CN116020397A - Preparation method of manganese-titanium composite lithium ion sieve adsorbent - Google Patents
Preparation method of manganese-titanium composite lithium ion sieve adsorbent Download PDFInfo
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Abstract
The invention discloses a preparation method of a granular manganese-titanium composite lithium ion sieve adsorbent, which comprises the following steps: lithium meta-titanate, mn 2 O 3 Adding lithium hydroxide into an autoclave for reaction, and calcining to obtain a powdery manganese-titanium composite lithium ion adsorbent; mixing gelatin water solution, polyvinyl alcohol water solution, dispersing agent and water under stirring to obtain water phase; mixing styrene, divinylbenzene, methyl methacrylate, an initiator and a pore-forming agent to obtain an oil phase; the aqueous phase is addedAfter heating to a certain temperature, adding a powdery manganese-titanium composite lithium ion sieve adsorbent and an oil phase into the water phase to carry out suspension polymerization reaction; heating, hardening, filtering, screening and grading the hardened spherical particles to obtain a granulation product; purifying the granulated product to obtain the granular manganese-titanium composite lithium ion sieve adsorbent. The invention has simple process, stable granulation process, short granulation time, high production efficiency and low cost; the obtained product has good performance, high strength, uniform granularity and good fluidity.
Description
Technical Field
The invention relates to the technical field of lithium ion sieve adsorbents, in particular to a preparation method of a manganese-titanium composite lithium ion sieve adsorbent.
Background
Along with the movement of pushing energy conservation and emission reduction, the development of new energy automobiles also sharply increases the demand of lithium. Because the lithium reserves in liquid lithium resources such as salt lake brine are large, the lithium extraction has the advantage of low cost, and the increase of the demand for lithium carbonate is expected to be satisfied by the lithium extraction capacity of the salt lake brine at home and abroad.
The adsorption method is more suitable for extracting and separating lithium from the brine with high magnesium-lithium ratio, and the method has the advantages of simpler process, low energy consumption and little environmental pollution, and is an ideal process method suitable for extracting lithium from salt lake brine at home and abroad. The key technology of the adsorption method is a lithium ion sieve adsorbent. The existing lithium ion sieve adsorbent is generally a powdery product, has poor fluidity and permeability and high dissolution loss rate, and can not be used for industrial production because a bed layer is easy to collapse during adsorption-desorption so as to completely block fluid. Therefore, the granulation of the adsorbent is a necessary process for meeting the industrial application of the lithium adsorbent. Only the powdered adsorbent is processed to prepare granular adsorbent, so that the industrialized application of the adsorption method for extracting lithium can be realized. In view of this, the formation of a porous, porous particulate form of a powdered lithium adsorbent has become one of the focus of the researchers in this field.
Those skilled in the art have attempted to prepare various granular or film-like adsorbents by different methods. The currently reported granulation methods of the powdery lithium ion sieve adsorbent mainly comprise the following two main types: one is direct bond molding, and the other is organic polymer molding. Among them, methods for producing granular adsorbents by direct bonding molding have been reported. For example, chinese patent CN101898113a discloses that granular adsorbent is prepared by mixing polyvinyl chloride or other organic polymer resin and lithium adsorbent powder, dissolving with organic solvent (such as DMF or NMP), and then dripping into water for shaping; (2) The paper literature reports that salt soluble in water such as KCl is taken as a pore-forming agent, DMF or NMP and the like are added into a mixture of PVC, KCl and powdery adsorbent, the mixture is subjected to size mixing, pressed into strips or sheets, dried, crushed or cut into particles, and the particles are dissolved out of the KCl by water to obtain a granular lithium adsorbent; (3) The Chinese patent CN103316623A discloses that polysaccharide and solvent are heated, dissolved and mixed, then an adsorbent precursor is added into the solution, the mixture is stirred uniformly to obtain a viscous solution, and then the viscous solution is dripped into petroleum ether and other oil phases to obtain the solid spherical adsorbent with the particle size of 2-5 mm. Methods for preparing granular adsorbents by organic polymerization molding have also been reported. For example, (1) chinese patent CN101955210a discloses that in the process of forming a crosslinked polymer by inverse suspension polymerization of an acrylic monomer, a particulate lithium ion adsorbent is obtained by coating a lithium ion adsorbent powder in the polymer; (2) Chinese patent CN1511963 discloses that acrylamide is used as a polymerization forming monomer, an ion sieve powder is suspended in a monomer solution, and an initiator and a cross-linking agent are added to initiate a cross-linking polymerization reaction, so as to prepare a granular polyacrylamide-lithium ion sieve; (3) Chinese patent CN10684102a discloses that a spherical lithium ion adsorbent of styryl group is obtained by adding lithium adsorbent powder at the time of polymerization of styrene.
