Adsorbing material as well as preparation method and application thereof

Abstract

The invention relates to an adsorption material as well as a preparation method and application thereof. The adsorption material comprises functional resin balls with macroporous structures, the functional resin ball with the macroporous structure contains an active adsorption group; the active adsorption group comprises beta-diketone structure and / or phosphine oxide structure functional groups; and the surface of the functionalized resin ball with the macroporous structure is also coated with a layer of nano-pore film. According to the preparation method provided by the invention, functional resin balls are obtained through grafting reaction, and then the surfaces of the resin balls are coated with a layer of nanopore film through Friedel-Crafts reaction. The adsorption material provided by the invention has excellent adsorption capacity and selectivity on lithium, good fluidity, large solution treatment capacity and strong cycling stability, and the preparation method provided by the invention is simple to operate and relatively low in cost and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lithium extraction, in particular to an adsorption material and a preparation method and use thereof. BACKGROUND

[0002] There are a large number of low-magnesium salt lake lithium resources in Tibet Autonomous Region of China and South America. The concentration of lithium in salt lake resources is generally low, and is usually associated with a certain amount of calcium and / or magnesium, and also contains a large amount of SO4 2- and CO3 2- , which brings great difficulty to lithium extraction technology. Adsorption lithium extraction technology has the characteristics of environmental protection, low cost and simple process, and has a significant advantage in lithium extraction technology. However, if lithium is directly adsorbed from brine containing a large amount of calcium and magnesium, the adsorption efficiency of lithium is generally less than 40%. In addition, in the field of lithium salt production and lithium secondary resource recovery, waste liquid containing low concentration of lithium and a large amount of other monovalent ions is often produced, especially a solution containing a large amount of sodium impurities. The presence of sodium ions and other monovalent ions also interferes with the recovery of lithium.

[0003] Adsorption separation materials are materials that achieve the functions of separation, purification, concentration and enrichment of substances through ion exchange and adsorption of exchanged substances, and are widely used in industrial water treatment, food and drinking water, nuclear industry, electronics, biomedicine, environmental protection, hydrometallurgy and other industrial fields. Adsorption materials are generally materials containing porous structures, interstitial channel structures or adsorption functional groups. The purpose is to make the solution to be treated pass through the material smoothly through the porous structure or interstitial channel, increase the contact area with the adsorption functional group, and make the adsorption functional group adsorb the target element. The existing lithium adsorption material can provide a liquid flow path by constructing a pore structure, but it has no selectivity for metal ions in the solution and can only selectively adsorb and separate metal ions through functional groups. For example, CN114433007A discloses a method for preparing a lithium adsorbent by in-situ growth on an alumina ball and a lithium adsorbent. The method grows lithium adsorbent LiCl·Al2(OH)6·yH2O on the pores or surface of Al2O3 small balls, and uses LiCl·Al2(OH)6·yH2O to adsorb lithium. However, the pores of the Al2O3 small balls themselves have no selectivity for metal ions, and have low selectivity for lithium in the presence of multiple cations.

[0004] Therefore, it is of great significance to provide an adsorption material that can increase the contact area with the solution, has good adsorption and selectivity for lithium, and has strong cycle stability. SUMMARY

[0005] To solve the above problems, the present application aims to provide an adsorption material and its preparation method and use. Compared with the prior art, the adsorption material provided by the present application has a large pore structure, thereby increasing the contact area of the solution with the adsorption material, and has good fluidity and cycle stability, and has excellent adsorption effect and selectivity for lithium.

[0006] To achieve the above object, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides an adsorption material, which comprises a functionalized resin ball with a large pore structure.

[0008] The functionalized resin ball with a large pore structure contains active adsorption groups.

[0009] The active adsorption groups comprise beta-diketone structure and / or phosphine oxide group functional groups.

[0010] The surface of the functionalized resin ball with a large pore structure is further coated with a layer of nanopore membrane.

[0011] In the adsorption material provided by the present application, the resin ball with a large pore structure can provide a flow path for the solution, thereby increasing the contact area of the solution with the adsorption material; the active adsorption groups contained on the resin ball have excellent adsorption capacity for lithium ions, and can coordinate and adsorb lithium ions through beta-diketone structure and phosphine oxide group, thereby greatly improving the adsorption effect for lithium; the surface-coated nanopore membrane has an intercepting effect on high-valence ions and Na + , K + , Mg 2+ , Ca 2+ and other ions with large ionic radius, thereby increasing the separation effect of lithium and impurity ions and improving the selectivity for lithium. Furthermore, the adsorption material provided by the present application uses a functionalized resin ball as a carrier, and has good fluidity, large solution treatment capacity, strong cycle stability, and wide application prospect.

