A spherical porous carbonized resin based on 8-hydroxyquinoline chelate resin and its preparation method and application

Abstract

The present invention provides a kind of 8-hydroxyquinoline type chelate resin base spherical porous carbonized resin and its preparation method and application, belong to the technical field of porous carbon materials. The present invention fundamentally changes the introduction mode of heteroatoms, uses 8-hydroxyquinoline as the monomer raw material of polymer resin, 8-hydroxyquinoline itself has a rigid structure, and can utilize its aromatic ring and monomers such as formaldehyde, phenol to support the whole polymer skeleton in the form of polycondensation, N atom not only becomes the builder of the main skeleton, and its N atom introduction content is controllable, and distribution is more uniform. The present invention adopts the mode of reverse suspension polymerization, can obtain the resin precursor with high sphericity, high mechanical strength and good stability, can withstand strong alkali etching activation to expand pores; In the process of high temperature carbonization and strong alkali etching activation, uniformly distributed and abundant N atoms can help carbon escape and structural rearrangement, greatly increase the specific surface area of the resin, enrich the pore structure.

Description

Technical Field

[0001] The present invention relates to the technical field of porous carbon materials, in particular to an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin and a preparation method and application thereof. Background Art

[0002] Porous carbon materials have the advantages of adjustable pore structure, rich porosity, high specific surface area, and good structural stability. They are widely used in fields such as adsorption separation, new energy storage and conversion, and functional catalysis. The skeleton structure of the carbon precursor and the process conditions of the carbonization process significantly affect the pore structure and surface properties of porous carbon materials. In addition to adjusting the skeleton structure of the carbon precursor itself, the doping of non-metallic heteroatoms (such as N, P, B, and S) can also significantly affect the final structure and properties of the material. For example, the introduction of heteroatoms can not only increase the material's specific surface area, increase surface polarity and adsorption sites, but also improve the efficiency of electron conduction by changing the electron arrangement in the carbon layer. At the same time, it can create abundant defect sites on or near the carbon surface to generate redox reactions, thereby increasing additional energy capacity.

[0003] Currently, the introduction of non-metallic heteroatoms typically involves simple mixing / impregnation followed by co-carbonization, carbonization with ammonia gas purge, and fragmented linking of carbon precursors. However, these heteroatom introduction methods clearly present significant challenges: the amount and distribution of heteroatoms introduced are uncontrollable, experimental reproducibility, and product stability struggle to meet the requirements for large-scale industrial production. Furthermore, to ensure heteroatom introduction, the dosage of dopant is often excessive, and the violent overflow of dopant during the carbonization and heating phase can easily disrupt the structure and reduce the residual carbon yield. These uncertainties make it difficult to develop these methods into a mature process for industrial application. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide an 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin and its preparation method and application. The present invention uses an 8-hydroxyquinoline chelate resin with heteroatoms as the carbonized resin skeleton, introduces nitrogen atoms in situ, and the introduction of nitrogen atoms is controllable and uniformly distributed. The obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin has a high specific surface area.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing an 8-hydroxyquinoline-type chelate resin-based spherical porous carbonized resin, comprising the following steps:

[0007] Mixing 8-hydroxyquinoline, phenol, formaldehyde, a reaction solvent, and a catalyst to obtain a reaction phase;

[0008] mixing the dispersion medium and the dispersant to obtain a continuous phase;

[0009] adding the continuous phase to the reaction phase, and performing reverse phase suspension polymerization under stirring to obtain a spherical resin precursor;

[0010] Carbonizing the spherical resin precursor at high temperature to obtain a carbonized resin;

[0011] The carbonized resin is placed in a strong alkaline solution, soaked, taken out, and activated at high temperature to obtain an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin.

[0012] Preferably, the molar ratio of 8-hydroxyquinoline, phenol and formaldehyde is 1:(0.5-6):(1.75-10).

[0013] Preferably, the reaction solvent is one or more of an alcohol solvent, an ether solvent and water;

[0014] The catalyst is concentrated hydrochloric acid.