The manganese-based lithium ion sieve adsorbent is considered as a lithium ion sieve adsorbent with great potential because of high adsorption capacity and high adsorption speed on lithium ions, but has the problem of great dissolution loss during analysis. During granulation, it was found that granulation agglomeration (suspension granulation) occurred, and that the dispersion performance was poor, and the granulation stability was also to be improved. In view of the above, the invention adds the titanium compound into the manganese-based lithium ion sieve adsorbent to modify the manganese-based lithium ion sieve adsorbent, and simultaneously prepares the granular manganese-titanium composite lithium ion sieve adsorbent by optimizing a granulating method, so that the dissolution loss of the manganese-based lithium ion sieve can be reduced, and the application performance of the obtained adsorbent is improved.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a preparation method of a manganese-titanium composite lithium ion sieve adsorbent, and the manganese-titanium composite lithium ion sieve adsorbent prepared by the method can solve the technical problems of large dissolution loss, poor agglomeration dispersibility and poor pelleting stability of the existing manganese-based lithium ion sieve adsorbent.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the manganese-titanium composite lithium ion sieve adsorbent comprises the following steps:
s1, preparing a powdery manganese-titanium composite lithium ion sieve adsorbent: lithium meta-titanate, manganese sesquioxide (Mn) 2 O 3 ) Adding lithium hydroxide into a high-pressure reaction kettle for reaction, and then calcining to obtain a powdery manganese-titanium composite lithium ion adsorbent;
s2, preparing a granular manganese-titanium composite lithium ion sieve adsorbent:
s21, stirring and mixing a gelatin water solution, a polyvinyl alcohol (PVA) water solution, a dispersing agent and water to obtain a water phase;
s22, mixing styrene, divinylbenzene, methyl methacrylate, an initiator and a pore-forming agent to obtain an oil phase;
s23, heating the water phase to a certain temperature, and adding a powdery manganese-titanium composite lithium ion sieve adsorbent and an oil phase into the water phase to perform suspension polymerization reaction to obtain spherical particles;
s24, heating to harden spherical particles prepared by suspension polymerization, and sequentially filtering, screening and grading the hardened particles to obtain a granulation product;
s25, purifying the obtained granulation product, and removing the pore-forming agent to obtain the manganese-titanium composite lithium ion sieve adsorbent.
Preferably, the lithium meta-titanate is prepared by taking titanium dioxide and lithium hydroxide as raw materials and adopting a solid phase synthesis method, and calcining at 700-750 ℃ for 6-24 hours.
Preferably, the lithium meta-titanate and manganese sesquioxide (Mn 2 O 3 ) The molar ratio of Ti to Mn is 0.1-5:10.
preferably, in the step S1, the reaction temperature is 200-250 ℃, the reaction time is 10-12h, the calcination temperature is 400-450 ℃, and the calcination time is 4-6h.
Preferably, in step S22, the weight of the initiator is 1-8wt% of the sum of the volumes of styrene, divinylbenzene and methyl methacrylate.
Preferably, the dispersing agent is selected from one or a combination of more than two of sodium chloride, magnesium hydroxide, potassium chloride, calcium hydroxy phosphate or calcium phosphate.
Preferably, the pore-forming agent is one or more than two of toluene, solid paraffin, liquid paraffin, hexane, heptane, octane, n-heptane or 200# petroleum.
Preferably, in step S23, the surface modification treatment of the powdery manganese-titanium composite lithium ion sieve adsorbent with a surfactant is required before the powdery manganese-titanium composite lithium ion sieve adsorbent is added into the aqueous phase, and the specific steps are as follows: soaking the powdery manganese-titanium composite lithium ion sieve adsorbent in a solution containing a surfactant, stirring, and drying at 100-120 ℃ to obtain a modified powdery manganese-titanium composite lithium ion sieve adsorbent, so as to realize that the surface of the modified powdery manganese-titanium composite lithium ion sieve adsorbent has lipophilicity; the surfactant is, but not limited to, a coupling agent, a fatty acid, preferably one or a combination of more than two of a silane coupling agent, stearic acid and stearate; further preferred is a silane coupling agent.
