CN114538482B - Method for preparing lithium carbonate by purifying lithium-containing solution through adsorption-pressure desorption method - Google Patents
Method for preparing lithium carbonate by purifying lithium-containing solution through adsorption-pressure desorption method Download PDFInfo
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Abstract
The invention provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps: adsorbing the lithium-containing solution by using a lithium adsorbent, and obtaining a saturated lithium adsorbent after saturation of adsorption; pressurizing and desorbing the saturated lithium adsorbent by adopting a composite desorbing agent, wherein the composite desorbing agent comprises a gas-liquid mixture of acid gas and alkali metal bicarbonate solution to obtain lithium-rich desorption liquid; and (3) carrying out gas-liquid separation on the lithium-rich desorption liquid, and crystallizing after the obtained liquid phase is heated and decomposed to obtain a lithium carbonate product. The method adopts the composite desorbing agent to realize the pressurized desorption of the saturated lithium adsorbent, and the composite desorbing agent forms weak acid or acid-free environment to realize the efficient desorption of lithium ions; the composite desorbing agent adopted by the method can greatly reduce the dissolution loss of the lithium adsorbent, improve the recycling times of the lithium adsorbent and reduce the cost; the process for preparing lithium carbonate from the desorption liquid does not involve acid-base neutralization, and has no discharge of acid-base waste liquid and simple process.
Description
Technical Field
The invention belongs to the technical field of lithium extraction and resource utilization, and relates to a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressurization desorption method.
Background
Lithium is an important strategic metal and has wide application prospect in energy and materials. In recent years, with the rapid development of new energy industry, the technical demand for lithium resource development is rapidly increasing, and at present, lithium resources mainly exist in salt lake brine, pegmatite type lithium ores and novel carbonate clay type lithium ores, wherein the lithium resource amount in the salt lake brine accounts for the highest proportion, but the lithium concentration range in the salt lake brine is wider, and the lithium-magnesium ratio is high, so that the separation and extraction of lithium are difficult. In addition to the above-mentioned resources such as lithium-containing lake water and ores, recycling of lithium-containing wastewater is also one of important sources of lithium, such as lithium-containing industrial wastewater and oilfield wastewater, and research on lithium extraction process is a current research hotspot.
The adsorption method is an important method for extracting lithium from lithium-containing solution by utilizing the special adsorption performance of partial heterogeneous adsorbent on lithium ions and realizing selective enrichment and lithium extraction through the stepwise control process of adsorption and desorption ion exchange, and has the characteristics of high cycle stability, high selectivity, environmental protection and low cost. According to the types of the conventional adsorbents such as ion exchange resins, ion imprinting materials, aluminum salt layered materials, manganese ion screens, titanium ion screens and the like, the key of research is the adsorption performance, desorption performance and stability of the adsorption materials, however, the dissolution loss rate of the conventional adsorbents in the desorption process is usually large, so that the adsorption cycle performance is poor.
CN 101928828A discloses a method for extracting lithium from salt lake brine by adsorption, which comprises the following steps: at the temperature of 20-100 ℃, the salt lake brine passes through the aluminum salt-containing adsorption resin at the speed of 5-10 BV/h, and lithium ions in the salt lake brine are adsorbed on the adsorption resin; at the temperature of 20-100 ℃, lithium ions adsorbed on the aluminum salt-containing adsorption resin are eluted and desorbed into the eluent solution by using a lithium ion eluent at the speed of 5-10 BV/h to obtain desorption liquid; removing magnesium in the desorption solution by common sodium cation exchange resin at the speed of 5-10 BV/h, and concentrating to obtain lithium salt; in the method, the desorption of lithium is sequentially carried out by adopting deionized water for rapid elution and gradient elution, the desorption effect is limited, the consumption of desorbing agent is large, and a large amount of generated eluent needs to be treated additionally.
CN 112723395a discloses a process for recycling lithium in shale gas fracturing flowback fluid, which comprises five steps of lithium recovery, hard removal, membrane concentration, biochemical treatment and evaporative crystallization, wherein in the step of lithium recovery, an ion sieve adsorption method is adopted to separate a lithium-containing shale gas pressure flowback fluid, adsorption is carried out at a flow rate of 5-15 BV/h, lithium ions are desorbed into an eluent by using 0.2-2.5 mol/L hydrochloric acid as the desorption agent at a temperature of 40-80 ℃, and precipitant is added to precipitate lithium after the pH is regulated. The method aims at the problems that the treatment steps of shale gas fracturing flowback fluid are complex, and only in the lithium recovery step, strong acid is adopted as desorption liquid, so that the dissolution loss of the adsorbent is easy to occur, the stability and the circulation performance are poor, meanwhile, the composition in the desorption liquid is complex, and the lithium is difficult to directly recover.