[0015] Preferably, the dispersion medium is liquid paraffin and / or 1,2-dichloroethane;

[0016] The dispersant is span-80, or a compound of span-80 and tween-85;

[0017] The dispersant is 5‰~1% of the mass of the dispersion medium.

[0018] Preferably, the temperature of the reverse phase suspension polymerization is 75-120° C., and the time is 5-10 hours.

[0019] Preferably, the programmed temperature rising process of the high temperature carbonization includes:

[0020] In air atmosphere, heat from room temperature to 250~300℃ at a heating rate of 2~5℃ / min and hold for 1~3h;

[0021] Under an inert protective atmosphere, continue to heat up to 700~800℃ at a heating rate of 3~6℃ / min and keep warm for 2~3h.

[0022] Preferably, the strong alkaline solution is a KOH solution, and the concentration of the strong alkaline solution is 0.1-2 mol / L;

[0023] The soaking time is 2 to 8 hours.

[0024] Preferably, the temperature-programmed activation process includes:

[0025] Under an inert protective atmosphere, heat from room temperature to 340-360°C at a heating rate of 4-6°C / min and hold for 20-50 min.

[0026] Under an inert protective atmosphere, continue to heat up to 800~1000℃ at a heating rate of 8~12℃ / min and keep warm for 1~2h.

[0027] The present invention provides an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin prepared by the above-mentioned preparation method, wherein nitrogen atoms are in situ introduced into the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin, and the specific surface area of the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin is 1000-1300 m 2 / g.

[0028] The present invention provides the application of the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin in the fields of adsorption separation, functional catalysis and blood perfusion.

[0029] The present invention provides a method for preparing a spherical porous carbonized resin based on an 8-hydroxyquinoline chelate resin, comprising the following steps: mixing 8-hydroxyquinoline, phenol, formaldehyde, a reaction solvent, and a catalyst to obtain a reaction phase; mixing a dispersion medium and a dispersant to obtain a continuous phase; adding the continuous phase to the reaction phase and performing reverse suspension polymerization under stirring to obtain a spherical resin precursor; carbonizing the spherical resin precursor at high temperature to obtain a carbonized resin; and placing the carbonized resin in a strong alkaline solution, soaking it, removing it, and performing high-temperature activation to obtain an 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin. The present invention fundamentally changes the method for introducing heteroatoms. 8-hydroxyquinoline is used as the monomer raw material for the polymer resin. 8-hydroxyquinoline itself has a rigid structure, and its aromatic ring can be used to support the entire polymer backbone through condensation polymerization with monomers such as formaldehyde and phenol. Heteroatoms (N atoms) not only become builders of the main backbone, but also the introduced N atom content is controllable and the distribution is more uniform. Traditional phenolic resin beads prepared by suspension polymerization suffer from insufficient and uniform crosslinking, especially after the introduction of a third monomer containing heteroatoms, which significantly reduces the degree of crosslinking and mechanical strength, and can only be expanded by water vapor activation. The present invention uses reverse suspension polymerization to obtain a resin precursor with high sphericity, high mechanical strength, and good stability, which can withstand strong alkaline etching activation to expand pores. During high-temperature carbonization and strong alkaline etching activation, the evenly distributed and abundant N atoms can help carbon release and structural rearrangement, greatly increasing the specific surface area of the resin and enriching the pore structure.

[0030] Furthermore, the present invention can further enrich the internal pore structure of the carbonized resin and increase the specific surface area by controlling the temperature and programmed temperature rise process of high-temperature carbonization and high-temperature activation. The results of the examples show that the 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin prepared by the present invention has a good spherical shape, high mechanical strength, a spherical rate of 93-96% after grinding, and a specific surface area of 1000-1300 m2 measured by an N2 adsorption instrument.2 / g.