Preferably, in the suspension polymerization in step S23, the volume ratio of the aqueous phase to the oil phase is 1 to 10:10.
preferably, in step S23, the aqueous phase is heated to a temperature of 78-83 ℃, i.e. the temperature of the suspension polymerization reaction is 78-83 ℃, and the suspension polymerization reaction time is 2-3 hours; the stirring rate in the suspension polymerization is 50 to 400r/min, where the stirring rate is related to the size of the reactor used, for example in a 500mL reactor, and is preferably 200 to 350r/min.
Preferably, in step S24, the hardening time is 0.5 to 3 hours.
The invention also aims to provide the granular manganese-titanium composite lithium ion sieve adsorbent obtained by the preparation method, wherein in the granular manganese-titanium composite lithium ion sieve adsorbent, particles with the granularity of 0.2-0.9mm account for more than 90% of the total weight.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, firstly, the preparation formula of the powdery manganese-titanium composite lithium ion sieve adsorbent is optimized, and the preparation formula is mainly characterized in that the raw materials and the proportions are different, the invention adds the lithium metatitanate on the basis of the original lithium manganate, and controls the molar ratio of Ti to Mn to be 0.1-5:10, the powdery manganese-titanium composite adsorbent is prepared, has comprehensive advantage performances of manganese-series and titanium-series adsorbents, greatly improves stability, and reduces dissolution loss of the adsorbent while the adsorption performance is not reduced. Furthermore, the invention optimizes the preparation process for preparing the granular manganese-titanium composite lithium ion sieve adsorbent, which mainly comprises the following aspects: (a) Before the powdery Mn-Ti composite lithium ion sieve adsorbent is added into the water phase, the powdery Mn-Ti composite lithium ion sieve adsorbent is modified by adopting a silane coupling agent surfactant, so that the surface of the powdery Mn-Ti composite lithium ion sieve adsorbent has lipophilicity, namely, the hydrophilic powdery Mn-Ti composite lithium ion sieve adsorbent is modified to be hydrophobic (oleophilicity), and the compatibility of the powdery Mn-Ti composite lithium ion sieve adsorbent and the oil phase (organic phase) can be enhanced; in the process of forming a cross-linked polymer by suspension polymerization of monomers such as styrene, methyl methacrylate and divinylbenzene, the powdery manganese-titanium composite lithium ion sieve adsorbent can be coated inside the formed polymer, so that granulation is finished, and the spherical granular lithium ion adsorbent is obtained. (b) The invention controls the formula and the proportion of the water phase and the oil phase during granulation; the magnesium hydroxide is directly added into the aqueous phase formula as a dispersing agent instead of magnesium chloride and sodium hydroxide for reaction to obtain magnesium hydroxide, so that the problem of unstable granulation caused by the change of the pH value of a reaction system due to the fact that the addition amount is not easy to control is solved; the divinylbenzene is added into the oil phase formula, the addition amount of an initiator and the like is adjusted, and the granulation stability can be improved; the solid paraffin pore-forming agent is added during polymerization granulation, so that the porosity of a granulated product is increased, the specific surface area of the granulated adsorbent is increased, and the adsorption performance is improved; (c) The existing polymerization method is that the temperature is about 70 ℃, powder (powdery manganese titanium composite lithium ion sieve adsorbent) and an organic phase are added to start polymerization, then constant temperature is controlled to rise to about 80 ℃ to carry out heat preservation polymerization, the rising temperature of the process has great influence on the granulating stability of the adsorbent, the phenomenon of unstable granulating often occurs, and the granulating failure can occur due to explosive aggregation.
