CN111533145A - Method for recovering lithium from byproduct mirabilite mother liquor of lithium oxide hydrogen production from spodumene - Google Patents

Method for recovering lithium from byproduct mirabilite mother liquor of lithium oxide hydrogen production from spodumene Download PDF

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CN111533145A
CN111533145A CN202010384466.1A CN202010384466A CN111533145A CN 111533145 A CN111533145 A CN 111533145A CN 202010384466 A CN202010384466 A CN 202010384466A CN 111533145 A CN111533145 A CN 111533145A
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lithium
adsorbent
mother liquor
adsorption
titanium
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CN111533145B (en
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钟辉
张天刚
彭嘉惠
陈周秦
赖先熔
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Sichuan Panyu Lithium Energy New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/06—Sulfates; Sulfites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/308—Methods for converting an alkali metal orthophosphate into another one; Purification; Decolorasing; Dehydrating; Drying
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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Abstract

The invention relates to a method for recovering lithium from a mirabilite mother liquor which is a byproduct of lithium oxide hydrogen production from spodumene1(ii) a Adsorbing mother liquor B of the first stage by using manganese lithium adsorbent1Performing deep adsorption lithium extraction treatment to separate the lithium ion-loaded manganese lithium adsorbent and the second-stage adsorption mother liquor B2. Inorganic acid with certain concentration is used as desorption liquid to respectively desorb and desorb the lithium-loaded titanium-series lithium adsorbent and the lithium-loaded manganese-series lithium adsorbentThe absorption completion liquid is C1And C2. The invention utilizes manganese lithium adsorbent and titanium lithium adsorbent to Li+Has high adsorption rate to Li under different alkalinity+The method has the characteristics of good adsorption performance, and can be used for synergistically adsorbing and recovering lithium ions in the mirabilite mother liquor, so that the problem of large loss of the lithium ions in the existing production process is avoided, the total recovery rate of lithium is greatly improved, the material consumption is reduced, and the product value is improved.

Description

Method for recovering lithium from byproduct mirabilite mother liquor of lithium oxide hydrogen production from spodumene
Technical Field
The invention relates to the technical field of chemical separation, and particularly relates to a method for recovering lithium from a byproduct mirabilite mother liquor of lithium oxide hydrogen production from spodumene.
Background
Lithium hydroxide is one of the most important lithium salts, has wide application and is mainly used in the industries of chemical raw materials, chemical reagents, battery industry and the like. With the advent of high capacity lithium batteries, lithium hydroxide can provide high energy density for high nickel ternary positive electrode materials, resulting in a dramatic increase in lithium hydroxide demand.
At present, the lithium hydroxide produced in the market is mainly prepared by a spodumene acidification roasting-freezing method. In the production technology, spodumene is subjected to transformation calcination, acidification roasting, water leaching and filtration, and a large amount of mirabilite (Na) is separated from a leaching solution after causticization and freezing2SO4·10H2O), the mirabilite is entrained with a large amount of Li+After redissolving it, Li in solution+The content is higher (the content is about 2.5-3.5g/L and accounts for about 20 percent of the total lithium content). The prior art recovers the part of lithium by dissolving the mirabilite and evaporating, concentrating, crystallizing and separating out anhydrous Na2SO4The crystallization mother liquor (Li) is then added+The content is about 9-10 g/L) and returns to the main process freezing process for freezing, and the circulation is repeated.
However, the prior art recovery of lithium has various problems:
(1) the material circulation volume is very big. Mainly, the crystallization mother liquor after the anhydrous sodium sulfate is separated by evaporation crystallization has great amount, and 1 ten thousand tons of LiOH. H are produced every year2The production scale of O is taken as an example, the amount of the crystallization mother liquor reaches 10000-3Returning to the main process for freezing crystallization, filtration, evaporative crystallization and filtration in one year to ensure that the equipment load of the four working sections is large(increase by 20-30%), high investment, high cost and high consumption.
(2) The loss of lithium is large. Because a large amount of lithium in the crystallization mother liquor is not separated from the system and is continuously and circularly enriched, the by-product produced by evaporation crystallization contains anhydrous Na2SO4The entrained lithium content is 0.1-0.2%, resulting in a loss of 3-5% of the total lithium content.
Disclosure of Invention
The invention aims to: aiming at the technical problems of large consumption, high cost and low lithium recovery rate in the process of recovering lithium from a mirabilite by-product mother liquor which is a byproduct of lithium hydroxide and lithium oxide from spodumene in the prior art, the method for recovering lithium from the mirabilite by-product mother liquor which is a byproduct of lithium hydroxide and lithium oxide is provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for recovering lithium from a byproduct mirabilite mother solution of lithium oxide hydrogen production from spodumene comprises the following two-stage adsorption and desorption treatment steps:
first-stage adsorption treatment: carrying out lithium adsorption treatment on mirabilite mother liquor by using a titanium lithium adsorbent to generate the following adsorption reaction equation (1) to obtain a lithium-loaded titanium lithium adsorbent A1And the first stage adsorption mother liquor B1(ii) a The mass ratio of the total lithium in the mirabilite mother liquor to the use amount of the titanium lithium adsorbent is 0.003-0.01: 1;
H-TO+Li+＝Li-TO+H+(1)
H-TO is a hydrogen-type titanium adsorbent, Li-TO is a lithium-type titanium adsorbent (A)1) And TO is an adsorbent framework;
second-stage adsorption treatment: adsorbing mother liquor B of the first stage by using manganese lithium adsorbent1Performing lithium adsorption treatment to generate the following adsorption reaction equation (2) to obtain the lithium ion-loaded manganese-based lithium adsorbent A2And second-stage adsorption mother liquor B2(ii) a The first section adsorbs mother liquor B1The mass ratio of the total lithium content to the manganese lithium adsorbent is 0.005-0.008: 1;
H-MO+Li+＝Li-MO+H+(2)
H-MO is a hydrogen type manganese-based lithium adsorbent, and Li-MO is a lithium type manganese-based lithium adsorbent (A)2) MO is a manganese adsorbent framework;
desorption treatment: carrying out adsorption treatment on the first stage of the adsorption treatment to obtain a lithium ion-loaded titanium lithium adsorbent A1Desorbing with inorganic acid, wherein the desorption reaction is shown in equation (3), and obtaining lithium-containing desorption completion liquid C1(ii) a The inorganic acid and the lithium ion-loaded titanium-based lithium adsorbent A1The contact time is 0.5 h-12 h;
Li-TO+H+＝H-TO+Li+(3)
subjecting the lithium ion-loaded manganese-based lithium adsorbent (A) obtained by the second adsorption treatment2) Desorbing with inorganic acid, wherein the desorption reaction is shown in equation (3), and obtaining lithium-containing desorption completion liquid C2(ii) a The inorganic acid and the lithium ion-loaded manganese-based lithium adsorbent A2The contact time is 0.5 h-12 h; subjecting the lithium-containing desorption completion liquid C1And/or lithium-containing desorption completion liquid C2And (5) carrying out lithium product recovery treatment to obtain a lithium product.