[0031] At the same time, the preparation method provided by the present invention is simple to operate, low in cost, and easy to realize industrialized mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is the reaction process of polymerization reaction;

[0033] Figure 2 Optical microscope images of the carbon precursor resins in Examples 1, 2, and 3;

[0034] Figure 3 is the Fourier transform infrared spectrum of the carbon precursor resin in Example 1;

[0035] Figure 4 This is a scanning electron microscope photograph of the spherical porous carbonized resin obtained in Example 1;

[0036] Figure 5 This is a scanning electron microscope photograph of the spherical porous carbonized resin obtained in Example 2;

[0037] Figure 6 This is a scanning electron microscope photo of the spherical porous carbonized resin obtained in Example 3.

[0038] Figure 7 : is the nitrogen adsorption-desorption curve of the spherical porous carbonized resin obtained in Example 1;

[0039] Figure 8 : is the nitrogen adsorption-desorption curve of the spherical porous carbonized resin obtained in Example 2;

[0040] Figure 9 : This is the nitrogen adsorption-desorption curve of the spherical porous carbonized resin obtained in Example 3;

[0041] Figure 10 The pore size distribution diagram of the carbonized resin finally obtained in Example 1 is compared with the pore size distribution diagram of the precursor in Example 1 that was only carbonized but not activated;

[0042] Figure 11 The pore size distribution diagram of the carbonized resin finally obtained in Example 2 is compared with the pore size distribution diagram of the precursor only carbonized but not activated in Example 1;

[0043] Figure 12 The pore size distribution of the carbonized resin obtained in Example 3 is compared with the pore size distribution of the carbonized but unactivated precursor in Example 1;

[0044] Figure 13 This is the appearance of the precursor resin obtained in Comparative Example 2;

[0045] Figure 14This is the appearance of the carbonized resin obtained in Comparative Example 3;

[0046] Figure 15 This is the appearance of the spherical porous carbonized resin obtained in Comparative Example 4. DETAILED DESCRIPTION

[0047] The present invention provides a method for preparing an 8-hydroxyquinoline-type chelate resin-based spherical porous carbonized resin, comprising the following steps:

[0048] Mixing 8-hydroxyquinoline, phenol, formaldehyde, a reaction solvent, and a catalyst to obtain a reaction phase;

[0049] mixing the dispersion medium and the dispersant to obtain a continuous phase;

[0050] adding the continuous phase to the reaction phase, and performing reverse phase suspension polymerization under stirring to obtain a spherical resin precursor;

[0051] Carbonizing the spherical resin precursor at high temperature to obtain a carbonized resin;

[0052] The carbonized resin is placed in a strong alkaline solution, soaked, taken out, and activated at high temperature to obtain an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin.

[0053] Unless otherwise specified, the raw materials used in the present invention are all commercially available.

[0054] The present invention comprises mixing 8-hydroxyquinoline, phenol, formaldehyde, a reaction solvent, and a catalyst to obtain a reaction phase. In the present invention, the molar ratio of 8-hydroxyquinoline, phenol, and formaldehyde is preferably 1:(0.5-6):(1.75-10), and more preferably 1:6:10, 1:5:8, or 1:0.5:1.75.

[0055] In the present invention, the reaction solvent is preferably one or more of an alcohol solvent, an ether solvent, and water. In the present invention, the alcohol solvent is preferably ethylene glycol, and the ether solvent is preferably ethylene glycol monomethyl ether or ethylene glycol dimethyl ether. In the present invention, the reaction solvent is preferably miscible ethylene glycol and ethylene glycol monomethyl ether, or miscible ethylene glycol monomethyl ether and water; more preferably ethylene glycol monomethyl ether. In the present invention, the mass ratio of the total mass of 8-hydroxyquinoline, phenol, and formaldehyde to the reaction solvent is 1:1 to 3, more preferably 1:2.

[0056] In the present invention, the catalyst is preferably concentrated hydrochloric acid. In the present invention, when concentrated hydrochloric acid is used as the catalyst, the pH value of the reaction phase is 1-4, more preferably 1-2.

[0057] The present invention has no special requirements for the mixing method, and any mixing method well known to those skilled in the art can be used, such as stirring mixing.