(2) In the manganese-titanium composite lithium ion sieve adsorbent prepared by the method, the particles with the granularity of 0.2-0.9mm account for more than 90%, and the manganese-titanium composite lithium ion sieve adsorbent has high particle strength, good fluidity and better recycling. The manganese-titanium composite lithium ion sieve adsorbent prepared by the method has uniform granularity and high strength. In addition, the method has the advantages of simple technical process, stable granulating process, short granulating time, high production efficiency and low cost; the obtained granulated product has good performance, high strength, uniform granularity and good fluidity, and is favorable for industrialized repeated cyclic application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing a granular manganese-titanium composite lithium ion sieve adsorbent provided by the invention;
FIG. 2 is an SEM image of the surface of the particulate titanium-manganese composite lithium ion sieve adsorbent particles prepared in example 1;
FIG. 3 is a photograph of particles of the granular manganese-titanium composite lithium ion sieve adsorbent of 0.2 to 0.5mm in size prepared in example 1;
FIG. 4 is a photograph of particles of the granular manganese titanium composite lithium ion sieve adsorbent of 0.5 to 0.9mm in size prepared in example 1;
FIG. 5 is a graph showing the comparison of the adsorption capacity of the granular manganese-titanium composite lithium ion sieve adsorbent prepared in example 1 of the present invention and the pure manganese-based adsorbent prepared in comparative example 1 in a salt lake brine with a lithium concentration of 250mg/L with respect to the number of cycles;
FIG. 6 is a graph showing the relationship between the number of cycles and the dissolution rates of Mn and Ti when the granular Mn-Ti composite lithium ion sieve adsorbent prepared in example 1 of the present invention and the granular pure Mn-based adsorbent prepared in comparative example 1 are analyzed in 0.5mol/L hydrochloric acid.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Example 1
Referring to fig. 1, a preparation method of a manganese-titanium composite lithium ion sieve adsorbent comprises the following steps:
s1, preparing a powdery manganese-titanium composite lithium ion sieve adsorbent:
s11, weighing 153g of lithium hydroxide monohydrate and 146g of titanium dioxide, adding 10ml of alcohol, grinding and uniformly mixing, then placing in a resistance furnace, calcining at 720 ℃ for 6 hours to obtain lithium metatitanate, and grinding for later use;
s12, weighing 12g of the obtained lithium metatitanate, 520g of manganese sesquioxide, 1100g of lithium hydroxide monohydrate and 750mL of pure water, adding the obtained lithium metatitanate, the manganese sesquioxide, the lithium hydroxide monohydrate and the 750mL of pure water into a high-pressure reaction kettle, reacting for 11 hours at 200 ℃, filtering to obtain a filter cake which is a titanium-manganese composite material intermediate product, repeatedly using the filter cake (called reaction mother liquor) for a next reaction medium, washing and drying the filter cake, and calcining the filter cake at 430 ℃ for 4 hours to obtain a powdery titanium-manganese composite lithium ion sieve adsorbent;
s13, dispersing and soaking the obtained powdery titanium-manganese composite lithium ion sieve adsorbent in an aqueous solution containing a silane coupling agent, stirring and reacting for 1h, and then drying at 120 ℃ to obtain the surface-modified powdery titanium-manganese composite lithium ion sieve adsorbent;
s2, preparing a granular manganese-titanium composite lithium ion sieve adsorbent:
s21, uniformly stirring and mixing 125mL of gelatin water solution with the concentration of 14g/L, 125mL of polyvinyl alcohol (PVA) water solution with the concentration of 7g/L, 0.8g of magnesium hydroxide and 250mL of pure water to obtain a water phase;
s22, measuring 35ml of styrene, 0.35ml of divinylbenzene, 3.5ml of methyl methacrylate, uniformly mixing 1.1g of benzoyl peroxide serving as an initiator and 3.5g of solid paraffin serving as a pore-forming agent to obtain an oil phase;
s23, adding the obtained water phase into a reactor, stirring, heating to 80 ℃, adding 20g of surface-modified powdery manganese-titanium composite lithium ion sieve adsorbent into the water phase, slowly adding the obtained oil phase, and carrying out suspension polymerization for 2.5h;
s24, heating to 90 ℃ to harden spherical particles prepared by suspension polymerization for 1h, and then filtering, screening and grading the hardened particles to obtain a granulation product;
s25, extracting the obtained granulation product by petroleum ether to remove solid paraffin, thereby obtaining the granular manganese-titanium composite lithium ion sieve adsorbent.