CN 113244895a discloses a preparation method of lithium ion imprinting crosslinked chitosan porous microspheres, which comprises the following steps: taking hydrosol formed by acetic acid and chitosan powder as a disperse phase, and sodium hydroxide solution as a continuous phase, and forming chitosan gel beads through physical crosslinking; the preparation method comprises the steps of taking chitosan gel beads as a carrier, taking lithium ions as template ions, taking p-tert-butylphenol as a functional monomer for grafting modification, taking epichlorohydrin as a cross-linking agent, eluting the lithium ions by hydrochloric acid, and preparing the lithium ion imprinting cross-linked chitosan porous microspheres. The method improves the chitosan adsorbent through a crosslinking method, improves the adsorption performance and the recognition performance of the chitosan adsorbent, and improves the defects of easy dissolution, softening and loss of chitosan in an acidic medium to a certain extent, but the modification method is suitable for modifying a part of organic adsorbents with fewer types of adsorbents.
In summary, for the purification process of the lithium-containing solution by adopting the adsorption-desorption method, an appropriate desorption process is also required to be selected according to the type of the adsorbent, so that the desorption rate of lithium is improved, the dissolution loss of the adsorbent is reduced, the recycling performance of the adsorbent is improved, and the cost of raw materials is reduced.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressurization desorption method, which adopts a composite desorption agent to realize pressurization desorption of a saturated lithium adsorbent according to the composition of the lithium-containing solution and the selection of the lithium adsorbent, realizes high-efficiency desorption of lithium ions in weak acid or acid-free environment, has high desorption rate, does not cause dissolution loss of the lithium adsorbent, improves the recycling times of the lithium adsorbent, and reduces the cost of the lithium adsorption process.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing the lithium-containing solution by using a lithium adsorbent, and obtaining a saturated lithium adsorbent after saturation of adsorption;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent comprises a gas-liquid mixture of acid gas and alkali metal bicarbonate solution to obtain lithium-rich desorption liquid;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), and crystallizing after the obtained liquid phase is heated and decomposed to obtain a lithium carbonate product.
According to the invention, for recycling lithium in a low-concentration lithium-containing solution, enrichment and purification are needed, a lithium adsorbent is firstly adopted for adsorption, then the saturated lithium adsorbent is desorbed, a method of composite desorbing agent pressurization desorption is specifically adopted, lithium ions adsorbed by virtue of ion exchange in the saturated lithium adsorbent are converted into soluble lithium salt to enter a liquid phase, desorption of lithium ions in an acid-free or weak acid environment is realized, efficient utilization of lithium elements is promoted, a gas-liquid mixture of acid gas and alkali metal bicarbonate solution is adopted as the composite desorbing agent, a weak acid or acid-free environment is formed, instead of the traditional inorganic strong acid such as hydrochloric acid, sulfuric acid or nitric acid solution is adopted as the desorbing agent, the traditional desorption system is strong in acidity, the pH value is generally less than 1, the metal elements in the adsorbent are easily dissolved, the elements in the adsorbent are lost, the structure collapses, and the stability of the adsorbent and the performance of circularly adsorbing lithium are poor;
the composite desorbing agent adopted by the invention does not react with other elements except lithium ions in the saturated adsorbent, thereby being beneficial to improving the stability of the adsorbent; the bicarbonate radical in the composite desorbing agent enables lithium ions to easily generate stable lithium salt solution, so that desorption of lithium ions is realized, specifically, pressurized desorption is adopted, the solubility of acid gas in bicarbonate solution is improved, the desorption process is enhanced, the desorption rate of lithium ions is improved, and therefore, the cyclic adsorption performance of the adsorption material is greatly improved, zero solution loss of the adsorbent can be realized, the cyclic use times of the lithium adsorbent are improved, and the cost of the lithium adsorption process is reduced;
the lithium ions in the desorbed solution mainly exist in the form of lithium bicarbonate, the gas phase is discharged after gas-liquid separation, the liquid phase is heated for decomposition and crystallization to obtain lithium carbonate, the process does not involve an acid-base neutralization process, no acid-base waste liquid is discharged, the process is simple, and the direct conversion of the lithium bicarbonate into the lithium carbonate is realized.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the lithium-containing solution in step (1) includes any one or a combination of at least two of salt lake brine, oilfield wastewater, lithium precipitation mother liquor, and lithium raffinate, and typical but non-limiting examples of the combination are: the combination of salt lake brine and oilfield wastewater, the combination of salt lake brine and lithium precipitation mother liquor, the combination of oilfield wastewater, lithium precipitation mother liquor and raffinate, and the like are preferably salt lake brine or lithium precipitation mother liquor.