Li-MO+H+＝H-MO+Li+(4)
The invention adopts a two-stage adsorption and desorption method to recover lithium in the byproduct mirabilite mother liquor, uses a titanium lithium adsorbent and a manganese lithium adsorbent in sequence, and fully exerts the effect of the titanium lithium adsorbent on Li under strong alkalinity by controlling proper adsorption conditions+Good adsorption performance, and the manganese lithium adsorbent can adsorb Li under neutral condition+The method has the characteristics of good adsorption performance, and can be used for synergistically adsorbing and recovering lithium ions in the mirabilite mother liquor, so that the problem of large loss of the lithium ions in the existing production process is avoided, the total recovery rate of lithium is greatly improved, the dissolution loss rate of the adsorbent is lower, and the adsorbent is ensured to obtain good reusability.
Further, the concentration of the mirabilite mother liquor in the first stage of adsorption treatment is 2.5-3.5 g/L.
Further, in the first stage of adsorption treatment, the mass ratio of the total lithium content in the mirabilite mother liquor to the amount of the titanium lithium adsorbent is 0.005-0.08: 1.
furthermore, in the first stage of adsorption treatment, the adsorption reaction temperature is 20-95 ℃. Preferably, in the first stage of adsorption treatment, the temperature of the mirabilite mother liquor is 40-90 ℃. The inventor discovers through a large number of experimental researches that the temperature of adsorption reaction in the first section of adsorption process affects the total recovery efficiency of lithium in the whole process, the change of temperature in the second section of adsorption process has little influence on the total recovery efficiency of lithium, the total recovery rate of lithium can be improved along with the increase of temperature in the first section of adsorption process, but researches show that the loss rate of the adsorbent can be increased along with the increase of temperature in each adsorption-desorption cycle period, the increase of the loss rate can reduce the cycle use times of the adsorbent, and the adsorption reaction temperature is 20-95 ℃. Within the range, the whole process can achieve higher total lithium recovery rate and lower loss rate by adjusting various influencing factors, and preferably, the adsorption reaction temperature is 60-90 ℃.
Further, a lithium-supporting titanium-based lithium adsorbent A1Lithium-loaded titanium-based lithium adsorbent A1Manganese-based lithium adsorbent A for desorbing and loading lithium ions2In the desorption process, the addition of the inorganic acid is calculated according to H+Molar amount of (2) H+The molar amount of (b) is 100% to 130% of the molar amount of the lithium supported by the adsorbent.
Further, the desorbed lithium ion-supporting titanium-based lithium adsorbent A1The titanium lithium adsorbent used in the first stage adsorption treatment step is subjected to cyclic adsorption.
Further, the desorbed lithium ion-supporting manganese-based lithium adsorbent A2The manganese-based lithium adsorbent used in the second-stage adsorption treatment step is subjected to cyclic adsorption.
Further, in the first stage adsorption treatment, the first stage adsorption mother liquor B is separated1And titanium-based lithium adsorbent A1Then, the titanium-based lithium adsorbent was washed with water. The mirabilite mother liquor remained on the surface of the titanium-series lithium adsorbent is removed by washing, so that the pollution of the lithium-containing solution desorbed due to the attachment of sodium ions on the surface of the manganese-series lithium adsorbent is avoided. Preferably, the titanium-based lithium adsorbent is washed with water until SO is in the wash water4 2-The content is less than 0.3 g/l.
Further, in the second stage adsorption treatment, the second stage adsorption is separatedAttached mother liquor B2And manganese-based lithium adsorbent A2Then, the manganese-based lithium adsorbent was washed with water. The residual mirabilite mother liquor on the surface of the manganese-based lithium adsorbent is removed by water washing, so that the pollution of the lithium-containing solution desorbed due to the attachment of sodium ions on the surface of the manganese-based lithium adsorbent is avoided. Preferably, the manganese-based lithium adsorbent is washed with water until SO is in the wash water4 2-The content is less than 0.3 g/l.
Further, the titanium-based lithium adsorbent is doped metatitanic acid type lithium adsorbent Li2MxTi1-xO3Doped lithium orthotitanate type adsorbent Li4MxTi5-xO12Wherein M is one or more of Ce, Sn, Nb, Zr, Mo, Ta, Mg, Mn and Hf; the adsorption capacity of each gram of the titanium lithium adsorbent to lithium is 4-40 mg.
