A waste water derived micrometer-sized flower-like phenolic resin and a method for preparing the same

Abstract

The present application relates to waste resource utilization and new material preparation technical field, specifically relates to a kind of Lan carbon wastewater derived flower-like phenolic resin microspheres and preparation method thereof, phenolic resin is pickled, and pretreated phenolic resin is obtained;The ethanol dispersion liquid of pretreated phenolic resin is stirred and mixed with melamine aqueous solution, to obtain precursor mixture;The precursor mixture is hydrothermally reacted, and aftertreatment is carried out, to obtain the Lan carbon wastewater derived flower-like phenolic resin microspheres.The present application realizes the resource utilization of high value of Lan carbon wastewater, preparation process is simple, repeatability is good, and the prepared microspheres have unique flower-like morphology, and have wide application prospect in adsorption, catalytic carrier and energy storage and other fields.

Description

Technical Field

[0001] This invention relates to the field of waste resource utilization and new material preparation technology, specifically to a flower-shaped phenolic resin microsphere derived from semi-coke wastewater and its preparation method. Background Technology

[0002] The semi-coke wastewater produced by low-temperature pyrolysis of coal contains a large amount of phenolic compounds. These compounds are complex in composition, highly toxic, and difficult to degrade, and direct discharge would cause enormous pollution to the ecological environment. Traditional wastewater treatment processes are costly and not economically viable. In recent years, using phenolic substances from semi-coke wastewater as raw materials to prepare phenolic resins through condensation reactions, thus achieving "waste treatment and turning waste into treasure," has become a research hotspot in this field.

[0003] However, primary phenolic resins directly prepared from semi-coke wastewater often suffer from problems such as high impurity levels and irregular morphology. Among various material morphologies, flower-like micro / nano structures exhibit excellent performance in environmental adsorption, catalyst support, and electrochemical energy storage due to their interconnected nanosheets, abundant pore structure, and extremely high specific surface area. However, the process for preparing microspheres with regular flower-like morphologies from phenolic resins derived from semi-coke wastewater is still immature. This immaturity mainly stems from the contradiction between the complex and fluctuating composition of semi-coke wastewater and the low tolerance for error in controlling the morphology of microspheres. Even after pretreatment, semi-coke wastewater inevitably contains various heterogeneous phenols, polycyclic aromatic hydrocarbons, or trace amounts of inorganic salts in its derived phenolic resin. These impurities severely interfere with the copolymerization nucleation and molecular self-assembly kinetics of melamine and phenolic resin during the hydrothermal reaction. This leads to unstable self-assembly driving forces in microspheres, resulting in poor batch-to-batch morphology reproducibility, irregular flower-like structures, and excessively wide particle size distribution, making it difficult to achieve precise quality construction in scale-up production. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater. Using phenolic resin derived from semi-coke wastewater as raw material, impurities are effectively removed through hydrofluoric acid washing pretreatment, and melamine is introduced as a morphology modifier and adjuster. Through precise control of stepwise stirring and mixing, hydrothermal reaction (preferably at 200℃ for 8 hours), and centrifugal washing and drying processes, self-assembly is successfully induced, producing flower-shaped phenolic resin microspheres with regular morphology, high specific surface area, and abundant pore structure. This preparation method not only effectively realizes the resource utilization of semi-coke wastewater but also successfully prepares resin microspheres with a unique flower-shaped structure, showing broad application prospects in related fields.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater includes the following steps: The phenolic resin was acid-washed to obtain pretreated phenolic resin.

[0006] The ethanol dispersion of phenolic resin and the aqueous solution of melamine were mixed by stirring to obtain a precursor mixture.

[0007] The precursor mixture was subjected to a hydrothermal reaction and then post-processed to obtain the flower-shaped phenolic resin microspheres derived from semi-coke wastewater.

[0008] The mass ratio of pretreated phenolic resin to melamine is 8:15~25.

[0009] The hydrothermal reaction temperature is 180℃~200℃, and the reaction time is 8h~10h.

[0010] In a preferred embodiment of the present invention, the phenolic resin dispersion is prepared by mixing and stirring pretreated phenolic resin with ethanol; the melamine aqueous solution is prepared by heating and stirring melamine with water; the mixing and stirring time is 20-30 min, the stirring temperature is 20-25°C; the heating and stirring temperature is 50-60°C, and the heating and stirring time is 20-30 min.

[0011] In a preferred embodiment of the present invention, the pickling agent is any one of hydrochloric acid, phosphoric acid and hydrofluoric acid, and the concentration of the pickling agent is 1 g / L to 1.15 g / L.