Preferably, the lithium element content in the lithium-containing solution in step (1) is 1g/L or less, for example, 1g/L, 0.8g/L, 0.7g/L, 0.6g/L, 0.5g/L, 0.3g/L, or 0.1g/L, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the lithium adsorbent of step (1) comprises any one or a combination of at least two of a lithium adsorption resin, a manganese-based ion sieve, a titanium-based ion sieve, an aluminum salt material, or an ion imprinting material, typical but non-limiting examples of such combinations being: the combination of the lithium ion-adsorbing resin and the manganese ion-adsorbing sieve, the combination of the manganese ion-adsorbing sieve and the titanium ion-adsorbing sieve, the combination of the lithium ion-adsorbing resin, the aluminum salt material, the manganese ion-adsorbing sieve and the ion-imprinting material, the combination of the manganese ion-adsorbing sieve, the titanium ion-adsorbing sieve and the ion-imprinting material, and the like are preferable.
In the invention, the selection of the components of the composite desorbent is also closely related to the composition of the adsorbent, for example, for a manganese ion sieve, mn is always present in manganese element in the adsorbent 3+ And Mn of 4+ Mn in an acidic solution 3+ The composite desorbing agent is unstable, and is easy to cause oxidation-reduction reaction to produce manganese dissolution loss, so that the ion sieve structure is destroyed, and the industrial application is difficult, and when the composite desorbing agent is adopted, the pH value of a desorption system is often more than 4, so that the oxidation-reduction reaction and dissolution reaction of manganese ions are limited, and the stable structure in the manganese ion sieve is facilitated.
In a preferred embodiment of the present invention, the temperature of the adsorption in the step (1) is 20 to 80 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, but the adsorption is not limited to the values listed, and other values not listed in the range are applicable, and preferably 30 to 80 ℃.
Preferably, during the adsorption process described in step (1), the flow rate of the lithium-containing solution through the lithium adsorbent is 2.5-30 BV/h, such as 2.5BV/h, 5BV/h, 10BV/h, 15BV/h, 20BV/h, 25BV/h or 30BV/h, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable, preferably 5-25 BV/h.
As a preferable technical scheme of the invention, the saturated lithium adsorbent in the step (1) is washed with water before desorption to obtain a lithium-poor solution.
In the invention, the purpose of washing the saturated lithium adsorbent before desorption is to elute impurities adsorbed by the lithium adsorbent, so as to prevent impurity elements from being desorbed in desorption liquid.
The temperature of the water washing is preferably 20 to 40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the flow rate of the water wash is 5-25 BV/h, such as 5BV/h, 8BV/h, 10BV/h, 12BV/h, 15BV/h, 20BV/h or 25BV/h, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the water is used in the water washing process in an amount of 1 to 3BV, for example, 1BV, 1.2BV, 1.5BV, 1.8BV, 2BV, 2.4BV, 2.7BV or 3BV, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the gas phase in the composite desorbent in the step (2) comprises an acid gas and air, and the acid gas comprises CO 2 And/or SO 2 。
Preferably, the volume fraction of the air in the gas phase is 0 to 50%, for example, 0, 10%, 20%, 30%, 40% or 50%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the effect of adding air into the gas phase component of the composite desorbing agent is to regulate and control the system pressure to realize pressurized desorption; when the acid gas includes CO 2 When dissolved in water, bicarbonate can be generated, and water can be selected as the liquid phase component of the composite desorbent.
Preferably, the liquid phase in the composite desorbent of step (2) comprises any one or a combination of at least two of sodium bicarbonate, lithium bicarbonate or potassium bicarbonate, typical but non-limiting examples of which are: a combination of sodium hydrogencarbonate and lithium hydrogencarbonate, a combination of lithium hydrogencarbonate and potassium hydrogencarbonate, a combination of sodium hydrogencarbonate, lithium hydrogencarbonate and potassium hydrogencarbonate, and the like.
Preferably, the concentration of bicarbonate in the composite desorbent in step (2) is 0.001 to 1moL/L, for example, 0.001moL/L, 0.005moL/L, 0.01moL/L, 0.05moL/L, 0.1moL/L, 0.5moL/L, or 1moL/L, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the concentration of the alkali metal in the composite desorbent in step (2) is 0 to 1moL/L, for example, 0moL/L, 0.001moL/L, 0.005moL/L, 0.01moL/L, 0.05moL/L, 0.1moL/L, 0.5moL/L or 1moL/L, etc., but is not limited to the values recited, other non-recited values within the range are equally applicable, and when the alkali metal concentration is 0, CO is selected for the gas phase component 2 The liquid phase component selects a composite desorbing agent of water.
