CN110484725B - Pre-enrichment extraction system and pre-enrichment method for potassium and lithium in brine - Google Patents
Pre-enrichment extraction system and pre-enrichment method for potassium and lithium in brine Download PDFInfo
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- CN110484725B CN110484725B CN201910891160.2A CN201910891160A CN110484725B CN 110484725 B CN110484725 B CN 110484725B CN 201910891160 A CN201910891160 A CN 201910891160A CN 110484725 B CN110484725 B CN 110484725B
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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
- C22B26/10—Obtaining alkali metals
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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
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
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- 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
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Abstract
The invention discloses a pre-enrichment extraction system and a pre-enrichment method for potassium and lithium in brine. The pre-enrichment method of potassium and lithium in the brine comprises the following steps: (1) extracting brine by using an extracting agent, a diluent and a co-extracting agent to obtain an extraction liquid rich in potassium and sodium and a raffinate rich in magnesium, boron and lithium, wherein the extracting agent comprises dibenzo-18-crown ether-6, and the co-extracting agent comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl iminium salt; (2) performing back extraction on the extraction liquid to obtain an aqueous solution rich in potassium and sodium, and then separating the aqueous solution rich in potassium and sodium to obtain potassium salt; (3) and (2) separating the raffinate obtained in the step (1) to obtain lithium salt. The pre-enrichment method of potassium and lithium in brine has the advantages of simple process, high pre-enrichment efficiency, low production cost and the like, is beneficial to sustainable development of comprehensive utilization of salt lake resources, and has better economic benefit and social benefit.
Description
Technical Field
The invention relates to the field of comprehensive utilization of salt lake brine resources, in particular to a pre-enrichment extraction system and a pre-enrichment method for potassium and lithium in salt lake brine.
Background
The salt lake brine has rich mineral resources and huge development and utilization values, and particularly, the development and utilization of potassium and lithium resources are related to national civilization and have great strategic significance. In the traditional process for developing potassium salt in salt lake brine, a salt field beach drying process is mostly adopted to pre-enrich potassium salt in salt lake raw brine. Carnallite obtained by solarization is used as a production raw material of potassium salt, and old brine is used as a production raw material of lithium salt, boric acid and the like. But the beach sunning process of the brine salt field is long, and the extraction efficiency of target elements is not high; the salt pan occupies a large area, has high investment and maintenance cost, and brings potential harm to the ecological environment of the salt lake, and the development process of potassium salt, lithium salt and the like in the traditional salt lake brine needs to be improved urgently.
The solvent extraction method is a very mature and reliable modern separation and extraction technology, has a series of advantages of large production capacity, high-efficiency extraction, fine separation, energy conservation, low carbon, easy realization of continuous operation and automatic control and the like, and is widely applied to the fields of wet metallurgy, inorganic chemical industry, organic and petrochemical industry, bio-pharmaceuticals, wastewater treatment, analytical chemistry and the like. In the reported method for extracting lithium from old brine in salt lake, the organic phosphorus extraction system, especially the neutral phosphorus synergistic extraction system, has high selectivity to lithium, and is a hot spot for the research and application of extracting lithium from brine in salt lake at home and abroad.
For example, CN104404268A discloses a novel co-extraction system for extracting lithium from brine with high magnesium-lithium ratio and a co-extraction method thereof, the method adopts tributyl phosphate or triisobutyl phosphate, and obtains a better effect on extracting lithium from brine with high magnesium-lithium ratio in a salt lake.
For another example, CN105152190A discloses a method for producing lithium carbonate by separating magnesium from low-lithium brine and enriching lithium, in which trialkyl phosphate is mainly used to extract low-lithium salt lake brine, the extraction process is performed under weak acid or neutral condition, the production cost is low, and the method is particularly suitable for producing lithium carbonate by separating magnesium from salt lake brine with a magnesium-lithium mass ratio of less than 120.
The methods obtain good lithium extraction effect, but most of the methods use a brine system obtained by evaporating salt lake old brine or salt lake raw brine as a production raw material, and the method still cannot avoid the loss of potassium and lithium in the salt lake raw brine caused by adopting the traditional brine salt field beach sun-drying process to pretreat the salt lake raw brine.
Disclosure of Invention
The invention mainly aims to provide a pre-enrichment extraction system of potassium and lithium in salt lake brine and a pre-enrichment method of potassium and lithium, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pre-enrichment extraction system for potassium and lithium in brine comprises an extractant and a synergist, wherein the extractant comprises dibenzo-18-crown ether-6, and the synergist comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl iminium salt.