[0012] Preferably, the average pore size of the large pore structure is 40-50 nm, for example, it can be 40 nm, 45 nm, or 50 nm, but is not limited to the listed values, and other unlisted values within the value range are also applicable.

[0013] Preferably, the average thickness of the nanopore membrane is 5-8 nm, for example, it can be 5 nm, 6 nm, or 8 nm, but is not limited to the listed values, and other unlisted values within the value range are also applicable.

[0014] Preferably, the average pore size of the nanopore membrane is 1-2 nm, for example, it can be 1 nm, 1.1 nm, 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm or 2 nm, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0015] In the present application, the thickness and pore size of the nanopore membrane are preferably controlled within a specific range, which can play a good selective adsorption effect.

[0016] In a second aspect, the present application provides a preparation method of the adsorbent material according to the first aspect of the present application, which comprises the following steps:

[0017] (1) mixing chloromethylated resin beads containing macroporous structure and nucleophilic functional substances, and performing grafting reaction under vacuum and heating to obtain functional resin beads;

[0018] (2) mixing the functional resin beads obtained in step (1) and dichlorobenzene, and performing Friedel-Crafts reaction under the condition of anhydrous aluminum chloride as catalyst to obtain functional resin beads wrapped with nanopore membrane, i.e. the adsorbent material.

[0019] In the preparation method provided by the present application, first, the functional groups with adsorption function are fixed on the resin beads by grafting reaction of chloromethylated resin beads and nucleophilic functional substances, so as to improve the adsorption capacity for lithium; then, a layer of nanopore membrane is coated on the surface of the functional resin beads through Friedel-Crafts reaction, and the interception capacity for high-valence ions and Na + , K + , Mg 2+ , Ca 2+ ions with larger ionic radius is improved through the nanopore membrane, so as to increase the separation effect of lithium and impurity ions.

[0020] Preferably, the average pore size of the chloromethylated resin beads in step (1) is 40-50 nm, for example, it can be 40 nm, 45 nm or 50 nm, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0021] In the present application, the average pore size of the chloromethylated resin beads is preferably controlled within a specific range, which can improve the flowability of the solution between the pores, thereby improving the adsorption efficiency of ions.

[0022] Preferably, the chloromethylated resin beads and the nucleophilic functional substances in step (1) are mixed in a solvent.

[0023] Preferably, the solvent comprises dimethylbenzene.

[0024] Preferably, the solvent has a mass percentage of 30-50% of the total mass of the chloromethylated resin beads and the nucleophilic functionalized substance, for example, it can be 30%, 35%, 40%, 45% or 50%, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0025] Preferably, the nucleophilic functionalized substance includes a β-diketone and / or a phosphine oxide compound.

[0026] Preferably, the β-diketone contains active hydrogen.

[0027] Preferably, the β-diketone includes any one of 3,3'-(1,3-phenylene) bis(1-phenylpropane-1,3-dione), 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione or 4,4-difluoro-1-phenyl-1,3-butanedione or a combination of at least two thereof.

[0028] Preferably, the phosphine oxide compound includes any one of diphenylphosphine oxide, methyldiphenylphosphine oxide or dimethyldiphenylphosphine oxide or a combination of at least two thereof.

[0029] Preferably, the mass ratio of the chloromethylated resin beads and the nucleophilic functionalized substance is (1-5):1, for example, it can be 1:1, 2:1, 3:1, 4:1 or 5:1, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0030] In the present application, preferably, the mass ratio of the chloromethylated resin beads and the nucleophilic functionalized substance is controlled in a specific range, which can cover the surface of the macroporous microstructure to form a thin film structure with a thickness of 5-8 nm, so that the adsorption material has high selectivity and high adsorption performance.

[0031] Preferably, the mole ratio of the β-diketone and the phosphine oxide compound in the nucleophilic functionalized substance is (1-3):1, for example, it can be 1:1, 1.5:1, 2:1, 2.5:1 or 3:1, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0032] In the present application, the nucleophilic functionalized substance is preferably a β-diketone and a phosphine oxide compound, because both of them contain functional groups that can coordinate with Li + to form a cyclic chelate coordination structure, thereby being able to synergistically increase the adsorption effect on lithium. In the present application, preferably, the mole ratio of the two is controlled in a specific range, which can effectively utilize the geometric distribution of the functional groups, thereby increasing the ability to synergistically adsorb lithium.