Preferably, the pH of the composite desorbent in step (2) is 4 to 8, such as 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8, but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present invention, the pressure of the pressure desorption in the step (2) is 0.5 to 3MPa, for example, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa or 3MPa, but the pressure is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, the pressure desorption temperature in the step (2) is 0 to 50 ℃, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, in the pressure desorption in the step (2), the flow rate of the composite desorbent is 0.5-5 BV/h, for example, 0.5BV/h, 1BV/h, 1.5BV/h, 2BV/h, 2.5BV/h, 3BV/h, 4BV/h or 5BV/h, etc., but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the amount of the composite desorbent used in the pressure desorption in the step (2) is 3-5 BV, for example, 3BV, 3.5BV, 4BV, 4.5BV or 5BV, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, the lithium concentration of the lithium-rich desorption liquid obtained after the pressure desorption in the step (2) is 4 to 15g/L, for example, 4g/L, 6g/L, 8g/L, 10g/L, 12g/L, 15g/L, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are applicable.
Preferably, the lithium adsorbent obtained after the pressure desorption in the step (2) is returned to the step (1) for reuse.
In a preferred embodiment of the present invention, the temperature of the gas-liquid separation in the step (3) is 0 to 50 ℃, for example, 0 ℃, 10 ℃, 15 ℃, 25 ℃, 30 ℃, 45 ℃, 50 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable; the pressure is 0 to 1MPa, for example, 0MPa, 0.1MPa, 0.3MPa, 0.5MPa, 0.8MPa, 1MPa, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable, and the pressure is gauge pressure.
Preferably, the gas phase obtained by the gas-liquid separation in the step (3) is returned to the step (2) as a component of the composite desorbent.
In a preferred embodiment of the present invention, the decomposition reaction of lithium bicarbonate into lithium carbonate occurs in the thermal decomposition in the step (3).
Preferably, the temperature of the thermal decomposition in the step (3) is 80 to 100 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like, but the thermal decomposition is not limited to the values listed, and other values not listed in the range are applicable.
Preferably, in the thermal decomposition process of the step (3), water evaporates, and lithium carbonate is crystallized.
Preferably, the total amount of evaporated water in step (3) is 30-40%, such as 30%, 32%, 34%, 36%, 38% or 40% of the original volume of the lithium-rich desorption liquid, but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the crystallization raffinate obtained after the crystallization in the step (3) is returned to the step (2) as a component of the composite desorbent.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the content of lithium elements in the lithium-containing solution is less than 1g/L, the lithium adsorbent comprises any one or a combination of at least two of lithium adsorption resin, manganese ion sieve, titanium ion sieve, aluminum salt material and ion imprinting material, the adsorption temperature is 20-80 ℃, the flow rate of the lithium-containing solution is 2.5-30 BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 20-40 ℃, the flow rate is 5-25 BV/h, and the water consumption is 1-3 BV, so that a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent comprises a gas-liquid mixture of acid gas, air and alkali metal bicarbonate solution, and the acid gas comprises CO 2 And/or SO 2 The volume fraction of air in the gas phase is 0-50%, the concentration of bicarbonate in the composite desorbing agent is 0.001-1 moL/L, the concentration of alkali metal is 0-1 moL/L, the pH value is 4-8, the pressure of pressurized desorption is 0.5-3 MPa, the temperature is 0-50 ℃, the flow rate of the composite desorbing agent is 0.5-5 BV/h, the using amount of the composite desorbing agent is 3-5 BV, and the lithium-rich desorption liquid is obtained, the pressure of the pressurized desorption is 0.5-3 MPa, the temperature of the composite desorbing agent is 0-5 BV/h, the using amount of the composite desorbing agent is 3-5 BV, the lithium-rich desorption liquid is obtainedThe lithium concentration of the lithium-rich desorption liquid is 4-15 g/L, and the lithium adsorbent obtained after the pressure desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas-liquid separation temperature is 0-50 ℃ and the pressure is 0-1 MPa, the gas phase obtained by gas-liquid separation returns to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating and decomposing, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during the heating and decomposing, the heating and decomposing temperature is 80-100 ℃, the water is evaporated during the heating and decomposing process, the lithium carbonate is crystallized and separated out, the lithium carbonate product is obtained, the total evaporation water accounts for 30-40% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after the crystallization returns to the step (2) as a component of the composite desorption agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, according to the composition of the lithium-containing solution and the selection of the lithium adsorbent, the composite desorbing agent is adopted to realize the pressurized desorption of the saturated lithium adsorbent, and the composite desorbing agent adopts the gas-liquid mixture of acid gas and alkali metal bicarbonate solution to form a weak acid or acid-free environment, so that the high-efficiency desorption of lithium ions is realized, and the desorption rate is more than 90%;
(2) The composite desorbing agent adopted by the method does not react with other elements except lithium ions in the saturated adsorbent, is favorable for improving the stability of the adsorbent, improves the recycling times, effectively reduces the dissolution loss of the adsorbent, and reduces the dissolution loss of the lithium adsorbent by less than 0.01 percent in the processes of cyclic adsorption and desorption, thereby reducing the cost;
(3) The lithium ions in the solution after the desorption of the method mainly exist in the form of lithium bicarbonate, and the lithium carbonate is obtained by heating, decomposing and crystallizing the liquid phase after the gas-liquid separation, and the process does not involve the acid-base neutralization process, has no discharge of acid-base waste liquid and simple process, and realizes the direct conversion of the lithium bicarbonate into the lithium carbonate.