Example 2
The preparation method of the manganese-titanium composite lithium ion sieve adsorbent comprises the following steps:
s1, preparing a powdery manganese-titanium composite lithium ion sieve adsorbent:
s11, weighing 153g of lithium hydroxide monohydrate and 146g of titanium dioxide, adding 10ml of alcohol, grinding and uniformly mixing, then placing in a resistance furnace, calcining at 720 ℃ for 6 hours to obtain lithium metatitanate, and grinding for later use;
s12, weighing 12g of the obtained lithium metatitanate, 520g of manganese sesquioxide, 280g of lithium hydroxide monohydrate and 750mL of reaction mother liquor (in the embodiment 1), adding into a high-pressure reaction kettle, reacting for 10 hours at 220 ℃, filtering to obtain a filter cake which is a titanium manganese composite intermediate product, repeatedly using the filter cake (serving as the reaction mother liquor) in a next reaction medium, washing and drying the filter cake, and calcining for 4 hours at 410 ℃ to obtain the powdery titanium manganese composite lithium ion sieve adsorbent.
S13, dispersing and soaking the obtained powdery titanium-manganese composite lithium ion sieve adsorbent in an aqueous solution containing a silane coupling agent, stirring and reacting for 1h, and then drying at 100 ℃ to obtain the surface-modified powdery titanium-manganese composite lithium ion sieve adsorbent;
s2, preparing a granular manganese-titanium composite lithium ion sieve adsorbent:
s21, uniformly stirring and mixing 125mL of gelatin water solution with the concentration of 14g/L, 125mL of polyvinyl alcohol (PVA) water solution with the concentration of 7g/L, 0.8g of magnesium hydroxide and 250mL of pure water to obtain a water phase;
s22, measuring 35ml of styrene, 0.7ml of divinylbenzene, 3.5ml of methyl methacrylate, uniformly mixing 1.1g of benzoyl peroxide serving as an initiator and 1.75g of solid paraffin serving as a pore-forming agent to obtain an oil phase;
s23, adding the obtained water phase into a 500mL reactor, stirring, heating to 78 ℃, and then sequentially adding 20g of the surface-modified powdery manganese-titanium composite lithium ion sieve adsorbent and the obtained oil phase into the water phase for suspension polymerization for 3h;
s24, heating to 90 ℃ to harden spherical particles prepared by suspension polymerization for 0.5h, and then filtering, screening and grading the hardened particles to obtain a granulation product;
s25, extracting the obtained granulation product by petroleum ether to remove solid paraffin, thereby obtaining the granular manganese-titanium composite lithium ion sieve adsorbent.
Example 3
The preparation method of the manganese-titanium composite lithium ion sieve adsorbent comprises the following steps:
s1, preparing a powdery manganese-titanium composite lithium ion sieve adsorbent:
s11, weighing 153g of lithium hydroxide monohydrate and 146g of titanium dioxide, adding 10ml of alcohol, grinding and uniformly mixing, then placing in a resistance furnace, calcining at 720 ℃ for 6 hours to obtain lithium metatitanate, and grinding for later use;
s12, weighing 24g of the obtained lithium metatitanate, 1040g of manganese sesquioxide, 560g of lithium hydroxide monohydrate, and 750mL of reaction mother liquor (from example 2), adding the obtained mixture into a high-pressure reaction kettle, reacting for 12 hours at 250 ℃, filtering to obtain a filter cake which is a titanium-manganese composite intermediate product, repeatedly using the filter liquor (reaction mother liquor) in a next reaction medium, washing and drying the filter cake, and calcining the filter cake at 450 ℃ for 5 hours to obtain the powdery titanium-manganese composite lithium ion sieve adsorbent;
s13, dispersing and soaking the obtained powdery titanium-manganese composite lithium ion sieve adsorbent in an aqueous solution containing a silane coupling agent, stirring and reacting for 1.5 hours, and then drying at 110 ℃ to obtain the surface-modified powdery titanium-manganese composite lithium ion sieve adsorbent;
s2, preparing a granular manganese-titanium composite lithium ion sieve adsorbent:
s21, uniformly stirring and mixing 125mL of gelatin water solution with the concentration of 7g/L, 125mL of polyvinyl alcohol (PVA) water solution with the concentration of 14g/L, 0.8g of magnesium hydroxide and 250mL of pure water to obtain a water phase;
s22, measuring 35ml of styrene, 0.35ml of divinylbenzene, 3.5ml of methyl methacrylate, uniformly mixing 1.1g of benzoyl peroxide serving as an initiator and 3.5g of liquid paraffin serving as a pore-forming agent to obtain an oil phase;
s23, adding the obtained water phase into a reactor, stirring, heating to 83 ℃, and then sequentially adding 20g of the surface-modified powdery manganese-titanium composite lithium ion sieve adsorbent and the obtained oil phase into the water phase for suspension polymerization for 2.5h;
s24, heating to 90 ℃ to harden spherical particles prepared by suspension polymerization for 3 hours, and then filtering, screening and grading the hardened particles to obtain a granulation product;
s25, extracting the obtained granulation product by petroleum ether to remove liquid paraffin, thereby obtaining the granular manganese-titanium composite lithium ion sieve adsorbent.