[0058] The present invention mixes a dispersion medium and a dispersant to obtain a continuous phase. In the present invention, the dispersion medium is preferably liquid paraffin and / or 1,2-dichloroethane; the dispersant is preferably Span-80, or a compound of Span-80 and Tween-85. When Span-80 and Tween-85 are used separately, the mass ratio of the compounded Span-80 to Tween-85 is preferably 5-9:1, more preferably 6-8:1.

[0059] In the present invention, the dispersant is preferably 5‰ to 1% of the mass of the dispersion medium, more preferably 6‰ to 8‰.

[0060] The present invention has no special requirements for the mixing method, and any mixing method well known to those skilled in the art can be used, such as stirring mixing.

[0061] After obtaining the reaction phase and the continuous phase, the present invention adds the continuous phase to the reaction phase and performs reverse phase suspension polymerization under stirring to obtain a spherical resin precursor. In the present invention, the volume ratio of the reaction phase to the continuous phase is preferably 1:3 to 5, more preferably 1:4.

[0062] In the present invention, when the reaction phase is added to the continuous phase, the reaction phase is slowly added along the wall of the container, and the interface between the two phases remains flat; stirring is started after the addition is completed, and the stirring rate is preferably 150~200r / min, more preferably 160~180r / min.

[0063] In the present invention, the temperature of the reverse phase suspension polymerization is preferably 75-120° C., more preferably 90-120° C., and the time is preferably 5-10 h, more preferably 6-8 h.

[0064] In the present invention, the reaction process of the reverse phase suspension polymerization is as follows Figure 1 shown.

[0065] After the inverse suspension polymerization reaction, the present invention preferably performs post-treatment on the obtained polymerization reaction mixture, and the post-treatment preferably comprises the following steps:

[0066] The reverse phase suspension polymerization reaction mixture is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain a spherical resin precursor solid.

[0067] The present invention has no special requirements for the solid-liquid separation method, and any solid-liquid separation method well known to those skilled in the art can be used, such as filtration.

[0068] In the present invention, the detergents used for washing are preferably ethanol, petroleum ether, and distilled water in that order; and the pH value of the obtained solid is preferably washed to neutral.

[0069] The present invention has no special requirements for the drying method, and any drying method well known to those skilled in the art can be used.

[0070] After obtaining the spherical resin precursor, the present invention performs high-temperature carbonization on the spherical resin precursor to obtain a carbonized resin. In the present invention, the high-temperature carbonization is preferably performed in a tube furnace. In the present invention, the temperature-programmed process of the high-temperature carbonization preferably includes:

[0071] In an air atmosphere, the temperature is raised from room temperature to 250-300°C, preferably 260-280°C; the heating rate is preferably 2-5°C / min, more preferably 3-4°C / min; the holding time is preferably 1-3 hours, more preferably 2 hours;

[0072] Under an inert protective atmosphere, continue to heat to 700-800°C, preferably 750°C; the heating rate is preferably 3-6°C / min, more preferably 4-5°C / min; the holding time is preferably 2-3h, more preferably 2.5h.

[0073] In the present invention, the inert protective atmosphere is preferably N2 atmosphere. In the present invention, carbonization is preferably carried out in a sealed inert gas atmosphere.

[0074] The present invention performs high-temperature carbonization under the above conditions, which can remove the low-crosslinked part and amorphous carbon in the skeleton, and simultaneously rearrange the main carbon skeleton, which ultimately manifests as further enrichment of the pore structure and further improvement of the specific surface area.

[0075] After obtaining the carbonized resin, the present invention places the carbonized resin in a strong alkaline solution, soaks it, removes it, and performs high-temperature activation to obtain an 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin. In the present invention, the strong alkaline solution is preferably a KOH solution, and the concentration of the strong alkaline solution is preferably 0.1 to 2 mol / L, more preferably 1 mol / L; in the present invention, the soaking time is preferably 2 to 8 hours, more preferably 4 to 6 hours.