Drawings
Fig. 1 is a process flow chart of a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method provided in example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The invention provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing the lithium-containing solution by using a lithium adsorbent, and obtaining a saturated lithium adsorbent after saturation of adsorption;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent comprises a gas-liquid mixture of acid gas and alkali metal bicarbonate solution to obtain lithium-rich desorption liquid;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), and crystallizing after the obtained liquid phase is heated and decomposed to obtain a lithium carbonate product.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, wherein a process flow chart of the method is shown in fig. 1, and the method comprises the following steps:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the lithium-containing solution is salt lake brine with the lithium element content of 1g/L, the lithium adsorbent is a manganese ion sieve, the adsorption temperature is 80 ℃, the flow rate of the lithium-containing solution is 30BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 30 ℃, the flow rate is 25BV/h, the water consumption is 3BV, and a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent is CO 2 A gas-liquid mixture of air and lithium bicarbonate solution, the volume fraction of air in the gas phase being 25%,the concentration of bicarbonate in the composite desorbing agent is 1moL/L, the pH value is 4, the pressure of the pressurized desorption is 3MPa, the temperature is 0 ℃, the flow rate of the composite desorbing agent is 5BV/h, the dosage of the composite desorbing agent is 5BV, the lithium-rich desorption liquid is obtained, the lithium concentration of the lithium-rich desorption liquid is 15g/L, and the lithium adsorbent obtained after the pressurized desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas phase obtained by gas-liquid separation is returned to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating and decomposing, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating and decomposing, the temperature of the heating and decomposing is 90 ℃, water is evaporated during heating and decomposing, the lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water amount accounts for 30% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization is returned to the step (2) as a component of the composite desorption agent.
Measuring the concentration of lithium elements in the solution by adopting an inductively coupled plasma emission spectrometer (ICP-OES), and subtracting the initial concentration and the solution volume of the lithium elements in the lithium-containing solution from the initial concentration and the solution volume of the lithium elements in the lithium-poor solution to calculate the adsorption quantity of the lithium adsorbent, and subtracting the desorption quantity of the lithium from the concentration and the solution volume of the lithium elements in the lithium-rich desorption liquid and the concentration and the solution volume of the lithium elements in the composite desorption liquid to obtain the desorption rate eta of the lithium; and calculating the dissolution loss rate of the lithium adsorbent according to the concentration of the dissolved active elements in the lithium-rich desorption liquid, the volume of the solution and the mass of the active elements in the adsorbent.
In the embodiment, the lithium-containing solution is treated by the process, and the desorption rate of lithium in the step (2) reaches 95%, and the dissolution loss of manganese in the lithium adsorbent is only 0.008%.
Example 2:
the embodiment provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the lithium-containing solution is raffinate wastewater with the content of lithium element of 0.8g/L, the lithium adsorbent is lithium adsorption resin, the adsorption temperature is 20 ℃, the flow rate of the lithium-containing solution is 2.5BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 20 ℃, the flow rate is 5BV/h, the water consumption is 1BV, and a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent is SO 2 The concentration of bicarbonate radical in the composite desorbing agent is 0.001moL/L, the pH value is 6, the pressure of the pressurized desorption is 0.5MPa, the temperature is 50 ℃, the flow rate of the composite desorbing agent is 0.5BV/h, the using amount of the composite desorbing agent is 3BV, a lithium-rich desorption solution is obtained, the lithium concentration of the lithium-rich desorption solution is 4g/L, and the lithium adsorbent obtained after the pressurized desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas phase obtained by gas-liquid separation is returned to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating decomposition, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating decomposition, the temperature of the heating decomposition is 80 ℃, water is evaporated in the heating decomposition process, the lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water amount accounts for 40% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization is returned to the step (2) as a component of the composite desorption agent.