Further, the manganese-based lithium adsorbent is a doped lithium manganate adsorbent LiNxMn4-xO2、Li4NxMn5-xO12Wherein N is one or more of Ce, Cr, Mo, Zr, Ti, Mg, Mn and Hf; the adsorption capacity of each gram of the titanium lithium adsorbent to lithium is 4-40 mg.
Further, the concentration of hydrogen ions in the inorganic acid is 0.10mol/L to 0.40 mol/L. Preferably, the concentration of hydrogen ions in the inorganic acid is 0.20mol/L to 0.30 mol/L.
Further, the inorganic acid is dilute sulfuric acid, and the concentration of the dilute sulfuric acid is 0.05mol/L-0.2 mol/L.
Further, in the first stage of adsorption treatment, the treatment for adsorbing lithium is a column type treatment for adsorbing lithium or a stirring treatment for adsorbing lithium.
Further, in the second adsorption treatment, the lithium adsorption treatment is a column-type lithium adsorption treatment or a stirring lithium adsorption treatment.
Further, column type desorption or stirring desorption is adopted in the desorption process.
Furthermore, the first section of adsorption treatment and the second section of adsorption treatment are carried out in a column form, the desorption treatment is carried out in a column form, and the adsorption treatment of mirabilite mother liquor is carried out in an adsorption column form, so that the adsorption efficiency can be improved, and the difficulty in separating the adsorbent from the mother liquor can be reduced; and mutual collision of the adsorbents can be reduced, and the structural form of the adsorbents is kept stable.
Further, desorption treatment: carrying out adsorption treatment on the first stage of the adsorption treatment to obtain a lithium ion-loaded titanium lithium adsorbent A1Performing column desorption with inorganic acid to obtain solution C containing lithium1(ii) a The inorganic acid and the lithium ion-loaded titanium-based lithium adsorbent A1The contact time is 0.5 h-12 h;
the manganese lithium adsorbent A loaded with lithium ions obtained by the second stage adsorption treatment2Performing column desorption with inorganic acid to obtain solution C containing lithium2(ii) a The inorganic acid and the lithium ion-loaded manganese-based lithium adsorbent A2The contact time is 0.5 h-12 h.
Furthermore, the titanium lithium adsorption substance in the column is mainly prepared by granulating a titanium lithium adsorption active substance and an adhesive, wherein the weight of the titanium lithium adsorption active substance in the titanium lithium adsorption substance accounts for 75-90% of the total weight; the particle size of the titanium lithium adsorbing substance is 0.5 mm-2 mm.
Furthermore, the manganese-based lithium adsorbing substance in the column is mainly prepared by granulating a manganese-based lithium adsorbing active substance and a binder, wherein the weight of the manganese-based lithium adsorbing active substance in the manganese-based lithium adsorbing substance accounts for 75-90% of the total weight; the particle size of the manganese lithium adsorbing substance is 0.5 mm-2 mm.
Further, the flow rate of the adsorbed or desorbed liquid passing through the column is 5mL/min to 30 mL/min.
Further, in the desorption treatment, the inorganic acid used is dilute sulfuric acid having a concentration of 0.05mol/L to 0.2 mol/L. The obtained desorption completion liquid was a lithium sulfate solution. Lithium in the byproduct mirabilite mother liquor of the hydrogen-producing lithium oxide can be recovered in the form of lithium sulfate, and can also be used for preparing various high-purity lithium products (more than 99.99 percent) and further processed into Li3PO4、Li2CO3LiF, etc., and simultaneously separating to obtain sodium sulfate crystals。
Further comprises the step of adsorbing mother liquor B in the first section and the second section1And B2After mixing, evaporation crystallization treatment is carried out to obtain anhydrous sodium sulfate by-product.
Further, the lithium-containing desorption completion liquid C1And/or lithium-containing desorption completion liquid C2Carrying out lithium product recovery treatment, comprising the following steps: desorbing solution C containing lithium1And/or lithium-containing desorption solution C2Evaporating, concentrating and precipitating to obtain the lithium product.
Preferably, the precipitation treatment is a precipitation treatment by adding a precipitant.
Further, the precipitating agent is an agent containing carbonate, fluoride or phosphate. Such as sodium carbonate reagents, sodium fluoride reagents, sodium phosphate reagents.
Since Na is contained in the desorption completion solution+The content is extremely low, and the lithium sulfate can be used as lithium-containing raw material liquid (lithium sulfate), high-purity lithium products (such as high-purity lithium carbonate, high-purity lithium fluoride, high-purity lithium phosphate and the like) with the purity of 99.99 percent are directly produced through evaporation concentration and precipitation treatment, meanwhile, mother liquor is obtained through separation after the high-purity lithium products are produced, and a byproduct, namely anhydrous sodium sulfate is produced through evaporation and crystallization.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention adopts a two-stage adsorption method to recover lithium in the byproduct mirabilite mother liquor, uses a titanium lithium adsorbent and a manganese lithium adsorbent, fully exerts the technical advantages of two different adsorbents, fully adsorbs and recovers lithium ions in the mirabilite mother liquor, greatly improves the total recovery rate of lithium, can reach more than 95 percent, greatly reduces the amount of frozen causticized materials, and greatly reduces the cost.
2. After lithium ions in the mirabilite mother liquor are recovered by a two-stage adsorption method, the adsorbent is desorbed, and Na in the obtained desorption liquid completion liquid+The content is extremely low, high-purity lithium products (such as high-purity lithium carbonate, lithium fluoride and lithium phosphate) with the purity of 99.99 percent can be produced, the value of the products is 4 to 8 times of the value of the original products, and the value of the lithium products is greatly improved。
Drawings
FIG. 1 is a flow chart of the process for separating lithium from the by-product mirabilite mother liquor of spodumene.