[0076] In the present invention, the temperature-programmed activation process preferably includes:

[0077] Under an inert protective atmosphere, the temperature is raised from room temperature to 340-360°C, preferably 350°C, at a heating rate of preferably 4-6°C / min, more preferably 5°C / min, and the holding time is preferably 20-50 min, more preferably 30-40 min;

[0078] Under an inert protective atmosphere, continue to heat to 800-1000°C, preferably 850-950°C; the heating rate is preferably 8-12°C / min, more preferably 9-10°C / min, and the holding time is preferably 1-2h, more preferably 1.5h.

[0079] In the present invention, the inert gas is preferably N2.

[0080] The present invention performs high-temperature activation under the above conditions and can utilize the etching effect of a strong base to form and expand pores, so that the final carbonized resin has a richer pore structure and a higher specific surface area.

[0081] After the high-temperature activation, the present invention preferably washes and dries the obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin.

[0082] The present invention provides an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin prepared by the above-mentioned preparation method, wherein nitrogen atoms are in situ introduced into the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin, and the specific surface area of the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin is 1000-1300 m 2 / g.

[0083] The present invention provides applications of the above-mentioned 8-hydroxyquinoline-type chelate resin-based spherical porous carbonized resin in the fields of adsorption separation, functional catalysis, and new energy storage and conversion.

[0084] The 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin provided by the present invention, its preparation method and application are described in detail below with reference to the examples, but they should not be construed as limiting the scope of protection of the present invention. Example 1

[0085] Liquid wax is used as the dispersion medium, 8-hydroxyquinoline:phenol = 1:1

[0086] Prepare the reaction phase in a three-necked flask: Add 10.56g of 8-hydroxyquinoline, 6.84g of phenol, and 5.46g of trioxymethylene. Add 39g of ethylene glycol monomethyl ether to fully dissolve the monomers, then add concentrated hydrochloric acid, mix thoroughly, and adjust the pH to 1-2. Prepare the continuous phase in a beaker: Weigh 0.9g of Span-80, 0.1g of Tween-85, and 199g of liquid paraffin, and mix thoroughly. Add the prepared continuous phase to the reaction phase in the three-necked flask. Stir at 170 rpm until the mixture is dispersed into uniform droplets. Heat to 90°C and react for 7 hours. After the reaction, wash the resulting spherical resin repeatedly with ethanol, petroleum ether, and distilled water until neutral, then dry to obtain a spherical resin precursor.

[0087] Weigh 5 g of the prepared spherical resin precursor into a crucible, place it in a high-temperature tube furnace, heat it from room temperature to 300 ° C in air at a heating rate of 3 ° C / min, and keep it warm for 2 hours. Then seal the tube tightly to isolate the outside air, introduce N2 into the tube, continue to heat to 800 ° C in an inert atmosphere at a heating rate of 4 ° C / min, and keep it warm for 150 minutes. After the reaction is completed, cool it to room temperature and take it out to obtain carbonized resin.

[0088] The carbonized resin was mixed with a 1 mol / L KOH solution in a mass ratio of 1:2 and placed in a crucible for full immersion for 5 hours. The mixture was then placed in the middle of a muffle furnace tube and purged with N2 for 30 minutes to exclude air. The mixture was then heated from room temperature to 350°C at a heating rate of 5°C / min under an inert atmosphere for 30 minutes. The mixture was then heated to 900°C at a heating rate of 10°C / min for 90 minutes. The mixture was cooled to room temperature after the reaction was completed and removed. Finally, the obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin was washed with distilled water until neutral, dried, and stored at room temperature.