The test method was the same as that in example 1.
In this embodiment, the lithium-containing solution is treated by the above process, and the desorption rate of lithium in the step (2) is calculated to be 90%, and the metal dissolution loss in the lithium adsorbent is only 0.005%.
Example 3:
the embodiment provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the lithium-containing solution is a lithium precipitation mother solution with the content of lithium elements of 0.75g/L, the lithium adsorbent is a manganese ion sieve, the adsorption temperature is 40 ℃, the flow rate of the lithium-containing solution is 10BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 40 ℃, the flow rate is 10BV/h, the water consumption is 2BV, and a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent is CO 2 And water, wherein the concentration of bicarbonate in the composite desorbing agent is 0.01moL/L, the pH value is 6.5, the pressure of the pressurized desorption is 1MPa, the temperature is 20 ℃, the flow rate of the composite desorbing agent is 2BV/h, the using amount of the composite desorbing agent is 4BV, a lithium-rich desorption solution is obtained, the lithium concentration of the lithium-rich desorption solution is 10g/L, and the lithium adsorbent obtained after the pressurized desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas phase obtained by gas-liquid separation is returned to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating and decomposing, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating and decomposing, the temperature of heating and decomposing is 100 ℃, water is evaporated during heating and decomposing, lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water amount accounts for 35% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization is returned to the step (2) as a component of the composite desorption agent.
The test method was the same as that in example 1.
In the embodiment, the lithium-containing solution is treated by the process, and the desorption rate of lithium in the step (2) reaches 92% through calculation, so that the lithium adsorbent has no manganese dissolution loss.
Example 4:
the embodiment provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the lithium-containing solution is salt lake brine with the lithium element content of 0.9g/L, the lithium adsorbent is a titanium ion sieve, the adsorption temperature is 50 ℃, the flow rate of the lithium-containing solution is 20BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 25 ℃, the flow rate is 15BV/h, and the water consumption is 1.5BV, so that a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent is CO 2 The volume fraction of the air in the gas phase is 40%, the concentration of bicarbonate radical in the composite desorbing agent is 0.5moL/L, the pH value is 8, the pressure of the pressurized desorption is 1.5MPa, the temperature is 35 ℃, the flow rate of the composite desorbing agent is 3BV/h, the using amount of the composite desorbing agent is 4.5BV, the lithium-rich desorption liquid is obtained, the lithium concentration of the lithium-rich desorption liquid is 6g/L, and the lithium adsorbent obtained after the pressurized desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas phase obtained by gas-liquid separation is returned to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating decomposition, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating decomposition, the temperature of the heating decomposition is 85 ℃, water is evaporated during the heating decomposition, the lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water amount accounts for 32% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization is returned to the step (2) as a component of the composite desorption agent.
The test method was the same as that in example 1.
In this embodiment, the lithium-containing solution is treated by the above process, and the desorption rate of lithium in the step (2) is calculated to be 94%, and the metal dissolution loss in the lithium adsorbent is only 0.01%.
Example 5:
the embodiment provides a method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which comprises the following steps:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the lithium-containing solution is a lithium precipitation mother solution with the content of lithium elements of 0.6g/L, the lithium adsorbent is an ion imprinting material, the adsorption temperature is 70 ℃, the flow rate of the lithium-containing solution is 15BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 35 ℃, the flow rate is 20BV/h, the water consumption is 2.5BV, and a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent is SO 2 The volume fraction of the air in the gas phase is 10%, the concentration of bicarbonate radical in the composite desorbing agent is 0.05moL/L, the pH value is 5, the pressure of the pressurized desorption is 2MPa, the temperature is 10 ℃, the flow rate of the composite desorbing agent is 4BV/h, the using amount of the composite desorbing agent is 3.6BV, the lithium-rich desorption liquid is obtained, the lithium concentration of the lithium-rich desorption liquid is 12g/L, and the lithium adsorbent obtained after the pressurized desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas phase obtained by gas-liquid separation is returned to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating decomposition, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating decomposition, the temperature of the heating decomposition is 95 ℃, water is evaporated in the heating decomposition process, the lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water amount accounts for 36% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization is returned to the step (2) as a component of the composite desorption agent.
The test method was the same as that in example 1.
In this embodiment, the lithium-containing solution is treated by the above process, and the desorption rate of lithium in the step (2) is calculated to be 94%, and the metal dissolution loss in the lithium adsorbent is only 0.007%.