FIG. 2 is a flow chart of the process for preparing lithium products according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1000mL of mirabilite mother liquor (composition shown in Table 1) which is a byproduct from a spodumene hydrogen and lithium oxide plant is introduced into a self-made granular titanium adsorbent (Li) at the flow rate of 20.0mL/min at the temperature of 25 DEG C2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column is as the total amount of lithium in the adsorbed mother liquor: the dosage of the titanium lithium adsorbent is 0.005: 1 (mass ratio), adding 625.0g (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 20.0mL/min, and all the mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1And the composition thereof was measured. Then 1000mL of dilute sulfuric acid (prepared by analytically pure sulfuric acid and pure water) with the concentration of 0.2mol/L is introduced into the adsorption column at the flow rate of 5.0mL/min at the temperature of 25 ℃ for desorption, and the outflow rate of desorption liquid is controlled at 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother solution L and the desorption washing solution L are collectedDesorption 1-1And the adsorption mother liquor and the analysis solution were analyzed, and the results are shown in Table 2, in which case the adsorbent was regenerated and can be recycled。
TABLE 1 Main composition of by-product mirabilite mother liquor used in the examples
Figure BDA0002481303790000081
Table 2 example 1 adsorption solution and desorption analysis by titanium adsorption column
Figure BDA0002481303790000082
Example 2
1000mL of mirabilite mother liquor (composition shown in Table 1) which is a byproduct from a spodumene hydrogen and lithium oxide plant is introduced into a self-made granular titanium adsorbent (Li) at the flow rate of 20.0mL/min at the temperature of 25 DEG C2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column I is the total amount of lithium in the adsorbed mother liquor: the dosage of the titanium lithium adsorbent is 0.005: 1 (mass ratio), adding 625.0g (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 20.0mL/min, and all the mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1And the composition thereof was measured. Then 1000mL of dilute sulfuric acid (prepared by analytically pure sulfuric acid and pure water) with the concentration of 0.2mol/L is introduced into the adsorption column at the flow rate of 5.0mL/min at the temperature of 25 ℃ for desorption, and the outflow rate of desorption liquid is controlled at 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother liquor L is collectedDesorption 1And desorbing the washing solution LDesorption 1-1The composition was measured and the results of analysis are shown in Table 3, at which time the adsorbent was regenerated and recycled. Adsorbing the mother liquor L1And adsorption of washing liquid L1-1Mixing to obtain mother liquor LAIs prepared by mixing LAIntroducing a self-made granular titanium adsorbent (Li) at a flow rate of 30.0mL/min2MxTi1-xO3M is Mn and x is 0.02, column II (bore diameter 5.0cm, adsorbent bulk density 0.55 g/cm)3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column II is as follows according to the total amount of lithium in the adsorbed solution: the dosage of the titanium lithium adsorbent is 0.006: 1 (mass ratio), adding 143.1g of titanium adsorbent (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the granularity range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. Obtaining an adsorption mother liquor L2Wait for L2All the solution flows out of the adsorption column, 200mL of distilled water is introduced to wash the adsorption column, and the washing solution L is collected2-2And mixed into mother liquor LB. Then, 165mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) having a concentration of 0.20mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of 5.0mL/min to effect desorption, and an outflow rate was controlled to be 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and desorption mother liquor L is collectedDesorption 2And desorbing the washing solution LDesorption 2-2The composition was measured and analyzed, and the results are shown in Table 4, at which time the adsorbent was regenerated and recycled.
Table 3 example 2 adsorption solution and desorption solution composition and analysis of titanium-based adsorption column i
Figure BDA0002481303790000091
Figure BDA0002481303790000101
TABLE 4 example 2 adsorption and desorption liquid composition and analysis of titanium adsorption column II
Figure BDA0002481303790000102
The total lithium recovery rate of the titanium adsorption column I and the titanium adsorption column II in the following tables 3 and 4 was 86.87%.
Example 3
The process flow shown in FIG. 1 is obtained from1000mL of mirabilite mother liquor (the composition is shown in Table 1) which is a byproduct in a plant for preparing lithium hydroxide and lithium oxide from spodumene is introduced into a self-made granular titanium adsorbent (Li) at the temperature of 25 ℃ and the flow rate of 20.0mL/min2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column I is the total amount of lithium in the adsorbed mother liquor: the dosage of the titanium lithium adsorbent is 0.008: 1 (mass ratio), adding 390.6g (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 20.0mL/min, and all the mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1The composition was measured and analyzed, and as a result, 1000mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) having a concentration of 0.2mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of 5.0mL/min, to desorb the solution, with an outflow rate of the desorption solution being controlled at 5.0mL/min, as shown in Table 5. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother liquor L is collectedDesorption 1And desorbing the washing solution LDesorption 1-1And (4) determining the composition, wherein the adsorbent is regenerated and can be recycled. Adsorbing the mother liquor L1And adsorption of washing liquid L1-1Mixing to obtain mother liquor LAMeasuring pH to 8.5, and adding LAIntroducing a self-made granular manganese adsorbent (LiN) at a flow rate of 30.0mL/minxMn4-xO2N ═ Mo and x ═ 0.02) column ii (internal diameter 5.0cm, loose packed density of adsorbent 0.45g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column II is as follows according to the total amount of lithium in the adsorbed solution: the dosage of the manganese lithium adsorbent is 0.006: 1 (mass ratio), adding 143.1g of manganese adsorbent (the active substance, namely manganese lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. Obtaining an adsorption mother liquor L2Wait for L2All the solution flows out of the adsorption column, and 200mL of distilled water is introduced to wash the adsorption column and collectThe washing solution L2-2And mixed into mother liquor LBThe pH was measured to be 6.5. Then 890mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) with a concentration of 0.08mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of 5.0mL/min for desorption. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and desorption mother liquor L is collectedDesorption 2And desorbing the washing solution LDesorption 2-2The composition was measured and analyzed, and the results are shown in Table 6, at which time the adsorbent was regenerated and recycled.