The embodiment of the invention also provides a pre-enrichment method of potassium and lithium in brine, which comprises the following steps:
(1) extracting brine by using an extracting agent, a diluent and a co-extracting agent to obtain an extraction liquid rich in potassium and sodium and a raffinate rich in magnesium, boron and lithium, wherein the extracting agent comprises dibenzo-18-crown ether-6, and the co-extracting agent comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl iminium salt;
(2) performing back extraction on the extraction liquid to obtain an aqueous solution rich in potassium and sodium, and then separating the aqueous solution rich in potassium and sodium to obtain potassium salt;
(3) and (2) separating the raffinate obtained in the step (1) to obtain lithium salt.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, an organic extraction system with very high selectivity to potassium and sodium is used, and the solutions rich in potassium and lithium are respectively obtained through a solvent extraction method, so that the separation and pre-enrichment of potassium and lithium in brine are realized in one step, and the potassium-rich solution and the lithium-rich solution can be directly used as raw materials for the subsequent production of potassium salt and lithium salt. The problems of huge occupied area, high salt field construction and maintenance cost, long beach sunning time, low target element recovery rate and the like caused by beach sunning of the brine salt field are solved.
(2) The reaction temperature in the whole extraction and back extraction process is normal temperature, pH is not required to be adjusted, the energy consumption is low, and the requirement on equipment is not high.
(3) Compared with the brine salt field beach sunning process, the method has the advantages of simpler process, high pre-enrichment efficiency, low production cost and the like, is beneficial to the sustainable development of comprehensive utilization of salt lake resources, and has better economic benefit and social benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of an extraction process flow in an exemplary embodiment of the invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
In one aspect of the technical scheme, the invention relates to a pre-enrichment extraction system for potassium and lithium in brine, which comprises an extractant and a synergist, wherein the extractant comprises dibenzo-18-crown ether-6 (DB 18C6 for short), and the synergist comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ([ C4mim+][NTf2 -]Abbreviated as ILs).
In some embodiments, the extraction system further comprises a diluent comprising 1,2 dichloroethane (C)2H4Cl2) Any one or combination of more than two of n-octanol, chloroform, xylene, nitrobenzene and ethyl acetate.
As another aspect of the technical scheme of the invention, the invention relates to a method for pre-enriching potassium and lithium in brine, which comprises the following steps:
(1) extracting brine by using an extracting agent, a diluent and a co-extracting agent to obtain an extraction liquid (namely an oil phase) rich in potassium and sodium and a raffinate (namely a water phase) rich in magnesium, boron and lithium, wherein the extracting agent comprises dibenzo-18-crown ether-6, and the co-extracting agent comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl iminium salt;
(2) performing back extraction on the extraction liquid to obtain an aqueous solution rich in potassium and sodium, and then separating the aqueous solution rich in potassium and sodium to obtain potassium salt;
(3) and (2) separating the raffinate obtained in the step (1) to obtain lithium salt.
Wherein the brine can be salt lake brine, the extract rich in potassium and sodium is oil phase, and the raffinate rich in magnesium, boron and lithium is water phase. The volume ratio of the extract to the raffinate obtained in step (1) was 1: 1.
In the step (1), the extracting agent, the diluent and the co-extracting agent form an extracting system together.
In some embodiments, the diluent to synergist is in a volume ratio of 2:1 to 9: 1.
In some embodiments, the extractant has a molar concentration of 0.05 to 0.5 mol/L.
In some embodiments, the extract is stripped with an ammonium nitrate solution in step (2).
In some more preferred embodiments, the ammonium nitrate solution has a molar concentration of 2 to 3 mol/L.
In some preferred embodiments, the volume ratio of the oil phase to the aqueous phase during stripping is 1:1, and both the extraction and stripping are performed at ambient temperature.
Wherein, the brine does not need to adjust the pH value.
In some embodiments, the aqueous solution enriched in potassium and sodium is separated in step (2) using conventional methods such as flotation. Other conventional potassium-sodium separation methods may also be employed, such as potassium-sodium separation processes that are familiar and commonly used by those skilled in the art.
In some embodiments, step (3) comprises: and (2) separating the raffinate obtained in the step (1) by adopting an ionic membrane or a conventional method for extracting lithium by extraction separation and the like to obtain the lithium salt. Other conventional methods of lithium extraction may also be employed, such as by using lithium extraction processes familiar and commonly used by those skilled in the art.
The flow of the extraction process of the present invention can be seen in figure 1.