[0012] In a preferred embodiment of the present invention, the hydrothermal reaction temperature is 200°C and the reaction time is 8 hours.

[0013] In a preferred embodiment of the present invention, the stirring time during mixing is 20-30 minutes.

[0014] In a preferred embodiment of the present invention, the post-treatment is centrifugal washing and drying. The specific steps of centrifugal washing are as follows: washing with water and anhydrous ethanol 3 to 5 times in sequence; the drying temperature is 80℃ to 100℃ and the drying time is 10h to 12h.

[0015] Another objective is to obtain flower-shaped phenolic resin microspheres derived from semi-coke wastewater using the aforementioned preparation method.

[0016] The semi-coke wastewater-derived flower-shaped phenolic resin microspheres of the present invention have a flower-like morphology assembled by cross-linking of nanosheets, and the nanosheets form an open multi-level porous structure.

[0017] Compared with the prior art, the beneficial effects of the present invention are: This invention uses phenolic resin derived from semi-coke wastewater as raw material. Impurities are effectively removed through acid washing pretreatment, and melamine is introduced as a morphology regulator and modifier. By precisely controlling stepwise stirring and mixing, hydrothermal reaction, and centrifugal washing and drying processes, self-assembly is successfully induced to prepare flower-like phenolic resin microspheres with regular morphology, high specific surface area, and abundant pore structure. In the preparation method of this invention, the amount of melamine added and the temperature and time of the hydrothermal reaction are the most important. The amount of melamine added and the temperature and time of the hydrothermal reaction are key parameters for controlling the microstructure and properties of the material. Melamine, as a nitrogen source and structure directing agent, directly determines the assembly density of the nanosheets and the integrity of the flower-like morphology. The temperature (180℃~200℃) and time (8h~10h) of the hydrothermal reaction regulate the copolymerization rate and nucleation growth kinetics of the phenolic resin and melamine, ensuring that the nanosheets can be uniformly cross-linked and oriented, thereby forming microspheres with an open, multi-level porous structure. Compared with existing technologies, the improvement of this technology lies in the controlled hydrothermal self-assembly induced by a specific concentration of melamine. This not only realizes the high-value resource utilization of waste phenolic resin from semi-coke wastewater, but also significantly improves the specific surface area and pore accessibility of the material through the "flower-like" construction of nanosheets at the micron level. This solves the defects of low porosity and limited mass transfer of traditional phenolic resin particles, thus exhibiting superior activity and loading performance in adsorption or catalytic applications. Attached Figure Description

[0018] Figure 1 A flowchart illustrating the preparation method of flower-shaped phenolic resin microspheres derived from semi-coke wastewater.

[0019] Figure 2 SEM image of the preparation of flower-shaped phenolic resin microspheres derived from semi-coke wastewater. Detailed Implementation

[0020] The following detailed description, in conjunction with embodiments of the present invention and accompanying drawings, provides a clear and complete illustration of the technical solutions in these embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0021] It should be noted that all technical terms used in this invention are for the purpose of describing specific embodiments only and are not intended to limit the scope of protection of this invention. Unless otherwise specified, all raw materials, reagents, instruments and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0022] Phenolic resins possess excellent physicochemical stability and tunable cross-linking structures, making them ideal precursors for preparing high-performance micro / nanomaterials. On the other hand, semi-coke wastewater generated from low-temperature pyrolysis of coal contains a large amount of phenolic compounds that are difficult to degrade, and there is no mature treatment process, causing significant environmental pollution. This invention uses semi-coke wastewater as a raw material to recover and utilize the phenolic substances within it to synthesize phenolic resins, achieving high-value-added resource utilization of industrial wastewater. The effects of pretreatment and hydrothermal conditions on the morphology and structure of the resin microspheres were investigated, and semi-coke wastewater-derived flower-like phenolic resin microspheres with high specific surface area and regular morphology were prepared.

[0023] Micro- and nano-sized polymer resin materials have attracted much attention in fields such as adsorption, catalytic support, and energy storage, and have become one of the most promising basic materials due to their low cost and structural designability. Although conventionally synthesized phenolic resin microspheres usually have a smooth, solid structure with a relatively low specific surface area, this can be improved by morphology control and heteroatom doping. Therefore, this invention uses hydrofluoric acid to pretreat wastewater-derived phenolic resin, while adding melamine as a morphology regulator and modifier to induce self-assembly and prepare flower-like phenolic resin microspheres, thereby increasing the porosity and active sites of the material and improving its overall application performance.