As shown in the process flow of the lithium product in fig. 2, the method for directly preparing battery-grade lithium carbonate from the lithium-containing desorption solution after evaporation and concentration comprises the following steps: subjecting the lithium-containing desorption solution L toDesorption 1、LDesorption 1-1、LDesorption 2And LDesorption 2-2Mixing, evaporating and concentrating, adding 51ml of sodium carbonate saturated solution prepared from analytically pure water and pure water when the content of lithium ions in the solution reaches 15g/L, stirring at 90 ℃ for lithium precipitation reaction for 1.0h, aging for 4h after the reaction is finished, filtering, washing the filtered product with distilled water, and drying the filter cake by blowing at 100 ℃ for 8h to obtain the battery-grade lithium carbonate (the purity of the lithium carbonate is shown in Table 7).
Adsorbing the mother liquor LBMiddle Li+If the content is extremely low, the Na can be directly evaporated or frozen to obtain Na2SO4·10H2O。
TABLE 5 example 3 adsorption solution and desorption solution composition and analysis of titanium-based adsorption column I
Figure BDA0002481303790000111
Figure BDA0002481303790000121
TABLE 6 example 3 manganese-based adsorption column II adsorption solution and desorption solution composition and analysis
Figure BDA0002481303790000122
The total lithium recovery rate of the titanium adsorption column I and the manganese adsorption column II in the table 5 and the table 6 is 93.7%.
Table 7 example 3 purity and quality of lithium carbonate obtained by evaporation precipitation of lithium from stripping solution
Figure BDA0002481303790000123
Example 4
As shown in the process flow of FIG. 1, 1000mL of mirabilite mother liquor (composition shown in Table 1) from a lithium pyroxene hydrogen and lithium oxide plant by-product is taken, and a self-made granular titanium adsorbent (Li) is introduced at 25 ℃ and at a flow rate of 15.0mL/min2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column I is the total amount of lithium in the adsorbed mother liquor: the dosage of the titanium lithium adsorbent is 0.005: 1 (mass ratio), adding 625.0g (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 15.0mL/min, and all mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1And the composition thereof was measured. After analysis, as shown in Table 8, 1100mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) having a concentration of 0.2mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of the desorption solution was controlled to 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother liquor L is collectedDesorption 1And desorbing the washing solution LDesorption 1-1And (4) determining the composition, wherein the adsorbent is regenerated and can be recycled. Adsorbing the mother liquor L1And adsorption of washing liquid L1-1Mixing to obtain mother liquor LAMeasuring pH to 8.5, and adding LAIntroducing a self-made granular manganese adsorbent (LiN) at a flow rate of 30.0mL/minxMn4-xO2N ═ Mo and x ═ 0.02) column ii (internal diameter 5.0cm, adsorbent bulk density 0.45g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column II is the total amount of lithium in the adsorbed mother liquor: the dosage of the manganese lithium adsorbent is 0.006: 1 (mass ratio), adding 125.7g of manganese adsorbent (the active substance, namely manganese lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. Obtaining an adsorption mother liquor L2Wait for L2All the solution flows out of the adsorption column, 200mL of distilled water is introduced to wash the adsorption column, and the washing solution L is collected2-2And mixed into mother liquor LBThe pH was measured to be 6.5. Then, 830mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) with a concentration of 0.08mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of 5.0mL/min for desorption, and an outflow rate was controlled at 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and desorption mother liquor L is collectedDesorption 2And desorbing the washing solution LDesorption 2-2The composition was measured and analyzed, and the results are shown in Table 9, at which time the adsorbent was regenerated and recycled.
As shown in the process flow of the lithium product in fig. 2, the method for directly preparing battery-grade lithium fluoride from the lithium-containing desorption solution after evaporation and concentration comprises the following steps: subjecting the lithium-containing desorption solution L toDesorption 1、LDesorption 1-1、LDesorption 2And LDesorption 2-2Mixing, evaporating and concentrating, adding the mother liquor into 16.17g of sodium fluoride when the content of lithium ions reaches 15g/L, washing and separating in an acid solution at 60-100 ℃, and drying by blowing for 6h at 100-150 ℃ to obtain the battery grade lithium fluoride (the purity of the battery grade lithium fluoride is shown in Table 10).
Adsorbing the mother liquor LBMiddle Li+If the content is extremely low, the Na can be directly evaporated or frozen to obtain Na2SO4·10H2O。
TABLE 8 example 4 adsorption solution and desorption solution composition of titanium-based adsorption column I and analysis
Figure BDA0002481303790000141
TABLE 9 example 4 manganese adsorption column II adsorption liquid desorption liquid composition and analysis
Figure BDA0002481303790000142
In Table 8, the total lithium recovery rate of the titanium adsorption column I and the manganese adsorption column II is 98.90%.