The invention provides a pre-enrichment extraction system of potassium and lithium in salt lake brine and a pre-enrichment method of potassium and lithium, which change the comprehensive pretreatment method of salt lake raw brine in the process of producing salt lake chemical products such as potassium salt, lithium salt and the like by using the traditional salt lake brine. The solvent extraction method can be applied to the pre-enrichment and separation of potassium and lithium in the early element stage of the salt lake brine, and has good development prospect and great economic benefit.
The technical solutions of the present invention will be described in further detail with reference to several preferred embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
A process for pre-enriching K and Li in bittern of salt lake includes such steps as pre-enriching K and Li in the bittern of salt lake according to C2H4Cl2And ILs in a volume ratio of 9:1, and then adding an appropriate amount of DB18C6 into the solvent to ensure that the molar concentration of the DB18C6 extractant is 0.2 mol/L. Then carrying out extraction reaction on 0.2mol/L DB18C6 organic extractant and brine, and collecting an extracted oil phase; extracting the raffinate for 1-2 times according to the steps, and collecting the raffinate. Collecting all oil phases, mixing with 2mol/L ammonium nitrate solution, and performing back extraction to obtain back extraction raffinate and oil phases. Table 1 shows the results of DB18C6 salt lake brine extraction simulation, and Table 2 shows the results of DB18C6 salt lake brine real extraction.
TABLE 1 results of DB18C6 extraction of salt lake brine simulant
TABLE 2 DB18C6 results of real brine extraction from salt lake
Wherein the real brine is intercrystalline brine in the lake region of the Baylor beach of the Carlo sweat salt lake.
As can be seen from tables 1 and 2, the pre-concentration method for potassium and lithium in brine has the advantages of high pre-concentration efficiency, simple process and low production cost.
Example 2
A process for pre-enriching K and Li in bittern of salt lake includes such steps as pre-enriching K and Li in the bittern of salt lake according to C2H4Cl2And ILs in a volume ratio of 5:1, and then adding an appropriate amount of DB18C6 into the solvent to ensure that the molar concentration of the DB18C6 extractant is 0.5 mol/L. Then carrying out extraction reaction on 0.5mol/L DB18C6 organic extractant and brine, and collecting an extracted oil phase; extracting the raffinate for 1-2 times according to the steps, and collecting the raffinate. Collecting all oil phases, mixing with 3mol/L ammonium nitrate solution, and performing back extraction to obtain back extraction raffinate and oil phases.
Example 3
A process for pre-enriching K and Li in bittern of salt lake includes such steps as pre-enriching K and Li in the bittern of salt lake according to C2H4Cl2And ILs in a volume ratio of 2:1, and then adding an appropriate amount of DB18C6 into the solvent to ensure that the molar concentration of the DB18C6 extractant is 0.05 mol/L. Then carrying out extraction reaction on 0.05mol/L DB18C6 organic extractant and brine, and collecting an extracted oil phase; extracting the raffinate for 1-2 times according to the steps, and collecting the raffinate. Collecting all oil phases, mixing with 2.5mol/L ammonium nitrate solution, and performing back extraction to obtain back extraction raffinate and oil phases.
In addition, the inventor also carries out corresponding tests by using other process conditions and the like listed in the foregoing to replace the corresponding process conditions in the examples 1 to 3, and the contents to be verified are similar to the products of the examples 1 to 3. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 3 are used as representatives to describe the excellent points of the present invention.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (2)
1. A pre-enrichment method of potassium and lithium in brine is characterized by comprising the following steps:
(1) extracting brine by using an extracting agent, a diluent and a co-extracting agent to obtain an extraction liquid rich in potassium and sodium and a raffinate rich in magnesium, boron and lithium, wherein the extracting agent is dibenzo-18-crown ether-6, the co-extracting agent is 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl iminium salt, the diluent is selected from any one or a combination of more than two of 1,2 dichloroethane, n-octanol, chloroform, xylene, nitrobenzene and ethyl acetate, the volume ratio of the diluent to the co-extracting agent is 2: 1-9: 1, and the molar concentration of the extracting agent is 0.05-0.5 mol/L;
(2) performing back extraction on the extraction liquid by adopting an ammonium nitrate solution to obtain a potassium and sodium rich aqueous solution, and then separating the potassium and sodium rich aqueous solution by adopting a flotation method to obtain potassium salt, wherein the molar concentration of the ammonium nitrate solution is 2-3 mol/L;
(3) and (2) separating the raffinate obtained in the step (1) by adopting an ionic membrane or a method for extracting lithium by extraction separation to obtain lithium salt.
2. The pre-enrichment method of potassium and lithium in brine as claimed in claim 1, wherein: the volume ratio of the oil phase to the water phase in the back extraction process is 1:1, and the extraction and the back extraction are both carried out at normal temperature.
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