Comparative example 1:
this example provides a method for preparing lithium carbonate by purifying a lithium-containing solution by adsorption-desorption, which is different from the method of example 1 only in that: and (3) carrying out normal pressure desorption in the step (1), wherein 0.1mol/L hydrochloric acid is adopted as a desorption agent.
In the comparative example, since hydrochloric acid is a strong acid, metallic manganese in the lithium adsorbent is easily dissolved during desorption, so that the element loss in the adsorbent is caused, the manganese dissolution loss at the moment reaches 1.52%, the structure of the adsorbent is easily collapsed, and the stability and the recycling performance are easily deteriorated; if the concentration of the hydrochloric acid is reduced, the dissolution loss of the adsorbent can be reduced, but the desorption rate at this time is also obviously reduced, and the desorption requirement cannot be met.
It can be seen from the above examples and comparative examples that the method of the present invention adopts a composite desorbing agent to realize the pressurized desorption of the saturated lithium adsorbent according to the composition of the lithium-containing solution and the selection of the lithium adsorbent, and the composite desorbing agent adopts a gas-liquid mixture of acid gas and alkali metal bicarbonate solution to form a weak acid or acid-free environment, so as to realize the efficient desorption of lithium ions, and the desorption rate reaches more than 90%; the composite desorbing agent adopted by the method does not react with other elements except lithium ions in the saturated adsorbent, is favorable for improving the stability of the adsorbent, improves the recycling times, effectively reduces the dissolution loss of the adsorbent, and reduces the dissolution loss of the lithium adsorbent by less than 0.01 percent in the processes of cyclic adsorption and desorption, thereby reducing the cost; the lithium ions in the solution after the desorption of the method mainly exist in the form of lithium bicarbonate, and the lithium carbonate is obtained through the crystallization of the liquid phase after the gas-liquid separation by heating decomposition, and the process does not involve the acid-base neutralization process, has no discharge of acid-base waste liquid and simple process, and realizes the direct conversion of the lithium bicarbonate into the lithium carbonate.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (30)
1. A method for preparing lithium carbonate by purifying a lithium-containing solution by an adsorption-pressure desorption method, which is characterized by comprising the following steps:
(1) Adsorbing the lithium-containing solution by using a lithium adsorbent, wherein the lithium adsorbent comprises any one or a combination of at least two of lithium adsorption resin, manganese ion sieve, titanium ion sieve, aluminum salt material and ion imprinting material, and obtaining a saturated lithium adsorbent after adsorption saturation;
(2) Carrying out pressurized desorption on the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the pressure of the pressurized desorption is 0.5-3 MPa, the composite desorbing agent comprises a gas-liquid mixture of acid gas and alkali metal bicarbonate solution, and the acid gas comprises CO 2 And/or SO 2 The pH value of the composite desorbing agent is 4-8, and the lithium-rich desorption liquid is obtained;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), and crystallizing after the obtained liquid phase is heated and decomposed to obtain a lithium carbonate product.
2. The method of claim 1, wherein the lithium-containing solution of step (1) comprises any one or a combination of at least two of salt lake brine, oilfield wastewater, lithium precipitation mother liquor, or lithium raffinate.
3. The method of claim 2, wherein the lithium-containing solution of step (1) is salt lake brine or lithium precipitation mother liquor.
4. The method according to claim 1, wherein the content of lithium element in the lithium-containing solution of step (1) is 1g/L or less.
5. The method of claim 1, wherein the lithium adsorbent of step (1) is a lithium adsorbent resin and/or a manganese-based ion sieve.
6. The method of claim 1, wherein the temperature of adsorption in step (1) is 20 to 80 ℃.
7. The method of claim 6, wherein the temperature of the adsorption in step (1) is 30 to 80 ℃.
8. The method of claim 1, wherein during the adsorption of step (1), the flow rate of the lithium-containing solution through the lithium adsorbent is 2.5 to 30BV/h.
9. The method of claim 8, wherein during the adsorption of step (1), the flow rate of the lithium-containing solution through the lithium adsorbent is 5 to 25BV/h.
10. The method of claim 1, wherein the saturated lithium adsorbent of step (1) is washed with water to obtain a lithium-depleted solution prior to desorption.
11. The method according to claim 10, wherein the water washing is carried out at a temperature of 20 to 40 ℃.
12. The method according to claim 10, wherein the flow rate of the water wash is 5-25 BV/h.
13. The method according to claim 10, wherein the amount of water used in the water washing process is 1-3 BV.
14. The method of claim 1 wherein the vapor phase in the composite desorbent of step (2) comprises an acid gas and air.
15. The method of claim 14, wherein the volume fraction of air in the gas phase is 0-50%.
16. The method of claim 1, wherein the liquid phase in the composite desorbent of step (2) comprises any one or a combination of at least two of sodium bicarbonate, lithium bicarbonate, or potassium bicarbonate.