Comparative example 1
The procedure was the same as in example 1, except that lithium meta-titanate was not added. The preparation method of the granular pure manganese lithium ion sieve adsorbent comprises the following steps:
SS1, preparation of powdery pure manganese lithium ion sieve adsorbent:
SS11, weighing 520g of Mn2O3, 1100g of lithium hydroxide monohydrate and 750mL of pure water, adding into a high-pressure reaction kettle, reacting for 11 hours at 200 ℃, filtering to obtain a filter cake which is an intermediate product of manganese materials, repeatedly using the filtrate (called reaction mother liquor) in a next reaction medium, washing and drying the filter cake, and calcining at 430 ℃ for 4 hours to obtain a powdery titanium-manganese composite lithium ion sieve adsorbent;
SS12, dispersing and soaking the obtained powdery manganese series lithium ion sieve adsorbent in an aqueous solution containing a silane coupling agent, stirring and reacting for 1h, and then drying at 120 ℃ to obtain a surface modified powdery manganese series lithium ion sieve adsorbent;
preparation of SS2, granular pure manganese lithium ion sieve adsorbent:
SS21, 125mL of gelatin water solution with the concentration of 14g/L, 125mL of polyvinyl alcohol (PVA) water solution with the concentration of 7g/L, 0.8g of magnesium hydroxide and 250mL of pure water are stirred and mixed uniformly to obtain a water phase;
SS22, 35ml of styrene, 0.35ml of divinylbenzene, 3.5ml of methyl methacrylate, 1.1g of benzoyl peroxide as an initiator and 3.5g of solid paraffin as a pore-forming agent are measured and uniformly mixed to obtain an oil phase;
SS23, adding the obtained water phase into a reactor, stirring, heating to 80 ℃, adding 20g of surface-modified powdery manganese-based lithium ion sieve adsorbent into the water phase, slowly adding the obtained oil phase, and carrying out suspension polymerization for 2.5h;
SS24, heating to 90 ℃ to harden spherical particles prepared by suspension polymerization for 1h, and then filtering, screening and grading the hardened particles to obtain a granulation product;
SS25, extracting the obtained granulation product by petroleum ether to remove solid paraffin, thus obtaining the granular pure manganese lithium ion sieve adsorbent.
SEM scanning is carried out on the surface of the granular manganese titanium composite lithium ion sieve adsorbent particles prepared in the example 1, and the morphology is observed, so that the result is shown in figure 2.
As can be seen from the results of FIG. 2, the granular manganese-titanium composite lithium ion sieve adsorbent prepared by the invention has a regular spherical shape and has a granularity of 0.2-0.9 mm.
Further, the manganese-titanium composite lithium ion sieve adsorbent with the granularity of 0.2-0.5mm and the granularity of 0.5-0.9mm are respectively photographed, and the obtained pictures are shown in fig. 3 and 4.
As can be seen from the results of FIG. 3 and FIG. 4, the manganese-titanium composite lithium ion sieve adsorbent prepared by the invention has the advantages that the granularity is 0.2-0.5mm and the granularity is 0.5-0.9mm, the granularity is uniform, the inorganic powder components are uniformly distributed, the granulation process is stable, the granulation agglomeration phenomenon is not generated, and the particles with the granularity of 0.2-0.9mm account for more than 90 percent through observation.
The granular manganese titanium composite lithium ion sieve adsorbent prepared in example 1 was subjected to a particle strength test for 10 times, and the results are shown in table 1 below.
TABLE 1 particle Strength results for the granular manganese titanium composite lithium ion Screen adsorbent prepared in example 1
As can be seen from the results in Table 1, the granular manganese titanium composite lithium ion sieve adsorbent particles prepared by the invention have higher strength.