[0033] Preferably, the temperature of the heating in step (1) is 90-110℃, for example, it can be 90℃, 95℃, 100℃, 105℃ or 110℃, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0034] Preferably, the vacuum degree of the grafting reaction is -0.05 to -0.09 MPa, for example, it can be -0.05 MPa, -0.06 MPa, -0.07 MPa, -0.08 MPa or -0.09 MPa, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0035] In the present application, the vacuum degree is preferably controlled in a specific range, which can facilitate the discharge of gas in the grafting reaction, make the reaction proceed more thoroughly, and thus improve the performance of the adsorbent material.

[0036] Preferably, the time of the grafting reaction is 5-12 h, for example, it can be 5 h, 6 h, 8 h, 10 h or 12 h, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0037] Preferably, the grafting reaction also produces hydrogen chloride gas.

[0038] Preferably, the hydrogen chloride gas is extracted from the reaction system.

[0039] Preferably, the mass ratio of the functionalized resin beads to dichlorobenzene in step (2) is (100-200):1, for example, it can be 100:1, 120:1, 150:1, 180:1 or 200:1, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0040] In the present application, the mass ratio of the functionalized resin beads to dichlorobenzene is preferably controlled in a specific range, which can form a uniform nanofiltration membrane.

[0041] Preferably, the mass ratio of the anhydrous aluminum chloride to dichlorobenzene is 1:(2-3), for example, it can be 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0042] In the present application, the mass ratio of the anhydrous aluminum chloride to dichlorobenzene is preferably controlled in a specific range, which can more effectively catalyze the progress of the Friedel-Crafts reaction.

[0043] Preferably, the temperature of the Friedel-Crafts reaction is 80-90℃, for example, it can be 80℃, 85℃ or 90℃, but is not limited to the listed values, other values not listed in the range of values are also applicable.

[0044] Preferably, the time of the Friedel-Crafts reaction is 12-24h, for example, it can be 12h, 16h, 18h, 20h, 22h or 24h, but is not limited to the listed values, other values not listed in the value range are also applicable.

[0045] As a preferred technical solution of the second aspect of the present application, the preparation method comprises the following steps:

[0046] (1) mixing chloromethylated resin balls with an average pore size of 40-50nm and a nucleophilic functional substance in dimethylbenzene, the mass percentage of dimethylbenzene in the total mass of the chloromethylated resin balls and the nucleophilic functional substance is 30-50%, the nucleophilic functional substance includes any one or a combination of at least two of β-diketone and / or phosphine oxide compound, the β-diketone contains active hydrogen, the β-diketone includes any one or a combination of at least two of 3,3'-(1,3-phenylene) bis(1-phenylpropane-1,3-dione), 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione or 4,4-difluoro-1-phenyl-1,3-butanedione, the phosphine oxide compound includes any one or a combination of at least two of diphenylphosphine oxide, methyldiphenylphosphine oxide or dimethyldiphenylphosphine oxide, the mass ratio of the chloromethylated resin balls and the nucleophilic functional substance is (1-5):1, the molar ratio of the β-diketone and the phosphine oxide compound in the nucleophilic functional substance is (1-3):1, and the grafting reaction is carried out under the conditions of a vacuum degree of -0.05 to -0.09 Mpa and heating at 90-110°C for 5-12h to obtain functional resin balls;

[0047] (2) mixing the functional resin balls obtained in step (1) and dichlorotoluene in a mass ratio of (100-200):1, and carrying out Friedel-Crafts reaction under the conditions of anhydrous aluminum chloride as a catalyst and a temperature of 80-90°C for 12-24h, the mass ratio of the anhydrous aluminum chloride and the dichlorotoluene is 1:(2-3), to obtain functional resin balls wrapped by nanopore membranes, i.e. the adsorbent material.

[0048] In a third aspect, the present application provides a use of the adsorbent material as described in the first aspect of the present application, and the adsorbent material is used for selectively adsorbing lithium elements in a lithium-containing solution.

[0049] The adsorbent material provided by the present application has excellent adsorption capacity and selectivity for lithium, good fluidity, large solution treatment capacity and strong cycle stability, and is suitable for selectively adsorbing lithium in a lithium-containing solution.

[0050] In the present application, the source of the lithium-containing solution is not particularly limited, for example, it can be a lithium-containing salt lake brine or a solution generated in a lithium production process, and the adsorbent material provided by the present application is particularly suitable for selectively adsorbing lithium from a lithium-containing solution containing Na + , K + , Mg2+ , Ca 2+ The lithium-containing solution with impurity ions has a good selective adsorption effect.

[0051] Preferably, the impurity ions contained in the lithium-containing solution include monovalent impurity ions and / or divalent impurity ions.