17. The method of claim 1, wherein the concentration of bicarbonate in the composite desorbent of step (2) is 0.001 to 1moL/L and the concentration of alkali metal is 0 to 1moL/L.
18. The process of claim 1 wherein the pressure desorption in step (2) is at a temperature of 0 to 50 ℃.
19. The method of claim 1, wherein the flow rate of the composite desorbent during the pressurized desorption in step (2) is 0.5-5 BV/h.
20. The method of claim 1, wherein the amount of the composite desorbent used in the pressure desorption in the step (2) is 3 to 5BV.
21. The method according to claim 1, wherein the concentration of lithium in the lithium-rich desorption liquid obtained after the pressure desorption in the step (2) is 4-15 g/L.
22. The method of claim 1, wherein the lithium adsorbent obtained after the pressure desorption in step (2) is returned to step (1) for reuse.
23. The method according to claim 1, wherein the temperature of the gas-liquid separation in the step (3) is 0 to 50 ℃ and the pressure is 0 to 1MPa.
24. The method of claim 1, wherein the gas phase resulting from the gas-liquid separation of step (3) is returned to step (2) as a component of the composite desorbent.
25. The method of claim 1, wherein the decomposition of lithium bicarbonate to lithium carbonate occurs during the thermal decomposition of step (3).
26. The method of claim 1, wherein the thermal decomposition temperature in step (3) is 80-100 ℃.
27. The method of claim 1, wherein the water evaporates during the thermal decomposition of step (3) and the lithium carbonate crystallizes out.
28. The method of claim 27, wherein the total amount of vaporized water in step (3) is 30-40% of the initial volume of the lithium-rich desorption liquid.
29. The process of claim 1 wherein the raffinate from said crystallization in step (3) is returned to step (2) as a component of the composite desorbent.
30. The method according to claim 1, characterized in that it comprises the steps of:
(1) Adsorbing a lithium-containing solution by using a lithium adsorbent, wherein the content of lithium elements in the lithium-containing solution is less than 1g/L, the lithium adsorbent comprises any one or a combination of at least two of lithium adsorption resin, manganese ion sieve, titanium ion sieve, aluminum salt material and ion imprinting material, the adsorption temperature is 20-80 ℃, the flow rate of the lithium-containing solution is 2.5-30 BV/h, and the saturated lithium adsorbent is obtained after adsorption saturation; the saturated lithium adsorbent is washed by water, the temperature of the water washing is 20-40 ℃, the flow rate is 5-25 BV/h, and the water consumption is 1-3 BV, so that a lithium-poor solution is obtained;
(2) Pressurizing and desorbing the saturated lithium adsorbent obtained in the step (1) by adopting a composite desorbing agent, wherein the composite desorbing agent comprises a gas-liquid mixture of acid gas, air and alkali metal bicarbonate solution, and the acid gas comprises CO 2 And/or SO 2 The volume fraction of air in the gas phase is 0-50%, the concentration of bicarbonate in the composite desorbing agent is 0.001-1 moL/L, the concentration of alkali metal is 0-1 moL/L, the pH value is 4-8, and the pressure of pressure desorption is 0.5-3 MPa, the temperature is 0-50 ℃, the flow rate of the composite desorbing agent is 0.5-5 BV/h, the dosage of the composite desorbing agent is 3-5 BV, the lithium-rich desorption liquid is obtained, the lithium concentration of the lithium-rich desorption liquid is 4-15 g/L, and the lithium adsorbent obtained after the pressurizing desorption is returned to the step (1) for reuse;
(3) And (3) carrying out gas-liquid separation on the lithium-rich desorption liquid obtained in the step (2), wherein the gas-liquid separation temperature is 0-50 ℃ and the pressure is 0-1 MPa, the gas phase obtained by gas-liquid separation returns to the step (2) as a component of the composite desorption agent, the obtained liquid phase is crystallized after heating and decomposing, the reaction of decomposing lithium bicarbonate into lithium carbonate occurs during heating and decomposing, the temperature of the heating and decomposing is 80-100 ℃, water is evaporated in the heating and decomposing process, the lithium carbonate is crystallized and separated out, a lithium carbonate product is obtained, the total evaporation water accounts for 30-40% of the initial volume of the lithium-rich desorption liquid, and the crystallized residual liquid obtained after crystallization returns to the step (2) as a component of the composite desorption agent.
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