[0089] The obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin has a spherical rate of 94% after grinding and a specific surface area of 1244.6m 2 / g. Example 2

[0090] 1,2-dichloroethane as dispersion medium, 8-hydroxyquinoline:phenol = 2:1

[0091] Prepare the reaction phase in a three-necked flask: Add 15.05g of 8-hydroxyquinoline, 4.88g of phenol, and 5.46g of trioxymethylene. Add 43g of ethylene glycol monomethyl ether to fully dissolve the reactants, then add concentrated hydrochloric acid and mix thoroughly to adjust the pH to 1-2. Prepare the continuous phase in a beaker: Weigh 0.9g of span-80, 0.1g of tween-85, and 199g of 1,2-dichloroethane and mix thoroughly. Add the prepared continuous phase to the three-necked flask containing the reaction phase. Stir at 150 rpm until the mixture is dispersed into small, uniform droplets. Heat to the azeotropic point of 75°C and react for 1 hour. Then, use a water separator to distill off the low-boiling-point solvent. For every 10mL removed, add 10mL of liquid paraffin to the flask until the temperature reaches 90°C. Maintain this temperature for 5 hours. After the reaction is completed, the obtained spherical resin is repeatedly washed with ethanol, petroleum ether and distilled water until it is neutral and then dried to obtain a spherical resin precursor.

[0092] Weigh 5 g of the prepared spherical resin precursor into a crucible, place it in the middle of the muffle furnace tube, heat it from room temperature to 300 ° C in air, at a heating rate of 3 ° C / min, and keep it warm for 2 hours, then seal the tube tightly to isolate the outside air, introduce N2 into the tube, continue to heat to 800 ° C in an inert atmosphere, at a heating rate of 4 ° C / min, and keep it warm for 150 minutes. After the reaction is completed, cool it to room temperature and take it out to obtain carbonized resin.

[0093] The carbonized resin was mixed with a 1 mol / L KOH solution at a mass ratio of 1:2 and placed in a crucible to fully soak for 5 hours. The mixture was then placed in a high-temperature tube furnace, and after nitrogen was introduced for 30 minutes to exclude air, the mixture was heated from room temperature to 350°C under an inert atmosphere at a heating rate of 5°C / min and kept warm for 30 minutes. The mixture was then heated to 900°C at a heating rate of 10°C / min and kept warm for 90 minutes. After the reaction was completed, the mixture was cooled to room temperature and removed. Finally, the obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin was washed with distilled water until neutral, dried, and stored at room temperature.

[0094] The obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin has a spherical rate of 92% after grinding and a specific surface area of 1326.9m 2 / g. Example 3

[0095] Liquid wax is used as the dispersion medium, 8-hydroxyquinoline: phenol = 1:5

[0096] Prepare the reaction phase in a three-necked flask: Add 3.07g of 8-hydroxyquinoline, 10.00g of phenol, and 5.46g of trioxymethylene. Add 32g of ethylene glycol monomethyl ether to fully dissolve the monomers, then add concentrated hydrochloric acid, mix thoroughly, and adjust the pH to 1-2. Prepare the continuous phase in a beaker: Weigh 0.9g of Span-80, 0.1g of Tween-85, and 199g of liquid paraffin, and mix thoroughly. Add the prepared continuous phase to the reaction phase in the three-necked flask. Stir at 170 rpm until the mixture is dispersed into uniform droplets. Heat to 110°C and react for 7 hours. After the reaction, wash the resulting spherical resin repeatedly with ethanol, petroleum ether, and distilled water until neutral, then dry to obtain a spherical resin precursor.

[0097] Weigh 5 g of the prepared spherical resin precursor into a crucible, place it in a high-temperature tube furnace, heat it from room temperature to 300 ° C in air at a heating rate of 3 ° C / min, and keep it warm for 2 hours. Then seal the tube tightly to isolate the outside air, introduce N2 into the tube, continue to heat to 800 ° C in an inert atmosphere at a heating rate of 4 ° C / min, and keep it warm for 150 minutes. After the reaction is completed, cool it to room temperature and take it out to obtain carbonized resin.

[0098] The carbonized resin was mixed with a 1 mol / L KOH solution at a mass ratio of 1:2 and placed in a crucible to fully soak for 5 hours. The mixture was then placed in the middle of a muffle furnace tube and purged with N2 for 30 minutes to exclude air. The mixture was then heated from room temperature to 350°C under an inert atmosphere at a heating rate of 5°C / min and kept warm for 30 minutes. The mixture was then heated to 900°C at a heating rate of 10°C / min and kept warm for 90 minutes. After the reaction was completed, the mixture was cooled to room temperature and removed. Finally, the obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin was washed with distilled water until neutral, dried, and stored at room temperature.