[0052] Preferably, the monovalent impurity ions include Na + and / or K + .

[0053] Preferably, the divalent impurity ions include Mg 2+ and / or Ca 2+ .

[0054] Preferably, the concentration of Li + in the lithium-containing solution is 0.1-0.5 g / L, for example, can be 0.1 g / L, 0.2 g / L, 0.3 g / L, 0.4 g / L or 0.5 g / L, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0055] Preferably, the concentration of Na + in the lithium-containing solution is 50-120 g / L, for example, can be 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L, 110 g / L or 120 g / L, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0056] Preferably, the concentration of Mg 2+ in the lithium-containing solution is 1-20 g / L, for example, can be 1 g / L, 2 g / L, 5 g / L, 8 g / L, 10 g / L, 12 g / L, 15 g / L, 18 g / L or 20 g / L, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0057] Preferably, the concentration of Ca 2+ in the lithium-containing solution is 0-5 g / L, for example, can be 0 g / L, 1 g / L, 2 g / L, 3 g / L, 4 g / L or 5 g / L, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0058] Compared with the prior art, the present application has the following beneficial effects:

[0059] (1) The adsorption material provided by the present application has excellent adsorption capacity and selectivity for lithium, good fluidity, large amount of solution to be treated, strong cycle stability, and is suitable for selectively adsorbing lithium in a lithium-containing solution.

[0060] (2) The preparation method provided by the application fixes the active adsorption groups on the resin balls through the grafting reaction, improves the cycle stability of the adsorption material, introduces the active adsorption groups of the beta-diketone structure and phosphine oxide group through the grafting reaction, and can synergistically improve the adsorption capacity for lithium; the nano-pore membrane is generated through the Friedel-Crafts reaction, the interception effect for impurity ions such as Na + + 2+ 2+ , and greatly improves the selectivity for lithium.

[0061] (3) The preparation method provided by the application is simple to operate, low in cost, and has a broad application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0062] Figure 1 is a schematic diagram of the grafting reaction described in embodiment 1 of the application;

[0063] Figure 2 is a schematic diagram of the Friedel-Crafts reaction described in embodiment 1 of the application;

[0064] Figure 3 is a schematic diagram of the principle of the adsorption material for selectively adsorbing lithium described in embodiment 1 of the application;

[0065] Figure 4 is a q static adsorption nano-membrane pore size determination result diagram of the adsorption material described in embodiment 1 of the application;

[0066] Figure 5 is an infrared spectrum diagram of the adsorption material described in embodiment 1 of the application. DETAILED DESCRIPTION

[0067] The technical solutions of the application will be further described through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the application and should not be regarded as specific limitations on the application.

[0068] Embodiment 1

[0069] The embodiment provides an adsorption material, which comprises a functionalized resin ball with a macroporous structure, the functionalized resin ball with the macroporous structure contains active adsorption groups, the active adsorption groups comprise a beta-diketone structure and a phosphine oxide group, and the surface of the functionalized resin ball with the macroporous structure is further coated with a nano-pore membrane, the average pore diameter of the macroporous structure is 45 nm, the average thickness of the nano-pore membrane is 6 nm, and the average pore diameter of the nano-pore membrane is 1.5 nm.

[0070] The embodiment also provides a preparation method of the adsorption material, and the preparation method comprises the following steps:

[0071] ​​​(1) mixing chloromethylated resin beads with an average pore size of 45 nm and a nucleophilic functional substance, 3,3'-(1,3-phenylene) bis(1-phenylpropane-1,3-dione) (abbreviated as H2BPOBP) containing active hydrogen and diphenyl phosphine oxide, in dimethylbenzene, the mass percentage of dimethylbenzene in the total mass of the chloromethylated resin beads and the nucleophilic functional substance is 40%, the mass ratio of the chloromethylated resin beads and the nucleophilic functional substance is 3:1, the molar ratio of H2BPOBP and diphenyl phosphine oxide in the nucleophilic functional substance is 2:1, and the grafting reaction is carried out at a vacuum degree of -0.07 Mpa and a temperature of 100°C for 8h to obtain functional resin beads;

[0072] The schematic diagram of the grafting reaction is shown in Figure 1 The chloromethylated resin beads, H2BPOBP and diphenyl phosphine oxide react to produce hydrogen chloride gas, and the β-diketone structure and phosphine oxide group are modified to the resin beads at the same time.