[0024] The green, high-value-added transformation of waste is currently the richest research resource in the fields of environmental governance and materials science. It is also a major approach to solving pollution emissions from industrial production and daily life. With the increasing depletion of traditional resources and environmental pollution problems, the activation, modification, and utilization of industrial wastewater have attracted growing attention. This invention uses phenolic resin derived from semi-coke wastewater and melamine as raw materials. Through a highly matched synthesis process involving ethanol / deionized water stirring and mixing, high-temperature hydrothermal reaction, and multiple water / ethanol centrifugal washings, the final product is dried and shaped, improving the integrity and stability of the flower-shaped microspheres in their microstructure.

[0025] Example 1 A method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater, such as... Figure 1 As shown, it includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0026] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0027] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0028] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0029] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0030] Example 2 A method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater, such as... Figure 1 As shown, it includes the following steps: (1) Phenolic resin pretreated with hydrochloric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrochloric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0031] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0032] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0033] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0034] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0035] Example 3 A method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater, such as... Figure 1 As shown, it includes the following steps: (1) Phosphoric acid pretreatment of phenolic resin The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute phosphoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0036] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0037] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0038] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0039] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0040] Example 4 A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (0) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0041] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.10g of phenolic resin and 0.16g of melamine that have been pretreated in step (1) for later use.

[0042] (3) Preparation of mixed solution Add 0.10 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.16 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0043] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air drying oven. The oven was heated to 180 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0044] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0045] Example 5 A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0046] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.12g of phenolic resin and 0.18g of melamine that have been pretreated in step (1) for later use.

[0047] (3) Preparation of mixed solution Add 0.12 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.18 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0048] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0049] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0050] Example 6 A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0051] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0052] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0053] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 180 °C at a rate of 5 °C / min and kept at that temperature for 10 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0054] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0055] Comparative Example 1 (without melamine) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreatment with hydrofluoric acid: Phenolic resin obtained from semi-coke wastewater was immersed in dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides on the resin surface; then deionized water was added to centrifuge tubes and repeatedly rinsed with a centrifuge until neutral.

[0056] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of pretreated phenolic resin for later use.

[0057] (3) Preparation of mixed solution Add the 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion. (4) Hydrothermal reaction The phenolic resin ethanol dispersion obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0058] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0059] Comparative Example 2 (Phenolic resin without pretreatment) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of untreated phenolic resin and 0.15g of melamine for later use.

[0060] (2) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (1) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0061] (3) Hydrothermal reaction The phenolic resin ethanol dispersion obtained in step (2) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0062] (4) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0063] Comparative Example 3 (changing the amounts of phenolic resin and melamine) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0064] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.10g of phenolic resin and 0.18g of melamine that have been pretreated in step (1) for later use.

[0065] (3) Preparation of mixed solution Add 0.10 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.18 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0066] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0067] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0068] Comparative Example 4 (Lowering the hydrothermal reaction temperature) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0069] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0070] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0071] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 160 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0072] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0073] Comparative Example 5 (Increasing the hydrothermal reaction temperature) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0074] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0075] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0076] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 220 °C at a rate of 5 °C / min and kept at that temperature for 8 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0077] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0078] Comparative Example 6 (Reducing Hydrothermal Reaction Time) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0079] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0080] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0081] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 6 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0082] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0083] Comparative Example 7 (increasing hydrothermal reaction time) A method for preparing flower-shaped phenolic resin microspheres derived from semi-coke wastewater includes the following steps: (1) Phenolic resin pretreated with hydrofluoric acid The phenolic resin obtained from the extraction of semi-coke wastewater was immersed in a dilute hydrofluoric acid solution and ultrasonically treated for 10 minutes to fully remove inorganic impurities and metal oxides from the resin surface; then deionized water was added to the centrifuge tube and the tube was repeatedly rinsed with a centrifuge until neutral.

[0084] (2) Weighing raw materials Using a precision electronic balance, accurately weigh 0.08g of phenolic resin and 0.15g of melamine that have been pretreated in step (1) for later use.

[0085] (3) Preparation of mixed solution Add 0.08 g of phenolic resin weighed in step (2) to an appropriate amount of anhydrous ethanol, and stir magnetically for 20 min at room temperature to fully disperse the phenolic resin in the ethanol to obtain a phenolic resin ethanol dispersion; at the same time, add 0.15 g of melamine to an appropriate amount of deionized water, and stir magnetically for 20 min at 60℃ in a water bath to fully dissolve the melamine to obtain a melamine aqueous solution; mix the above phenolic resin ethanol dispersion with the melamine aqueous solution, and continue to stir magnetically for 20 min at room temperature to fully mix and obtain a uniform mixture.