TABLE 10 example 4 purity and quality of lithium fluoride from evaporation precipitation of lithium from stripping solution
Figure BDA0002481303790000143
Figure BDA0002481303790000151
Example 5
As shown in the process flow of FIG. 1, 1000mL of mirabilite mother liquor (composition shown in Table 1) from a lithium pyroxene hydrogen and lithium oxide plant by-product is taken, and a self-made granular titanium adsorbent (Li) is introduced at a flow rate of 10.0mL/min at a temperature of 60 DEG C2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column I is the total amount of lithium in the adsorbed mother liquor: the dosage of the titanium lithium adsorbent is 0.005: 1 (mass ratio), adding 625.0g (active substance, namely titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the granularity range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 10.0mL/min, and all mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1The composition was measured and analyzed, and as a result, 1100mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) having a concentration of 0.2mol/L was introduced into the adsorption column at 25 ℃ and a flow rate of 5.0mL/min, to desorb the solution, while controlling the flow rate of the desorption solution at 5.0mL/min, as shown in Table 11. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother liquor L is collectedDesorption 1And desorbing the washing solution LDesorption 1-1And (4) determining the composition, wherein the adsorbent is regenerated and can be recycled. Adsorbing the mother liquor L1And adsorption of washing liquid L1-1Mixing to obtain mother liquor LAMeasuring pH to 8.5, and adding LAIntroducing a self-made granular manganese adsorbent (LiN) at a flow rate of 30.0mL/minxMn4-xO2N ═ Mo and x ═ 0.02) column ii (internal diameter 5.0cm, loose packed density of adsorbent 0.45g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column II is the total amount of lithium in the adsorbed mother liquor: the dosage of the manganese lithium adsorbent is 0.006: 1 (mass ratio), adding 117.2g of manganese adsorbent (the active substance, namely manganese lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. Obtaining an adsorption mother liquor L2Wait for L2All the solution flows out of the adsorption column, 200mL of distilled water is introduced to wash the adsorption column, and the washing solution L is collected2-2And mixed into mother liquor LBThe pH was measured to be 6.5. Then 740mL of dilute sulfuric acid (prepared from analytically pure sulfuric acid and pure water) with the concentration of 0.08mol/L is introduced into the adsorption column at the temperature of 25 ℃ and the flow rate is controlled at 5.0mL/min for desorption. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and desorption mother liquor L is collectedDesorption 2And desorbing the washing solution LDesorption 2-2The composition was measured and analyzed, and the results are shown in Table 12, at which time the adsorbent was regenerated and recycled.
As shown in the process flow of the lithium product in fig. 2, the method for directly preparing battery-grade lithium phosphate from the lithium-containing desorption solution after evaporation and concentration comprises the following steps: subjecting the lithium-containing desorption solution L toDesorption 1、LDesorption 1-1、LDesorption 2And LDesorption 2-2Mixing, evaporating and concentrating, adding 20.1g of sodium phosphate when the content of lithium ions reaches 15g/L, carrying out lithium precipitation reaction for 1.0h at a certain temperature, aging for 4h after the reaction is finished, washing the filtered product with distilled water, and carrying out forced air drying for 6h at 100 ℃ to obtain the battery-grade lithium phosphate (the purity of the battery-grade lithium phosphate is shown in Table 13).
Adsorbing the mother liquor LBMiddle Li+If the content is extremely low, the Na can be directly evaporated or frozen to obtain Na2SO4·10H2O。
TABLE 11 example 5 adsorption solution and desorption solution composition of titanium-based adsorption column I and analysis
Figure BDA0002481303790000161
TABLE 12 example 5 manganese-based adsorption column II adsorption solution and desorption solution composition and analysis
Figure BDA0002481303790000162
Figure BDA0002481303790000171
The total lithium recovery rate of the titanium adsorption column I and the manganese adsorption column II in the table 11 and the table 12 is 98.97%.
TABLE 13 example 5 purity and quality of lithium phosphate obtained by evaporation precipitation of lithium from stripping solution
Figure BDA0002481303790000172
Example 6
As shown in the process flow of FIG. 1, 1000mL of mirabilite mother liquor (composition shown in Table 1) as a by-product from lithium hydroxide factory was introduced into a self-made granular titanium adsorbent (Li) at 60 deg.C at a flow rate of 5.0mL/min2MxTi1-xO3M is Mn and x is 0.02, and the adsorbent has an inner diameter of 5.0cm and a bulk density of 0.55g/cm3And the heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column I is as the total amount of lithium in the adsorbed mother liquor: 1041.6g (active substance, namely the titanium lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive) is added into the titanium lithium adsorbent in a mass ratio of 0.003:1, and the granularity of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. When the outflow speed is 5.0mL/min, and all the mirabilite mother liquor flows out of the adsorption column, introducing 200mL of distilled water to wash the adsorption column, and collecting adsorption mother liquor L1And adsorbing the washing liquid L1-1And the composition thereof was measured. Then 1100mL of dilute sulfuric acid (prepared by analytically pure sulfuric acid and pure water) with the concentration of 0.2mol/L is introduced into the adsorption column at the flow rate of 5.0mL/min at the temperature of 25 ℃ for desorption, and the outflow rate of desorption liquid is controlled at 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and the desorption mother liquor L is collectedDesorption 1And desorbing the washing solution LDesorption 1-1The composition was measured and analyzed, and the results are shown in Table 14, at which time the adsorbent was regenerated and recycled. Adsorbing the mother liquor L1And adsorption of washing liquid L1-1Mixing to obtain mother liquor LAMeasuring pH to 8.5, and adding LAIntroducing a self-made granular manganese adsorbent (LiN) at a flow rate of 30.0mL/minxMn4-xO2N ═ Mo and x ═ 0.02) column ii (internal diameter 5.0cm, loose packed density of adsorbent 0.45g/cm3And a heat-preservation jacket) for adsorption, wherein the filling amount of the adsorbent in the adsorption column II is the total amount of lithium in the adsorbed mother liquor: the dosage of the manganese lithium adsorbent is 0.006: 1 (mass ratio), adding 97.4g of manganese adsorbent (the active substance of the manganese lithium adsorbent accounts for 80 wt% of the total amount of the granular adsorbent, and the balance is binder and additive), wherein the particle size range of the adsorbent is 0.5-2.0 mm and is more than or equal to 95%. Obtaining an adsorption mother liquor L2Wait for L2All the solution flows out of the adsorption column, 200mL of distilled water is introduced to wash the adsorption column, and the washing solution L is collected2-2And mixed into mother liquor LBThe pH was measured to be 6.5. Then 620mL of dilute sulfuric acid (prepared by analytically pure sulfuric acid and pure water) with the concentration of 0.08mol/L is introduced into the adsorption column at the flow rate of 5.0mL/min at the temperature of 25 ℃ for desorption, and the outflow rate is controlled at 5.0 mL/min. After the desorption solution completely flows out of the adsorption column, 100mL of distilled water is introduced to clean the filler, and desorption mother liquor L is collectedDesorption 2And desorbing the washing solution LDesorption 2-2The composition was measured and analyzed, and the results are shown in Table 15, at which time the adsorbent was regenerated and recycled.