The granular manganese-titanium composite lithium ion sieve adsorbent prepared in example 1 and the pure manganese-based adsorbent prepared in comparative example 1 were respectively tested for the adsorption capacity of lithium in salt lake brine with a lithium concentration of 250mg/L and the change of Mn and Ti dissolution conditions with the cycle number during the analysis, and the results are shown in fig. 5 and 6.
As is apparent from the results of fig. 5 and 6, the adsorption capacity of the granular pure manganese-based lithium ion sieve adsorbent prepared in comparative example 1 for lithium ions was substantially equivalent to that of the granular manganese-titanium composite (lithium ion sieve) adsorbent prepared in example 1 after 4 cycles, but the dissolution loss (manganese, titanium dissolution rate) of the granular manganese-titanium composite adsorbent prepared in example 1 upon desorption was much smaller than that of the pure manganese-based adsorbent, which indicates that the cyclic performance of the granular manganese-titanium composite lithium ion sieve adsorbent prepared in the present invention was better.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The preparation method of the manganese-titanium composite lithium ion sieve adsorbent is characterized by comprising the following steps of:
s1, preparing a powdery manganese-titanium composite lithium ion sieve adsorbent: adding lithium metatitanate, manganese oxide and lithium hydroxide into an autoclave for reaction, and then calcining to obtain a powdery manganese-titanium composite lithium ion adsorbent;
s2, preparing a granular manganese-titanium composite lithium ion sieve adsorbent:
s21, stirring and mixing the gelatin aqueous solution, the polyvinyl alcohol aqueous solution, the dispersing agent and the water to obtain a water phase;
s22, mixing styrene, divinylbenzene, methyl methacrylate, an initiator and a pore-forming agent to obtain an oil phase;
s23, heating the water phase to a certain temperature, and adding a powdery manganese-titanium composite lithium ion sieve adsorbent and an oil phase into the water phase to perform suspension polymerization reaction to obtain spherical particles;
s24, heating to harden the prepared spherical particles, filtering, screening and grading the hardened spherical particles to obtain a granulation product;
s25, purifying the obtained granulation product, and removing the pore-forming agent to obtain the granular manganese-titanium composite lithium ion sieve adsorbent.
2. The method for preparing the manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein the lithium meta-titanate is prepared by taking titanium dioxide and lithium hydroxide as raw materials and calcining at 700-750 ℃ for 6-24 hours by adopting a solid phase synthesis method.
3. The method for preparing the manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein in the step S1, the molar ratio of Ti to Mn in the lithium meta-titanate and the manganese sesquioxide is 0.1-5:10; the reaction temperature is 200-250 ℃, the reaction time is 10-12h, the calcination temperature is 400-450 ℃, and the calcination time is 4-6h.
4. The method for preparing a manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein in the step S22, the weight of the initiator is 1-8wt% of the sum of the volumes of styrene, divinylbenzene and methyl methacrylate.
5. The method for preparing the manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein the dispersing agent is selected from one or a combination of more than two of sodium chloride, magnesium hydroxide, potassium chloride, calcium hydroxy phosphate or calcium phosphate; the pore-forming agent is one or more than two of toluene, solid paraffin, liquid paraffin, hexane, heptane, octane, n-heptane or 200# petroleum.
6. The method for preparing the manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein in the step S23, the powdery manganese-titanium composite lithium ion sieve adsorbent needs to be subjected to surface modification treatment by using a surfactant before being added into an aqueous phase, and the surfactant is one or a combination of more than two of a silane coupling agent, stearic acid and an stearate.
7. The method for preparing the manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein the suspension polymerization reaction temperature is 78-83 ℃ and the polymerization reaction time is 2-3 h; the volume ratio of the water phase to the oil phase is 1-10:10.
8. The method for preparing a manganese-titanium composite lithium ion sieve adsorbent according to claim 1, wherein in step S24, the hardening time is 0.5-3h.
9. The granular manganese-titanium composite lithium ion sieve adsorbent prepared by the preparation method according to any one of claims 1 to 9, wherein in the granular manganese-titanium composite lithium ion sieve adsorbent, particles with the particle size of 0.2 to 0.9mm account for more than 90% of the total weight.
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