[0086] (4) Hydrothermal reaction The homogeneous mixture obtained in step (3) was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel high-pressure reactor, sealed, and placed in a pre-programmed forced-air drying oven. The oven was heated to 200 °C at a rate of 5 °C / min and kept at that temperature for 11 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature.

[0087] (5) Processing and drying Remove the reaction vessel, open it, transfer the product to a centrifuge tube, centrifuge at 9000 rpm for 5 min, discard the supernatant, add deionized water to redisperse, and repeat the water washing and centrifugation operation 3 times; then replace with anhydrous ethanol, and perform ethanol washing and centrifugation operation 3 times in the same way; finally, place the obtained solid product in an 80℃ forced-air drying oven for 12 h, and after taking it out, the flower-shaped phenolic resin microsphere product is obtained.

[0088] Results Analysis Figure 2 The image shows a SEM image of the fabricated flower-like phenolic resin microspheres derived from semi-coke wastewater. The SEM image reveals a regular, spherical, flower-like morphology, indicating that these microspheres are formed by the cross-linking and self-assembly of numerous extremely thin nanosheets. Based on the 10 μm scale bar in the image, the diameter of the microspheres is estimated to be between 5 and 10 μm, exhibiting good size uniformity. This open porous structure composed of nanosheets not only significantly increases the specific surface area of ​​the material but also provides abundant active sites for ion diffusion and chemical reactions, suggesting excellent application potential in electrochemical energy storage, catalysis, or environmental purification.

[0089] In summary, melamine acts as a morphology regulator and modifier in the preparation process. Without melamine, it is impossible to form microspheres with a unique flower-like structure through induced self-assembly, making it difficult to obtain high specific surface area, abundant pore structure, and active sites. The main function of hydrofluoric acid washing is to remove inorganic impurities and metal oxides from the surface of phenolic resin derived from semi-coke wastewater. Omitting the hydrofluoric acid washing step will result in more residual impurities in the raw materials, thus affecting the purity and application performance of the final product. Temperature is the core parameter controlling the structure formation. If the temperature deviates from the optimal 200℃, 180℃ may lead to incomplete reaction and insufficient formation of the flower-like morphology; while 220℃ may lead to overgrowth or collapse of the structure. The reaction time determines the integrity of the microsphere growth. If the time is less than 8 hours, the nanosheets may not develop fully; if the time is too long, it will affect the stability of the microstructure and even cause morphological damage.

[0090] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of the invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this invention.

[0091] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater, characterized in that, Includes the following steps: Phenolic resin is acid-washed to obtain pretreated phenolic resin; The ethanol dispersion of pretreated phenolic resin was mixed with melamine aqueous solution by stirring to obtain a precursor mixture. The precursor mixture was subjected to a hydrothermal reaction and then post-processed to obtain the flower-shaped phenolic resin microspheres derived from semi-coke wastewater. The mass ratio of pretreated phenolic resin to melamine is 8:15~25; The hydrothermal reaction temperature is 180℃~200℃, and the reaction time is 8h~10h.

2. The preparation method according to claim 1, characterized in that, The pickling reagent is any one of hydrochloric acid, phosphoric acid, and hydrofluoric acid, and the concentration of the pickling reagent is 1 g / L to 1.15 g / L.

3. The method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater according to claim 1, characterized in that, The hydrothermal reaction was carried out at a temperature of 200℃ for 8 hours.

4. The method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater according to claim 1, characterized in that, The phenolic resin dispersion is prepared by mixing and stirring pretreated phenolic resin with ethanol; the melamine aqueous solution is prepared by heating and stirring melamine with water; the heating and stirring temperature is 50℃~60℃, and the heating and stirring time is 20min~30min.

5. The method for preparing flower-like phenolic resin microspheres derived from semi-coke wastewater according to claim 1, characterized in that, The post-treatment involves centrifugal washing and drying. The specific steps of centrifugal washing are as follows: washing with water and anhydrous ethanol 3 to 5 times each; the drying temperature is 80℃ to 100℃ and the drying time is 10h to 12h.

6. A flower-shaped phenolic resin microsphere derived from semi-coke wastewater, prepared by the method described in claims 1-5.

7. The semi-coke wastewater-derived flower-shaped phenolic resin microspheres according to claim 6, characterized in that, The microspheres have a flower-like morphology formed by the cross-linking and assembly of nanosheets, with open hierarchical pore structures formed between the nanosheets.

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