As shown in the process flow of the lithium product in fig. 2, the method for directly preparing battery-grade lithium phosphate from the lithium-containing desorption solution after evaporation and concentration comprises the following steps: subjecting the lithium-containing desorption solution L toDesorption 1、LDesorption 1-1、LDesorption 2And LDesorption 2-2Mixing, evaporating and concentrating, adding 51.52ml of sodium carbonate saturated solution prepared by using analytically pure water and pure water when the content of lithium ions reaches 15g/L, carrying out lithium precipitation reaction for 1.0h at 90 ℃, aging for 4h after the reaction is finished, cleaning a filtered product by using distilled water, and carrying out forced air drying for 8h at 100 ℃ to obtain the battery-grade lithium carbonate (the purity of the lithium carbonate is shown in Table 16).
Adsorbing the mother liquor LBMiddle Li+If the content is extremely low, the Na can be directly evaporated or frozen to obtain Na2SO4·10H2O。
TABLE 14 example 6 adsorption solution and desorption solution composition of titanium-based adsorption column I and analysis
Figure BDA0002481303790000181
Figure BDA0002481303790000191
TABLE 15 EXAMPLE 6 manganese-based adsorption column II adsorption solution and desorption solution compositions and analysis
Figure BDA0002481303790000192
The total lithium recovery rate of the titanium adsorption column I and the manganese adsorption column II in the tables 14 and 15 is 99.1%.
TABLE 16 example 6 purity and quality of lithium carbonate obtained by evaporation precipitation of lithium from stripping solution
Figure BDA0002481303790000193
Comparative example 1
Comparative example 1 the influence of different mirabilite mother liquor temperatures on the total recovery rate of lithium and the loss rate of the titanium adsorbent in each adsorption-desorption cycle in the first stage of adsorption treatment was studied, and the experimental process and conditions of comparative example 1 were the same as those of example 6, and only the mirabilite mother liquor temperature was changed, and the results are shown in table 17.
TABLE 17 Effect of different mother liquor temperatures of Glauber's salt on overall recovery of lithium and loss of titanium based sorbent per adsorption-desorption cycle period in comparative example 1
Figure BDA0002481303790000201
In the first section of adsorption process, the temperature of the adsorption reaction can influence the total recovery efficiency of lithium in the whole process, in the second section of adsorption process, the influence of the temperature change on the total recovery efficiency of lithium is small, in the first section of adsorption process, the total recovery rate of lithium can be improved along with the increase of the temperature, but researches show that the loss rate of the adsorbent can also be increased in each adsorption-desorption cycle period along with the increase of the temperature, the increase of the loss rate can reduce the cycle use times of the adsorbent, and the adsorption reaction temperature is 20-95 ℃. Within the range, the whole process can achieve higher total lithium recovery rate and lower loss rate by adjusting various influencing factors, and preferably, the adsorption reaction temperature is 60-90 ℃.
Comparative example 2
Comparative example 2 the effect of the concentration of hydrogen ions in inorganic acid on the total recovery rate of lithium and the loss rate of the titanium-based and manganese-based adsorbents per adsorption-desorption cycle period was investigated, and comparative example 2 was the same in experimental procedure and conditions as example 6, only the concentration of hydrogen ions in acid solution used for desorption was changed, and the results are shown in table 18.
TABLE 18 Effect of hydrogen ion concentration in mineral acids different from comparative example 2 on the overall recovery of lithium and the loss rate of the titanium-based and manganese-based adsorbents per adsorption-desorption cycle period
Figure BDA0002481303790000211
Comparative example 3
Comparative example 3 the influence of the mass ratio of the total amount of lithium in the mirabilite mother liquor to the amount of the titanium-based lithium adsorbent in the first stage of adsorption treatment on the total recovery rate of lithium was investigated, and the experimental process and conditions of comparative example 3 were the same as those of example 6, except that the mass ratio of the total amount of lithium in the mirabilite mother liquor to the amount of the titanium-based lithium adsorbent was changed, and the results are shown in table 19.
Table 19 influence of mass ratio of total lithium amount and titanium-based lithium adsorbent amount in mirabilite mother liquor described in comparative example 3 on total recovery rate of lithium
Figure BDA0002481303790000212
Figure BDA0002481303790000221
When the total lithium content of the mirabilite mother liquor and the use amount of the titanium adsorbent are changed, the recovery rate of the titanium adsorbent to lithium is reduced in the first-stage adsorption process, the pH value of the first-stage desorption mother liquor is higher, the second-stage manganese adsorbent is not favorable for adsorption conversion, and finally the total recovery rate of lithium is influenced. Particularly, in the first-stage adsorption in the comparative example 3-e, the dosage of the titanium adsorbent is less, the pH of the first-stage adsorption mother liquor is higher, the total recovery rate of lithium is reduced, and the dissolution loss of the manganese adsorbent adsorbed by the second-stage adsorption is increased. Therefore, the amount of the titanium adsorbent used in the first-stage adsorption treatment is not too small.