[0073] (2) mixing the functional resin beads obtained in step (1) and dichloromethylbenzene in a mass ratio of 150:1, and carrying out a Friedel-Crafts reaction under the condition of anhydrous aluminum chloride as a catalyst and a temperature of 85°C for 18h, the mass ratio of the anhydrous aluminum chloride and dichloromethylbenzene is 1:2.5, to obtain functional resin beads wrapped by a nanopore membrane, i.e., the adsorbent material;

[0074] The schematic diagram of the Friedel-Crafts reaction is shown in Figure 2 As can be seen from Figure 2 , dichloromethylbenzene is converted into a nanopore membrane through the Friedel-Crafts reaction.

[0075] In this embodiment, the adsorbent material is used to adsorb Li + when the solution contains Li + , Na + , K 2+ , Mg 2+ , Ca + and other ions, and the adsorption principle diagram is shown in Figure 3 As can be seen from Figure 3 , the nanopore membrane plays an intercepting role for high-valence ions Mg 2+ , Ca 2+ , and after the monovalent Li + passes through the nanopore membrane, Li + is selectively adsorbed by the β-diketone structure and phosphine oxide group.

[0076] Example 2

[0077] The embodiment provides an adsorbing material, which comprises functionalized resin balls with a macroporous structure, the functionalized resin balls with the macroporous structure contain active adsorbing groups, the active adsorbing groups comprise a beta-diketone structure and a phosphine oxide group, and the surface of the functionalized resin balls with the macroporous structure is further coated with a nanoporous membrane, the average pore size of the macroporous structure is 40 nm, the average thickness of the nanoporous membrane is 5 nm, and the average pore size of the nanoporous membrane is 1 nm.

[0078] The embodiment further provides a preparation method of the adsorbing material, and the preparation method comprises the following steps:

[0079] (1) mixing chloromethylated resin balls with an average pore size of 40 nm and a nucleophilic functional substance in dimethylbenzene, the nucleophilic functional substance is H2BPOBP and diphenyl phosphine oxide containing active hydrogen, the mass percentage of dimethylbenzene in the total mass of the chloromethylated resin balls and the nucleophilic functional substance is 30%, the mass ratio of the chloromethylated resin balls and the nucleophilic functional substance is 5:1, the molar ratio of H2BPOBP and diphenyl phosphine oxide in the nucleophilic functional substance is 1:1, and the grafting reaction is carried out under the conditions of a vacuum degree of -0.09 Mpa and heating at 90 DEG C for 12 h to obtain functionalized resin balls;

[0080] (2) mixing the functionalized resin balls obtained in the step (1) and dichloromethylbenzene in a mass ratio of 100:1, and carrying out a Friedel-Crafts reaction under the conditions of anhydrous aluminum chloride as a catalyst and a temperature of 90 DEG C for 12 h, the mass ratio of the anhydrous aluminum chloride and the dichloromethylbenzene is 1:2, to obtain functionalized resin balls wrapped with a nanoporous membrane, namely the adsorbing material.

[0081] Embodiment 3

[0082] The embodiment provides an adsorbing material, which comprises functionalized resin balls with a macroporous structure, the functionalized resin balls with the macroporous structure contain active adsorbing groups, the active adsorbing groups comprise a beta-diketone structure and a phosphine oxide group, and the surface of the functionalized resin balls with the macroporous structure is further coated with a nanoporous membrane, the average pore size of the macroporous structure is 50 nm, the average thickness of the nanoporous membrane is 6 nm, and the average pore size of the nanoporous membrane is 2 nm.

[0083] The embodiment further provides a preparation method of the adsorbing material, and the preparation method comprises the following steps:

[0084] (1) mixing chloromethylated resin beads with an average pore size of 50 nm and nucleophilic functional substances, which are H2BPOBP and diphenyl phosphine oxide, in dimethylbenzene, the mass percentage of dimethylbenzene in the total mass of the chloromethylated resin beads and the nucleophilic functional substances is 50%, the mass ratio of the chloromethylated resin beads and the nucleophilic functional substances is 1:1, the molar ratio of H2BPOBP and diphenyl phosphine oxide in the nucleophilic functional substances is 3:1, and the grafting reaction is carried out at a vacuum degree of -0.05 Mpa and a temperature of 110°C for 5 hours to obtain functional resin beads;

[0085] (2) mixing the functional resin beads obtained in step (1) and dichloromethylbenzene in a mass ratio of 200:1, and carrying out a Friedel-Crafts reaction under the catalysis of anhydrous aluminum chloride at a temperature of 80°C for 24 hours, the mass ratio of the anhydrous aluminum chloride and dichloromethylbenzene is 1:3, to obtain functional resin beads wrapped with a nanoporous membrane, i.e., the adsorbent material.

[0086] Example 4

[0087] The embodiment provides a preparation method of an adsorbent material, which is different from example 1 only in that H2BPOBP is replaced by 1,3-diphenyl-1,3-propanedione with an equal molar amount, and diphenyl phosphine oxide is replaced by methyldiphenyl phosphine oxide with an equal molar amount.

[0088] Example 5

[0089] The embodiment provides a preparation method of an adsorbent material, which is different from example 1 only in that H2BPOBP is replaced by 4,4-difluoro-1-phenyl-1,3-butanedione with an equal molar amount, and diphenyl phosphine oxide is replaced by dimethyldiphenyl phosphine oxide with an equal molar amount.

[0090] Example 6

[0091] The embodiment provides a preparation method of an adsorbent material, which is different from example 1 only in that diphenyl phosphine oxide is replaced by H2BPOBP with an equal molar amount, i.e., no phosphine oxide compound is added.

[0092] Example 7

[0093] The embodiment provides a preparation method of an adsorbent material, which is different from example 1 only in that the molar ratio of H2BPOBP and diphenyl phosphine oxide in the nucleophilic functional substances is controlled to be 0.5:1 while the total mass of the nucleophilic functional substances remains unchanged.

[0094] Example 8

[0095] The present example provides a method for preparing an adsorbent material, which differs from example 1 only in that the total mass of the nucleophilic functionalizing substance is controlled, and the molar ratio of H2BPOBP and diphenyl phosphine oxide is 5:1.

[0096] Example 9

[0097] The present example provides a method for preparing an adsorbent material, which differs from example 1 only in that the mass ratio of chloromethylated resin beads and nucleophilic functionalizing substance is 0.5:1.

[0098] Example 10

[0099] The present example provides a method for preparing an adsorbent material, which differs from example 1 only in that the mass ratio of chloromethylated resin beads and nucleophilic functionalizing substance is 10:1.

[0100] Example 11

[0101] The present example provides a method for preparing an adsorbent material, which differs from example 1 only in that the mass ratio of functionalized resin beads and dichloromethylbenzene is 70:1.

[0102] The present example also provides an adsorbent material obtained by the above method, which differs from example 1 only in that the average thickness of the nanoporous membrane is 10 nm, and the average pore size is 5 nm.

[0103] Example 12

[0104] The present example provides a method for preparing an adsorbent material, which differs from example 1 only in that the mass ratio of functionalized resin beads and dichloromethylbenzene is 300:1.

[0105] The present example also provides an adsorbent material obtained by the above method, which differs from example 1 only in that the average thickness of the nanoporous membrane is 30 nm, and the average pore size is 10 nm.

[0106] Comparative Example 1

[0107] The present example provides an adsorbent material, which differs from example 1 only in that it does not contain a nanoporous membrane.

[0108] The present example also provides a method for preparing the above adsorbent material, which differs from example 1 only in that step (2) is not performed, and the functionalized resin beads obtained in step (1) are the adsorbent material.

[0109] Comparative Example 2

[0110] The present example provides an adsorbent material, which differs from example 1 only in that it does not contain active adsorption groups.

[0111] The embodiment also provides a preparation method of the adsorbent material, which is different from the method in the embodiment 1 only in that the step (1) is not performed, and the chloromethylated resin ball with a macroporous structure is used to replace the functionalized resin ball in the step (2) to perform the Friedel-Crafts reaction, so that the resin ball wrapped by the nanoporous membrane is obtained, that is, the adsorbent material.

[0112] The adsorbent materials provided in the embodiments 1-12 and the comparative examples 1-2 are used for lithium extraction test, and the adsorption effect of lithium is tested. The experimental method is as follows: the prepared adsorbent material is filled in an adsorption column with a volume of 120 mL, and the filling volume is 100 mL. Then, a lithium-containing solution is added from top to bottom at a flow rate of 10 mL / min, and adsorption is performed. The feed solution passes through 5 column volumes (50 min of feeding), and sampling analysis is performed. The adsorption efficiency (%) of Li and the separation coefficients of Li and impurity elements are calculated. The composition of the lithium-containing solution is as follows: Li, 0.3 g / L; Mg, 5 g / L; Ca, 1.5 g / L; Na, 43 g / L; K, 2 g / L; and B, 1.2 g / L. The element content in the lithium-containing solution after adsorption is detected by ICP-AES, and the adsorption rate of lithium, the Li / Mg separation coefficient, the Li / Ca separation coefficient, the Li / Na separation coefficient and the Li / K separation coefficient are calculated. The results are shown in Table 1.

[0113] The calculation method of the adsorption rate of lithium is as follows: (C-Li (0) -C-Li (f) ) / CLi (0) ×100%;

[0114] The calculation method of the separation coefficient is as follows: separation coefficient = [C-Li (0) / C-Li (f) ] / [Cimp (0) / Cimp (f) ];

[0115] Wherein, C-Li (0) is the concentration of lithium in the lithium-containing solution before adsorption; C-Li (f) is the concentration of lithium in the lithium-containing solution after adsorption; Cimp (0) is the concentration of impurity elements (for example, Mg, Ca, Na and K) in the lithium-containing solution before adsorption; and Cimp (f) is the concentration of impurity elements in the lithium-containing solution after adsorption.

[0116] Cyclic stability experiment: the adsorbent material after adsorption is desorbed, and then a plurality of cyclic adsorption experiments are performed. The adsorption rate of lithium after 20 cycles of the adsorbent materials provided in the embodiments 1-12 and the comparative examples 1-2 is tested. The results are shown in Table 1.

[0117] For example, the q static adsorption nanopore membrane pore size determination result graph and the infrared spectrum graph of the obtained adsorbent material are as follows:Figure 4 and Figure 5 As shown in the figure, the adsorption material has nano membrane pore size and bifunctional active material structure.

[0118] Table 1

[0119]

[0120]

[0121] From the data in Table 1, the following points can be seen:

[0122] (1) From the data of Examples 1-5, it can be seen that the adsorption material and the preparation method thereof provided by the present application can make the lithium adsorption rate reach 85.7% or more, the Li / Mg separation coefficient reach 89.5 or more, the Li / Ca separation coefficient reach 67.4 or more, the Li / Na separation coefficient reach 239 or more, the Li / K separation coefficient reach 322 or more, and the lithium adsorption rate after 20 cycles reach 86.3% or more.

[0123] (2) By comparing the data of Example 1 and Example 6, it can be seen that the difference between Example 6 and Example 1 is only that no phosphine oxide compound is added, and the lithium adsorption rate and the separation coefficient of lithium and each impurity ion in Example 6 are significantly lower than those in Example 1. Therefore, by using β-diketone structure and phosphine oxide coordination to adsorb lithium ions, the adsorption rate and selectivity of lithium can be greatly improved.

[0124] (3) By comparing the data of Example 1 and Examples 7-8, it can be seen that the difference between Examples 7-8 and Example 1 is only that the molar ratio of β-diketone and phosphine oxide compound is not within the preferred range of the present application, and the lithium adsorption rate and the separation coefficient of lithium and each impurity ion in Examples 7-8 are significantly lower than those in Example 1. Therefore, by controlling the molar ratio of β-diketone and phosphine oxide compound, the present application can effectively utilize the geometric distribution of functional groups, thereby increasing the ability to synergistically adsorb lithium.

[0125] (4) By comparing the data of Example 1 and Examples 9-10, it can be seen that the difference between Examples 9-10 and Example 1 is only that the mass ratio of chloromethylated resin beads and nucleophilic functionalized substances is not within the preferred range of the present application, and the lithium adsorption rate and the separation coefficient of lithium and each impurity ion in Examples 9-10 are significantly lower than those in Example 1. Therefore, by controlling the mass ratio of chloromethylated resin beads and nucleophilic functionalized substances, the present application can cover the surface of large pore microstructure and form a thin film structure with a thickness of 5-8 nm, so that the adsorption material has high selectivity and high adsorption performance.

[0126] (5) By comparing the data of example 1 and examples 11-12, it can be seen that the difference between examples 11-12 and example 1 is only that the mass ratio of functionalized resin balls to dichlorobenzene is not in the preferred range of the application, and the lithium adsorption rate and the separation coefficient of lithium and each impurity ion in examples 11-12 are significantly lower than those in example 1, so the application can form a uniform nanofiltration membrane by preferably controlling the mass ratio of functionalized resin balls to dichlorobenzene, thereby improving the adsorption rate and selectivity of lithium.

[0127] (6) By comparing the data of example 1 and comparative examples 1-2, it can be seen that the difference between comparative example 1 and example 1 is only that the nanoporous membrane is not prepared by the Friedel-Crafts reaction, and the difference between comparative example 2 and example 1 is only that the active adsorption group is not grafted by the grafting reaction, and the lithium adsorption rate and the separation coefficient of lithium and each impurity ion in comparative examples 1-2 are significantly lower than those in example 1, so the adsorption material provided by the application can coordinate and adsorb lithium ions through the β-diketone structure and phosphine oxide group, and can improve the selective adsorption by the nanoporous membrane coated on the surface, and finally can achieve excellent adsorption effect and selectivity for lithium.

[0128] In summary, the adsorption material and the preparation method thereof provided by the application can fix the active adsorption group on the resin ball by the grafting reaction, thereby improving the cycle stability of the adsorption material; the β-diketone structure and the phosphine oxide group active adsorption group introduced by the grafting reaction can synergistically improve the adsorption capacity for lithium; the nanoporous membrane produced by the Friedel-Crafts reaction can increase the interception effect for Na + , K + , Mg 2+ , Ca 2+ and other impurity ions, thereby greatly improving the selectivity for lithium, and having a broad application prospect.

[0129] The applicant declares that the above is only a specific embodiment of the application, but the protection scope of the application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the application can be easily thought of by those skilled in the art, and all fall within the protection scope and disclosure scope of the application.

Claims

1. An adsorbent material, characterized by, The adsorption material comprises functionalized resin balls with macroporous structure; The functionalized resin balls with macroporous structure contain active adsorption groups; The active adsorption groups comprise β-diketone structure and / or phosphine oxide group; The surface of the functionalized resin balls with macroporous structure is further coated with a layer of nanoporous membrane.

2. The adsorbent material of claim 1, wherein, The average pore size of the macroporous structure is 40-50 nm; Preferably, the average thickness of the nanoporous membrane is 5-8 nm; Preferably, the average pore size of the nanoporous membrane is 1-2 nm.

3. A method for producing the adsorbent material according to claim 1 or 2, characterized by, The preparation method comprises the following steps: (1) mixing chloromethylated resin balls with macroporous structure and nucleophilic functional substances, and performing grafting reaction under vacuum and heating to obtain functionalized resin balls; (2) mixing the functionalized resin balls obtained in step (1) and dichloromethylbenzene, and performing Friedel-Crafts reaction under the condition of using anhydrous aluminum chloride as catalyst to obtain functionalized resin balls wrapped with nanoporous membrane, i.e. the adsorption material.

4. The production method according to claim 3, characterized by, The average pore size of the chloromethylated resin balls in step (1) is 40-50 nm.

5. The production method according to claim 3 or 4, characterized by, The chloromethylated resin balls and the nucleophilic functional substances in step (1) are mixed in a solvent; Preferably, the solvent comprises dimethylbenzene; Preferably, the mass percentage of the solvent in the total mass of the chloromethylated resin balls and the nucleophilic functional substances is 30-50%.

6. The method of any one of claims 3-5, wherein, The nucleophilic functional substances in step (1) comprise β-diketone and / or phosphine oxide compound; Preferably, the β-diketone contains active hydrogen; Preferably, the β-diketone comprises any one or a combination of at least two of 3,3'-(1,3-phenylene) bis(1-phenylpropane-1,3-dione), 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione or 4,4-difluoro-1-phenyl-1,3-butanedione; Preferably, the phosphine oxide compound comprises any one or a combination of at least two of diphenylphosphine oxide, methyldiphenylphosphine oxide or dimethyldiphenylphosphine oxide; Preferably, the mass ratio of the chloromethylated resin balls to the nucleophilic functional substances is (1-5):1; Preferably, the molar ratio of the β-diketone to the phosphine oxide compound in the nucleophilic functional substances is (1-3):

1.

7. The method of any one of claims 3-6, wherein, The heating temperature in step (1) is 90-110℃; Preferably, the vacuum degree of the grafting reaction is -0.05 to -0.09 Mpa; Preferably, the grafting reaction time is 5-12 h; Preferably, the grafting reaction further produces hydrogen chloride gas; Preferably, the hydrogen chloride gas is extracted from the reaction system.

8. The method of any one of claims 3-7, wherein, The mass ratio of the functionalized resin balls to dichloromethylbenzene in step (2) is (100-200):1; Preferably, the mass ratio of the anhydrous aluminum chloride to dichloromethylbenzene is 1:(2-3); Preferably, the Friedel-Crafts reaction temperature is 80-90℃; Preferably, the Friedel-Crafts reaction time is 12-24 h.

9. Use of the adsorbent material according to claim 1 or 2, characterized in that, The adsorption material is used for selectively adsorbing lithium elements in a lithium-containing solution.

10. Use according to claim 9, characterized in that, The impurity ions contained in the lithium-containing solution comprise monovalent impurity ions and / or divalent impurity ions; Preferably, the monovalent impurity ions comprise Na + and / or K + ; Preferably, the divalent impurity ions comprise Mg 2+ and / or Ca 2+ .

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