[0099] The obtained 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin has a spherical rate of 96% after grinding and a specific surface area of 1062.8m 2 / g.

[0100] (1) The carbon precursor resins in Examples 1, 2, and 3 were characterized by optical microscopy. The results are as follows: Figure 2 As shown, Figure 2 In the figure, (a) is the carbon precursor resin of Example 1, (b) is the carbon precursor resin of Example 2, and (c) is the carbon precursor resin of Example 3. Figure 1 It can be seen that the precursor resin obtained in the present invention is a spherical resin with relatively high strength.

[0101] (2) The carbon precursor resin in Example 1 was characterized by Fourier transform infrared spectroscopy. The results are as follows: Figure 3 As shown. Figure 3 It can be seen that 8-hydroxyquinoline is successfully introduced into the resin of the present invention.

[0102] (3) The N element content of the precursor resins obtained in Examples 1 to 3 was analyzed, and the functional group content of the functional group 8-hydroxyquinoline was converted. The results are shown in Table 1.

[0103] Table 1 Analysis results of N element content in precursor resin and calculated functional group content

[0104] N element content (wt%) Functional group 8-hydroxyquinoline content (mmol / g) Example 1 1.76 1.26 Example 2 2.33 1.67 Example 3 0.81 0.58

[0105] (4) The scanning electron microscope photograph of the spherical porous carbonized resin obtained in Example 1 is as follows: Figure 4 As shown, the scanning electron microscope photo of the spherical porous carbonized resin obtained in Example 2 is as follows Figure 5 As shown, the scanning electron microscope photo of the spherical porous carbonized resin obtained in Example 3 is as follows Figure 6 shown. Figures 4 to 6In the middle, the left is the internal pores, and the right is the complete carbonized resin. The left picture shows the rich pore structure inside the resin and the good pore interconnectivity, which is consistent with the subsequent pore size distribution and BET specific surface area measurement results. The whole ball in the right picture shows that the spherical appearance of the carbonized resin is complete, indicating that the carbon precursor prepared by the present invention can withstand high-temperature carbonization and high-temperature activation, and maintains a good spherical appearance.

[0106] (5) The nitrogen adsorption-desorption curve of the spherical porous carbonized resin obtained in Example 1 is as follows: Figure 7 As shown, its specific surface area is 1224.6m 2 / g; The nitrogen adsorption and desorption curve of the spherical porous carbonized resin obtained in Example 2 is as follows Figure 8 As shown, its specific surface area is 1326.9m 2 / g; The nitrogen adsorption and desorption curve of the spherical porous carbonized resin obtained in Example 3 is as follows Figure 9 As shown, its specific surface area is 1062.8m 2 / g.

[0107] (6) The pore size distribution of the carbonized resin obtained in Example 1 is compared with the pore size distribution of the carbonized but unactivated precursor in Example 1. Figure 10 As shown, it can be seen that strong alkaline etching activation has an obvious pore expansion effect.

[0108] (7) The pore size distribution of the carbonized resin obtained in Example 2 is compared with the pore size distribution of the carbonized but unactivated precursor in Example 2. Figure 11 As shown, it can be seen that strong alkaline etching activation has an obvious pore expansion effect.

[0109] (8) The pore size distribution of the carbonized resin obtained in Example 3 is compared with the pore size distribution of the carbonized but unactivated precursor in Example 3. Figure 12 As shown, it can be seen that strong alkaline etching activation has an obvious pore expansion effect. Comparative Example 1

[0110] Comparison of polymerization solvent types

[0111] Based on the scheme of Example 1, only the type of reaction solvent was changed. The appearance of the obtained precursor resin is shown in Table 2.

[0112] Table 2 Appearance of precursor resin in different reaction solvents

[0113] Solvent type Appearance Ethylene glycol Spherical slightly sticky Ethylene glycol + ethylene glycol methyl ether Some spheres are slightly elliptical Ethylene glycol monomethyl ether Smooth sphere Ethylene glycol monomethyl ether + water Rough sphere Ethyl acetate Monomer precipitation Ethylene glycol dimethyl ether Ball adhesion Comparative Example 2

[0114] Based on the scheme of Example 1, only the polymerization temperature was changed to 70°C. The appearance of the obtained precursor resin was as follows: Figure 13It can be seen that when the reaction temperature is lower than 75 ° C, the reaction rate is greatly reduced, resulting in extremely poor ball shape and adhesion. If the reaction temperature is too high, energy is wasted and meaningless. Comparative Example 3

[0115] Based on the solution of Example 1, only the temperature of high temperature carbonization was changed to 900°C. The appearance of the resin after carbonization was as follows: Figure 14 As shown in the figure, it can be seen that the temperature of high-temperature carbonization is too high, and the sphere overflows and cracks. Comparative Example 4

[0116] Based on the scheme of Example 1, only the heating rate in the activation stage of 340℃~360℃ was changed to 10℃ / min. The appearance of the obtained spherical porous carbonized resin was as follows: Figure 15 It can be seen that when the heating rate in the activation stage of 340℃~360℃ is too fast, KOH reaches the boiling point and expands violently, releasing a large amount of gas, while the external accelerated curing prevents the internal gas from overflowing in time, resulting in a closed-cell structure.

[0117] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing an 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin, comprising the following steps: 8-hydroxyquinoline, phenol, formaldehyde, a reaction solvent, and a catalyst are mixed to obtain a reaction phase; the reaction solvent is ethylene glycol monomethyl ether; the molar ratio of 8-hydroxyquinoline, phenol, and formaldehyde is 1:(0.5-6):(1.75-10); Mixing a dispersion medium and a dispersant to obtain a continuous phase; the dispersion medium is liquid paraffin and / or 1,2-dichloroethane; the dispersant is span-80, or a mixture of span-80 and tween-85; The continuous phase is added to the reaction phase, and reverse phase suspension polymerization is carried out under stirring to obtain a spherical resin precursor; the reverse phase suspension polymerization temperature is 75-120°C; Carbonizing the spherical resin precursor at high temperature to obtain a carbonized resin; The programmed temperature rising process of the high temperature carbonization comprises: In air atmosphere, heat from room temperature to 250~300℃ at a heating rate of 2~5℃ / min and hold for 1~3h; Under an inert protective atmosphere, continue to heat up to 700~800℃ at a heating rate of 3~6℃ / min and keep warm for 2~3h; The carbonized resin is placed in a strong alkaline solution, soaked, taken out, and activated at high temperature to obtain an 8-hydroxyquinoline chelate resin-based spherical porous carbonized resin; The programmed temperature rising process of the high temperature activation comprises: Under an inert protective atmosphere, heat from room temperature to 340-360°C at a heating rate of 4-6°C / min and hold for 20-50 min. Under an inert protective atmosphere, continue to heat up to 800~1000℃ at a heating rate of 8~12℃ / min and keep warm for 1~2h.

2. The preparation method according to claim 1, characterized in that The catalyst is concentrated hydrochloric acid.

3. The preparation method according to claim 1, characterized in that The dispersant is 5‰~1% of the mass of the dispersion medium.

4. The preparation method according to claim 1, characterized in that The time of the reverse phase suspension polymerization is 5 to 10 hours.

5. The preparation method according to claim 1, characterized in that The strong base solution is a KOH solution, and the concentration of the strong base solution is 0.1-2 mol / L; The soaking time is 2 to 8 hours.

6. The 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin prepared according to any one of claims 1 to 5, wherein an N atom is originally introduced into the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin, and the specific surface area of the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin is 1000 to 1300 m 2 / g.

7. Use of the 8-hydroxyquinoline type chelate resin-based spherical porous carbonized resin according to claim 6 in the fields of adsorption separation, functional catalysis or blood perfusion.

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