The invention adopts a two-stage adsorption method to recover lithium in the byproduct mirabilite mother liquor, uses a titanium lithium adsorbent and a manganese lithium adsorbent, fully exerts the technical advantages of two different adsorbents, fully adsorbs and recovers lithium ions in the mirabilite mother liquor, greatly improves the total recovery rate of lithium, can reach more than 95 percent, greatly reduces the amount of frozen causticized materials, and greatly reduces the cost. After lithium ions in the mirabilite mother liquor are recovered by a two-stage adsorption method, the adsorbent is desorbed, and Na in the obtained desorption liquid completion liquid+The content is extremely low, high-purity lithium products (such as high-purity lithium carbonate, lithium fluoride and lithium phosphate) with the purity of 99.99 percent can be produced, the value of the products is 4-8 times of the value of the original products, and the value of the lithium products is greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A method for recovering lithium from a byproduct mirabilite mother solution of lithium oxide hydrogen production from spodumene is characterized by comprising two sections of adsorption and desorption treatment steps:
first-stage adsorption treatment: carrying out lithium adsorption treatment on the mirabilite mother liquor by using a titanium lithium adsorbent to obtain a lithium-loaded titanium lithium adsorbent A1And the first stage adsorption mother liquor B1(ii) a The mass ratio of the total lithium in the mirabilite mother liquor to the use amount of the titanium lithium adsorbent is 0.003-0.010: 1;
second-stage adsorption treatment: adsorbing mother liquor B of the first stage by using manganese lithium adsorbent1Performing lithium adsorption treatment to obtain lithium ion loaded manganese-based lithium adsorbent A2And second-stage adsorption mother liquor B2(ii) a The first section adsorbs mother liquor B1The mass ratio of the total lithium content to the manganese lithium adsorbent is 0.005-0.008: 1;
desorption treatment: carrying out adsorption treatment on the first stage of the adsorption treatment to obtain a lithium ion-loaded titanium lithium adsorbent A1Desorbing with inorganic acid to obtain solution C containing Li1(ii) a The inorganic acid and the lithium ion-loaded titanium-based lithium adsorbent A1The contact time is 0.5 h-12 h;
the manganese lithium adsorbent A loaded with lithium ions obtained by the second stage adsorption treatment2Desorbing with inorganic acid to obtain solution C containing Li2(ii) a The inorganic acid and the lithium ion-loaded manganese-based lithium adsorbent A2The contact time is 0.5 h-12 h;
subjecting the lithium-containing desorption completion liquid C1And/or lithium-containing desorption completion liquid C2And (5) carrying out lithium product recovery treatment to obtain a lithium product.
2. The method for recovering lithium from the mirabilite mother liquor as a byproduct of lithium hydroxide and lithium oxide hydrogen production from spodumene according to claim 1, wherein the concentration of the mirabilite mother liquor in the first stage of adsorption treatment is 2.5 g/L-3.5 g/L.
3. The method for recovering lithium from the mirabilite mother liquor as a byproduct of lithium hydroxide and lithium oxide hydrogen production from spodumene according to claim 1, wherein in the first stage of adsorption treatment, the mass ratio of the total amount of lithium in the mirabilite mother liquor to the amount of the titanium lithium adsorbent is 0.005-0.008: 1.
4. the method for recovering lithium from the mirabilite mother liquor, which is a byproduct of lithium hydroxide and lithium oxide production from spodumene according to claim 1, is characterized in that the adsorption reaction temperature in the first stage of adsorption treatment is 20-95 ℃.
5. The method for recovering lithium from the byproduct mirabilite mother liquor generated in the production of lithium hydroxide and lithium oxide from spodumene as claimed in claim 1, wherein the concentration of hydrogen ions in the inorganic acid is 0.10 mol/L-0.40 mol/L.
6. The method for recovering lithium from byproduct mirabilite mother liquor generated in the production of lithium hydroxide and lithium oxide from spodumene as claimed in claim 1, wherein the titanium-based lithium adsorbent A is loaded with lithium1Manganese-based lithium adsorbent A for desorbing and loading lithium ions2In the desorption process, the addition of the inorganic acid is calculated according to H+Molar amount of (2) H+The molar weight of the lithium ion adsorbent is 100% -130% of the molar weight of the lithium loaded on the adsorbent.
7. The method for recovering lithium from the mirabilite mother liquor as a byproduct of lithium hydroxide and lithium oxide production from spodumene as claimed in claim 1, wherein the titanium-based lithium adsorbent is a doped metatitanic acid type lithium adsorbent Li2MxTi1-xO3、Doped lithium orthotitanate type adsorbent Li4MxTi5 - xO12Wherein M is one or more of Ce, Sn, Nb, Zr, Mo, Ta, Mg, Mn and Hf; the adsorption capacity of each gram of the titanium lithium adsorbent to lithium is 4-40 mg.
8. The method for recovering lithium from the byproduct mirabilite mother liquor in the process of preparing lithium oxide and hydrogen from spodumene as claimed in claim 1, wherein the manganese-based lithium adsorbent is doped lithium manganate adsorbent LiNxMn4-xO2、Li4NxMn5-xO12Wherein N is one or more of Ce, C r, Mo, Zr, Ti, Mg, Mn and Hf; the adsorption capacity of each gram of the titanium lithium adsorbent to lithium is 4-40 mg.
9. The method for recovering lithium from the mirabilite mother liquor as a byproduct of lithium hydroxide and lithium oxide production from spodumene as claimed in claim 1, wherein the titanium-based lithium adsorbent A loaded with lithium ions after desorption treatment1Performing cyclic adsorption by using the titanium lithium adsorbent in the first stage of adsorption treatment; lithium ion-loaded manganese-based lithium adsorbent A subjected to desorption treatment2The manganese-based lithium adsorbent used in the second-stage adsorption treatment step is subjected to cyclic adsorption.
10. The method for recovering lithium from the mirabilite mother liquor, which is a byproduct of lithium hydroxide and lithium oxide hydrogen production from spodumene, according to any one of claims 1 to 9, is characterized in that the first stage adsorption treatment and the second stage adsorption treatment are performed in a column manner, the desorption treatment is performed in a column manner, and the flow rate of the adsorbed or desorbed liquid passing through the column is 5mL/min to 30 mL/min.
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