the obtained nickel enrichment solution after the back extraction to obtain nickel salt, and returning the obtained regenerated organic phase to the saponification process for recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011333083.8A CN112458281A (en) | 2020-11-24 | 2020-11-24 | Method for preparing nickel salt by using nickel-magnesium-containing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011333083.8A CN112458281A (en) | 2020-11-24 | 2020-11-24 | Method for preparing nickel salt by using nickel-magnesium-containing waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112458281A true CN112458281A (en) | 2021-03-09 |
Family
ID=74799821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011333083.8A Pending CN112458281A (en) | 2020-11-24 | 2020-11-24 | Method for preparing nickel salt by using nickel-magnesium-containing waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112458281A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085994A (en) * | 2021-11-09 | 2022-02-25 | 苏州博萃循环科技有限公司 | Method for recovering valuable metal from waste nickel-hydrogen battery |
| CN115652110A (en) * | 2022-11-16 | 2023-01-31 | 包头市世博稀土萃取装备有限公司 | Method for separating magnesium and nickel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9809290D0 (en) * | 1997-04-30 | 1998-07-01 | Sumitomo Metal Mining Co | Method of puriying nickel sulfate |
| 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 |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN105296753A (en) * | 2015-11-13 | 2016-02-03 | 广西师范大学 | Method for separating cobalt, nickel and magnesium from nickel oxide ore pickle liquor |
| CN111411228A (en) * | 2020-05-28 | 2020-07-14 | 中钢天源股份有限公司 | Method for extracting and separating nickel, cobalt and magnesium from nickel-cobalt-magnesium mixed solution |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
-
2020
- 2020-11-24 CN CN202011333083.8A patent/CN112458281A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9809290D0 (en) * | 1997-04-30 | 1998-07-01 | Sumitomo Metal Mining Co | Method of puriying nickel sulfate |
| 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 |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN105296753A (en) * | 2015-11-13 | 2016-02-03 | 广西师范大学 | Method for separating cobalt, nickel and magnesium from nickel oxide ore pickle liquor |
| CN111411228A (en) * | 2020-05-28 | 2020-07-14 | 中钢天源股份有限公司 | Method for extracting and separating nickel, cobalt and magnesium from nickel-cobalt-magnesium mixed solution |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085994A (en) * | 2021-11-09 | 2022-02-25 | 苏州博萃循环科技有限公司 | Method for recovering valuable metal from waste nickel-hydrogen battery |
| CN115652110A (en) * | 2022-11-16 | 2023-01-31 | 包头市世博稀土萃取装备有限公司 | Method for separating magnesium and nickel |
| CN115652110B (en) * | 2022-11-16 | 2024-02-27 | 包头市世博稀土萃取装备有限公司 | Method for separating magnesium and nickel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022000881A1 (en) | Carboxylic acid compound, and preparation method therefor and application thereof | |
| CN109097599B (en) | Method for separating manganese, calcium and magnesium by synergistic extraction | |
| CN112522517A (en) | Method for recycling nickel, cobalt, manganese and lithium | |
| CN111519031A (en) | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder | |
| US20230332269A1 (en) | Method for recycling nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese | |
| CN112538569B (en) | Method for separating nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese | |
| CN114457245B (en) | Method for preparing nickel sulfate and cobalt sulfate from cobalt nickel hydroxide | |
| CN112442596B (en) | Method for separating and recovering nickel, cobalt and manganese in battery intermediate feed liquid by carboxylic acid extracting agent | |
| US20230265540A1 (en) | Extraction method for removing aluminum from ternary battery material leachate | |
| CN112342387A (en) | Method for separating nickel and magnesium and application thereof | |
| CN112458281A (en) | Method for preparing nickel salt by using nickel-magnesium-containing waste liquid | |
| WO2022110821A1 (en) | Carboxylic acid compound, preparation method therefor and use thereof | |
| CN114561541A (en) | Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate | |
| CN112320860B (en) | Method for purifying nickel sulfate | |
| CN112501445B (en) | Method for preparing battery-grade nickel-cobalt-manganese | |
| WO2022048308A1 (en) | Method for separating copper and manganese from mixed solution containing copper, manganese, calcium and zinc | |
| WO2024124712A1 (en) | Method for recovering manganese and fluorine from manganese salt solution | |
| CN112458314B (en) | Method for separating nickel cobalt from calcium and magnesium | |
| EP4215630A1 (en) | Method for separating nickel from lithium, and application thereof | |
| CN114085994A (en) | Method for recovering valuable metal from waste nickel-hydrogen battery | |
| CN112725626B (en) | Method for preparing battery-grade nickel-cobalt-manganese by extracting organic feed | |
| CN112442605A (en) | Method for separating nickel and magnesium and application thereof | |
| CN111363919A (en) | Compound extracting agent for deep purification of lithium ore leaching solution and purification process | |
| KR100703226B1 (en) | Solvent extraction method for separation of cobalt and calcium | |
| CN116676482A (en) | Method for recycling cobalt chloride hexahydrate from waste lithium battery anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |