CN113952921A - Preparation method of functionalized silicon material and application of functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution - Google Patents

Preparation method of functionalized silicon material and application of functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution Download PDF

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CN113952921A
CN113952921A CN202110978109.2A CN202110978109A CN113952921A CN 113952921 A CN113952921 A CN 113952921A CN 202110978109 A CN202110978109 A CN 202110978109A CN 113952921 A CN113952921 A CN 113952921A
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rare earth
silicon material
hydroxyquinoline
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silica gel
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孙晓琦
刘晨浩
张鹤鹏
罗兵
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Xiamen Institute of Rare Earth Materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract

The invention belongs to the field of rare earth waste liquid treatment, and discloses a preparation method of a functional silicon material and application thereof in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution, wherein the silicon material with aminated surface and 8-hydroxyquinoline is synthesized by surface modification of the silicon material, silica gel is mainly used for concrete implementation, and the silica gel modified by amino and 8-hydroxyquinoline is used for treating Al3+Has enhanced affinity, wherein the silica gel modified by 8-hydroxyquinoline has Al affinity3+The affinity of the rare earth mineral leachate is stronger, and Al in the rare earth mineral leachate can be effectively removed through the silica gel modified by 8-hydroxyquinoline3+Can realize high-efficiency rare earth after adding the extracting agentThe adsorption of metal ions solves the problem of rare earth ion adsorption and extraction in the actual rare earth mineral product.

Description

Preparation method of functionalized silicon material and application of functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution
Technical Field
The invention belongs to the field of rare earth waste liquid treatment, and particularly relates to a preparation method of a functional silicon material and application of the functional silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution.
Background
Rare earth is called as a treasure house of new materials by people and is listed as a key element for developing high-technology industry by various national governments, and particularly, in the process of gradually converting traditional energy into green energy, the rare earth serving as an important resource is widely applied to the fields of medical treatment, national defense, energy, aerospace and automobiles. By 2020, global demand for rare earth oxides has increased at an annual growth rate of 5%. The yield of rare earth oxide in China is 85% of the world, wherein bastnaesite mainly based on bayan obo in Mongolia China accounts for a very high proportion, light rare earth with relatively low price is mainly used, and the southern adsorption type rare earth ore possibly contains heavy rare earth with higher value, so that the mining of southern ionic type rare earth ore has low energy requirement and small environmental impact compared with other mineral type rare earth. The industrial leaching with ammonium sulfate is generally adopted, the heap leaching with ammonium sulfate leachate or sodium chloride is great in damage to mountains, so the in-situ leaching is actively promoted at present, but the in-situ leaching with ammonium sulfate can cause the landslides of the mountains, the research on the magnesium sulfate leachate by Xiaoyanfei has been recently carried out, the industrial test has been carried out, and the good effect is achieved, and at present, the magnesium sulfate leachate mainly contains Mg2+，Al3+，Ca2+And the existence of a large amount of rare earth ions and complex components cause difficult circulation of the recovered rare earth and the leachate, particularly, because the existence of aluminum ions, the precipitation pH value of the aluminum ions is similar to that of rare earth elements, and impurity removal slag of aluminum causes large amount of rare earth loss, so that the aluminum is the element which has the greatest influence and the greatest difficulty in impurity removal, and in which process flow, the purification problem of the leachate is preferably considered.
At present, the aluminum removal process of the magnesium sulfate leaching solution mainly comprises a precipitation method and an extraction method, wherein the precipitation method mainly comprises a centrifugal sedimentation method, an ammonium bicarbonate precipitation impurity removal method and a magnesium oxide precipitation impurity removal method. The method mainly based on precipitation has the advantages of simple process, high precipitation efficiency and the like, but when the aluminum ion needs to be low, a large amount of industrial waste residues are generated, and the rare earth loss rate is high. The naphthenic acid impurity removal method and the centrifugal extraction method have the advantages of low rare earth loss rate, good effect, capability of effectively separating rare earth ions and aluminum ions, and the problem of easy emulsification and the like during high-concentration aluminum impurity removal. The non-equilibrium extraction method has the characteristics of easy continuous large-scale production, short process flow, low consumption, no need of saponification treatment, high rare earth yield, high impurity removal efficiency and the like, but has the problems of easy corrosion of equipment, high single machine energy consumption, oil removal of raffinate and the like. The ion exchange method is commonly used for various separation and impurity removal, but is often rarely used in ion type rare earth leachate, and is generally used for enriching rare earth elements, column separation and wastewater treatment, mainly because the traditional macroporous resin has long diffusion time due to the fact that adsorption functional groups are wrapped in a carrier, further has the problems of long equilibrium time (the equilibrium can be reached within about 30 min), need to maintain higher extraction rate by increasing the column length, poor selectivity, long leaching time and the like. Is difficult to be applied to the ion type rare earth mine with huge water quantity. Therefore, there is a need to develop a new type of ion exchanger with high efficiency.
Disclosure of Invention
Therefore, aiming at the defects in the prior art, the invention provides a preparation method of a functional silicon material and application thereof in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution.
The invention discloses a preparation method of a functional silicon material, which comprises the following steps:
step 1: activating the surface of the silicon material by a way of, but not limited to, crushing, polishing, pickling, drying and heating;
step 2: uniformly dispersing the activated silicon material in a solvent A, adding an aminosilane coupling agent for reaction, and modifying silicon hydroxyl groups on the surface of the silicon material into amino groups to obtain an aminated silicon material;
and step 3: uniformly dispersing the aminated silicon material in a solvent B, adding a formaldehyde solution of 8-hydroxyquinoline for reaction, and modifying the 8-hydroxyquinoline to the surface of the aminated silicon material to obtain the 8-hydroxyquinoline modified silicon material.
Preferably, the method also comprises the steps of 2',
the step 2': and uniformly dispersing the obtained aminated silicon material in a solvent C for reaction, removing the redundant aminosilane coupling agent, and recovering and drying to obtain the purified aminated silicon material.
Wherein, the solvent A, the solvent B and the solvent C are one of formaldehyde, ethanol, acetone, toluene, ethylbenzene and tetrahydrofuran.
Wherein the silicon material is one of silicon dioxide, amorphous silicic acid, silicate and silica gel.
Wherein the molecular structural formula of the aminosilane coupling agent is Y-Si (OR)3；
Wherein Y is an organofunctional group, SiOR is a siloxy group, and the end of the organofunctional group is an amino group.
The invention also discloses application of the functional silicon material in impurity removal and enrichment of the ionic rare earth ammonia-free leaching solution, and the functional silicon material is prepared by the preparation method.
Further, the application comprises the following steps:
step 1: adding the ion type rare earth ammonia-free leaching solution into the silicon material modified by 8-hydroxyquinoline for reaction,
step 2: and adding a rare earth extractant into the rare earth ore leachate after the silicon material modified by the 8-hydroxyquinoline is adsorbed, and separating to obtain a rare earth complex.
Preferably, the rare earth extractant has the following structure:
Figure BDA0003226568510000031
wherein the compound of the structure of the formula (I) at least comprises two groups
Figure BDA0003226568510000032
R is independently a optionally substituted carbon atomA linear alkyl group having 3 to 12 carbon atoms, an unsubstituted linear alkyl group having 3 to 12 carbon atoms, a substituted branched alkyl group having 3 to 12 carbon atoms, an unsubstituted branched alkyl group having 3 to 12 carbon atoms, a substituted aryl group or an unsubstituted aryl group.
Preferably, the rare earth complex is eluted by acid liquor to obtain rare earth precipitate and rare earth extractant solution.
Preferably, the molar ratio of the rare earth extraction agent to the rare earth elements in the rare earth ore leaching solution is (1.5-2): 1.
compared with the traditional rare earth ore waste liquid metal ion adsorption, the embodiment of the invention provides a preparation method and application of a functional silicon material, which at least comprise the following beneficial effects:
1. the application provides a silicon material with aminated surface and 8-hydroxyquinoline synthesized by surface modification of the silicon material, and is implemented by taking silica gel as a main material, and the silica gel modified by amino and 8-hydroxyquinoline is applied to Al3+Has enhanced affinity, wherein the silica gel modified by 8-hydroxyquinoline has Al affinity3+The affinity of the rare earth ions is stronger, and the affinity of the rare earth ions is not obviously enhanced. Both functional groups play a positive role in the separation of rare earth and aluminum.
2. In chromatographic column separation, Al3+The distribution coefficient of (A) is obviously larger than that of rare earth ions, which shows that Al is in the subsequent chromatographic experiment3+The retention time of the rare earth ions is longer than that of the rare earth ions, so that the subsequent separation is facilitated, and Al can be selectively adsorbed in magnesium sulfate type rare earth mineral liquid3+。
2. The synthesized 8-hydroxyquinoline modified silica gel does not use or generate volatile organic solvents, excessive acid and alkali consumption, waste water and waste residues in the separation process, and the generated acidic waste liquid and the magnesium oxide waste residues can form magnesium sulfate solution after being neutralized, and the magnesium sulfate solution is used as leachate to be returned to the mine for use, so that the closed-loop operation of the re-leaching process is realized.
3. Reabsorbing Al3+The extractant is added into the rare earth ore leaching solution formed later, and the extractant can better adsorb rare earth ions and avoidFree of Al3+Without the use of kerosene and other organic solvents, large-particle solid extraction complexes can be formed and stripped to produce high-concentration rare earth solutions, and the extraction precipitant can be stripped and recovered.
Drawings
FIG. 1 is a flow chart of the synthesis of the material of the present invention.
FIG. 2 is a photograph showing the properties of the synthetic product of example 2 of the present invention, and FIG. 2(a) is Si02FIG. 2(b) is NH2-SiO2FIG. 2(c) shows HQ-SiO2。
FIG. 3 is a SEM TEM image of a synthesized product of example 2 of the present invention, and FIG. 3(a) is Si02FIG. 3(b) is NH2-SiO2FIG. 3(c) shows HQ-SiO2。
FIG. 4 is an infrared spectrum of a synthesized product of example 2 of the present invention.
FIG. 5 shows the synthesis of NH in example 2 of the present invention2-SiO2，HQ-SiO2X-ray photoelectron spectrum of (1), NH in FIG. 5(a)2-SiO2FIG. 5(b) shows HQ-SiO2。
FIG. 6 shows the adsorption and desorption characteristics of N2 as a synthesized product in example 2 of the present invention, FIG. 6(a) shows the pore size characteristics, and FIG. 6(b) shows Si02FIG. 6(c) shows NH2-SiO2FIG. 6(d) shows HQ-SiO2The adsorption and desorption characteristics of N2.
FIG. 7 shows HQ-SiO as a synthetic product in example 2 of the present invention2Adsorption curves for Al3+ at different times.
FIG. 8 shows HQ-SiO as a synthetic product in example 2 of the present invention2
FIG. 9 shows HQ-SiO product synthesized in EXAMPLE 2 of the present invention2Experimental graph of affinity for different metal ions.
FIG. 10 shows HQ-SiO as a synthetic product in example 2 of the present invention2Desorption experimental diagrams for different metal ions.
FIG. 11 shows HQ-SiO as a synthetic product in example 2 of the present invention2Rare earth and aluminum separation coefficient plots at different pH.
FIG. 12 shows HQ-SiO, a synthetic product obtained in example 22FIG. 12(a) shows a cyclic adsorption experiment ofFor the breakthrough curves, FIG. 12(b) is the elution curve.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention discloses a preparation method of a functional silicon material, which comprises the following steps:
step 1: activating the surface of the silicon material by a way of, but not limited to, crushing, polishing, pickling, drying and heating;
step 2: uniformly dispersing the activated silicon material in a solvent A, adding an aminosilane coupling agent for reaction, and modifying silicon hydroxyl groups on the surface of the silicon material into amino groups to obtain an aminated silicon material;
step 2': and uniformly dispersing the obtained aminated silicon material in a solvent C for reaction, removing the redundant aminosilane coupling agent, and recovering and drying to obtain the purified aminated silicon material.
And step 3: and uniformly dispersing the purified aminated silicon material in a solvent B, adding a formaldehyde solution of 8-hydroxyquinoline for reaction, and modifying the 8-hydroxyquinoline to the surface of the aminated silicon material to obtain the 8-hydroxyquinoline modified silicon material.
Wherein the solvent A, the solvent B and the solvent C are one of formaldehyde, ethanol, acetone, toluene, ethylbenzene and tetrahydrofuran.
Wherein the silicon material is one of silicon dioxide, amorphous silicic acid, silicate and silica gel.
The invention also discloses application of the functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution, and the silicon material modified by 8-hydroxyquinoline is prepared by the preparation method.
The application comprises the following steps:
step 1: adding the ion type rare earth ammonia-free leaching solution into the silicon material modified by 8-hydroxyquinoline for reaction,
step 2: adding a rare earth extractant into the rare earth ore leachate subjected to the adsorption of the silicon material modified by the 8-hydroxyquinoline, and separating to obtain a rare earth complex, wherein the molar ratio of the rare earth extractant to the rare earth elements in the rare earth ore leachate is (1.5-2): 1.
wherein, the rare earth extractant has the following structure:
Figure BDA0003226568510000051
wherein the compound of the structure of the formula (I) at least comprises two groups
Figure BDA0003226568510000052
R is independently selected from a substituted linear alkyl group having 3-12 carbon atoms, an unsubstituted linear alkyl group having 3-12 carbon atoms, a substituted branched alkyl group having 3-12 carbon atoms, an unsubstituted branched alkyl group having 3-12 carbon atoms, a substituted aryl group or an unsubstituted aryl group.
Reabsorbing Al3+The extractant is added into the rare earth ore leaching solution formed later, so that the extractant can better adsorb rare earth ions, and Al is avoided3+Without the use of kerosene and other organic solvents, large-particle solid extraction complexes can be formed and stripped to produce high-concentration rare earth solutions, and the extraction precipitant can be stripped and recovered.
Example 2
In this embodiment, the silica gel is used as the main carrier for the experiment, and other silicon materials, i.e., silicon materials coated with silicon hydroxyl groups on the surface, can be used as a substitute. The preparation method is shown in figure 1.
Step 1: the silica gel is heated by 0.1mol/L nitric acid at 60 ℃, filtered and dried in a vacuum drying oven at 100 ℃ for 6 hours.
Step 2: 3.0g of activated silica gel was added to 50ml of toluene and sonicated for 30min, then 1.6g of (3-aminopropyl) triethoxysilane (APTES) was added dropwise, magnetically stirred at 80 ℃ for 18 hours, and filtered to give a milky white solid.
Step 2': collecting the solid, putting the solid into a Soxhlet extractor, heating the solid for 24 hours at 90 ℃ by using ethanol as a solvent, and removing the coupling agent on the surface of the silica gel. Then the mixture is put into a vacuum drying oven and dried for 12 hours at the temperature of 60 ℃. To obtain amino silica gel NH2-SiO2.
And step 3: 100ml of 0.1mol/L formaldehyde solution of 8-hydroxyquinoline are prepared, and 1.6g of aminosilicone NH are added2-SiO2Refluxing at 70 deg.C for 8 hr to obtain 8-hydroxyquinoline modified silica gel (HQ-SiO for short)2。
Example 3
8-Hydroxyquinoline-modified silica gel (HQ-SiO) obtained in example 22) In order to characterize the physicochemical properties of the experimental pair, the specific characterization method is based on the method of using the characterization device, and is not further described herein.
(1) Appearance of the product at different stages
As shown in FIG. 2, comparative Si02，NH2-SiO2，HQ-SiO2The appearance of the product is powdery, wherein Si0 is contained2，NH2-SiO2Is milky white and HQ-SiO2It appeared yellow.
(2) Microstructure of product in different stages
As shown in FIG. 3, Si0 in SEM image2，NH2-SiO2，HQ-SiO2Without any distinction, the sizes are kept in good consistency.
(3)NH2-SiO2，HQ-SiO2Infrared characterization map of
As shown in FIG. 4, it can be seen from the infrared spectrum that NH was passed2-SiO2At 1415cm-1A peak was observed, which was in the vicinity of-NH2The peak of (a) indicates successful amino silica gel modification;
HQ-SiO after modification2The infrared spectrum of the sample changed at 1504cm-1And 1464cm-1The peaks shown represent the shaking of the ring skeleton of C ═ C and C ═ N, respectively, indicating that 8-hydroxyquinoline was successfully grafted.
(4)NH2-SiO2，HQ-SiO2X-ray photoelectron spectrum of
As shown in FIG. 5, it is seen from FIG. 5(a) that there is a peak at 399.7eV, which is typical of-NH2The binding energy, and the peak at 401.7eV is the binding energy resulting from protonation of the amino group. The peak at 398.9eV in FIG. 5(b) is C-NH2The binding energy of (a) thus illustrates that 8-hydroxyquinoline is linked to the aminosilicone through a-C-N bond, while the binding energy appearing at 400.3eV exactly corresponds to the N1s binding energy corresponding to 8-hydroxyquinoline, indicating that the silica gel was successfully functionalized
(5)N2Adsorption and desorption characterization chart
As shown in FIG. 6, HQ-SiO in the low temperature nitrogen adsorption and desorption experiment2And SiO2Having the same adsorption isotherm indicates that the modification did not affect the structure of the silica gel, which has a typical type IV isotherm with a significant H1 hysteresis loop in the p/p0 range, and a p/p0 range of 0.4 to 1.0, indicating the presence of mesopores. At higher relative pressures, saturation of the isotherm can be clearly observed, a feature which indicates that the mesopores are completely filled and no macropores are present. HQ-SiO2Has a monomodal distribution. While HQ-SiO2The pore size of (a) is slightly smaller than that of the unmodified silica gel, which indicates that 8-hydroxyquinoline forms a monolayer structure by surface functionalization of the silica gel.
Example 4
8-Hydroxyquinoline-modified silica gel (HQ-SiO) obtained in example 22) The experiment of metal ion adsorption and desorption properties is carried out oppositely.
(1) Effect of time on adsorption
This example investigated Al at pH 4.5, 10mg/L3+The amount of adsorption in the solution (2) is changed. As shown in FIG. 7, the adsorption reached equilibrium within 1 min.
Adsorption data were analyzed by a pseudo first order (1) and pseudo second order (2) model described by the equations:
Figure BDA0003226568510000071
Figure BDA0003226568510000072
where t represents time in minutes. qt and qe represent the adsorption capacity of the metal ions at equilibrium and t time, k1 is the rate constant of a pseudo-first order kinetic model, k2 is the constant of the pseudo-second order kinetic model, and the adsorption kinetic data has important significance for guiding subsequent column research experiments. Comparing correlation coefficient R of the pseudo first-order model and the pseudo second-order model2，Al3+Pseudo second order model R of2The values are all greater than 0.99, which shows HQ-SiO2For Al3+Mainly adopts a chemical adsorption mechanism. The kinetic model shows that the chemical adsorption brought by the 8-hydroxyquinoline on the surface of the silica gel increases the chemical adsorption efficiency.
(2) Adsorption isotherm
FIG. 8 is HQ-SiO2For Al3+The adsorption isotherm diagram of (A) is shown in FIG. 8, and the correlation coefficient R of the two models is compared in Table 12It is clear that the correlation coefficient of Langmuir model is greater than 0.999 HQ-SiO2For Al3+The adsorption of the catalyst is more consistent with a Langmuir model which has a saturation adsorption limit and is surface single-layer adsorption, and the HQ-SiO is obtained through calculation2The maximum saturated adsorption amount of (2) was 10.644 mg/g.
TABLE 1 HQ-SiO2Isothermal adsorption model judgment
Figure BDA0003226568510000081
(3)HQ-SiO2Affinity assay of
The partition coefficient Kd is usually used to express the capacity of the adsorbent to adsorb metal ions, and it can be seen from FIG. 9 that in the silica gel modified with amino and 8-hydroxyquinoline,all to Al3+Has enhanced affinity of HQ-SiO2For Al3+The affinity of the rare earth ions is stronger, and the affinity of the rare earth ions is not obviously enhanced. Both functional groups play a positive role in the separation of rare earth and aluminum. Partition coefficient is a chromatographically important chromatographic parameter, Al3+Is significantly greater than the partition coefficient (Kd) of the rare earth ion, which indicates Al in the subsequent chromatographic column separation3+The retention time of (a) is also longer than that of the rare earth ions, which is beneficial to subsequent separation.
(4) Desorption of the adsorbent
In order to maintain the reuse of the adsorbent, we tried desorption with hydrochloric acid of different concentrations, and as a result, as shown in fig. 10, the rare earth ions were easily desorbed at a low pH, indicating that the complex of 8 hydroxyquinoline and rare earth is less stable, which is consistent with the conclusion drawn in fig. 9. And Al at pH 13+The desorption rate is only 25 percent, and the desorption rate is gradually increased along with the continuous increase of the concentration of the hydrochloric acid. When the concentration of hydrochloric acid reaches 3mol/L, Al3+Is almost completely desorbed. This is because an increase in the hydrochloric acid concentration causes the reaction to proceed toward the decomposition of the complex.
(5) Separation coefficient of rare earth and aluminum
The separation coefficient beta is expressed as the separation degree which can be achieved between rare earth and aluminum, fig. 11 shows that the rare earth and aluminum have good separation effect, wherein the beta value increases along with the increase of the pH value, when the pH value is more than 4.5, almost all the rare earth ions have separation coefficients more than 20, the rare earth ions (La, Pr and Nd) with high abundance are more than 50, and the separation effect is obvious.
(6) Cyclic adsorption experiment
As can be seen from FIG. 12, the 5-time breakthrough curve and the 5-time elution curve did not change significantly, indicating that HQ-SiO2Has good reproducibility, HQ-SiO2Can be repeatedly used for a plurality of times. The desorption of acidity can effectively avoid resource waste and loss caused by silica gel hydrolysis.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A preparation method of a functionalized silicon material is characterized by comprising the following steps:
step 1: activating the surface of the silicon material by a way of, but not limited to, crushing, polishing, pickling, drying and heating;
step 2: uniformly dispersing the activated silicon material in a solvent A, adding an aminosilane coupling agent for reaction, and modifying silicon hydroxyl groups on the surface of the silicon material into amino groups to obtain an aminated silicon material;
and step 3: uniformly dispersing the aminated silicon material in a solvent B, adding a formaldehyde solution of 8-hydroxyquinoline for reaction, and modifying the 8-hydroxyquinoline to the surface of the aminated silicon material to obtain the 8-hydroxyquinoline modified silicon material.
2. The method of claim 1, further comprising a step 2',
the step 2': and uniformly dispersing the obtained aminated silicon material in a solvent C for reaction, removing the redundant aminosilane coupling agent, and recovering and drying to obtain the purified aminated silicon material.
3. The method of claim 2, wherein the solvent A, the solvent B, and the solvent C are one of formaldehyde, ethanol, acetone, toluene, ethylbenzene, and tetrahydrofuran.
4. The method of claim 3, wherein the silicon material is one of silicon dioxide, amorphous silicic acid, silicate, and silica gel.
5. The method of claim 4, wherein the aminosilane coupling agent has the molecular formula Y-Si (OR)3；
Wherein Y is an organofunctional group, SiOR is a siloxy group, and the end of the organofunctional group is an amino group.
6. The application of the functional silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution is characterized in that the functional silicon material is prepared by the preparation method of any one of claims 1 to 5.
7. The application of the functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution according to claim 6, wherein the application comprises the following steps:
step 1: adding the ion type rare earth ammonia-free leaching solution into the silicon material modified by 8-hydroxyquinoline for reaction,
step 2: and adding a rare earth extractant into the rare earth ore leachate after the silicon material modified by the 8-hydroxyquinoline is adsorbed, and separating to obtain a rare earth complex.
8. The use according to claim 7, wherein the rare earth extractant has the structure:
Figure FDA0003226568500000021
wherein the compound of the structure of the formula (I) at least comprises two groups
Figure FDA0003226568500000022
R is independently selected from a substituted C3-12 linear alkyl group, an unsubstituted C3-12 linear alkyl group, a substituted C3-12 branched alkyl group, an unsubstituted C3-12 branched alkyl group, a substituted aryl group or an unsubstituted aryl group。
9. The use of claim 8, wherein the rare earth complex is eluted with an acid solution to obtain a rare earth precipitate and a rare earth extractant solution.
10. The use according to claim 9, wherein the molar ratio of the rare earth extractant to the rare earth element in the rare earth ore leaching solution is (1.5-2): 1.
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