Polyhydroxy phenolic crosslinking agents, methods of making and using the same

Abstract

The application relates to a polyhydroxy phenolic crosslinking agent and a preparation method and application method thereof, the preparation method comprising the following steps: completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution; continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain the polyhydroxy phenolic crosslinking agent. The polyhydroxy phenolic crosslinking agent is obtained by introducing a hydroxymethyl group into the molecular structure of the phenol through the paraformaldehyde, so that the phenol molecule has multiple active groups which can be crosslinked, thereby providing the polyhydroxy phenolic crosslinking agent for the transformation of petrochemical aromatic-rich oil into high-value condensed polycyclic polynuclear aromatic resin. The polyhydroxy phenolic crosslinking agent can be synthesized through a one-pot method, the preparation process has the advantages of low raw material cost, mild reaction condition, high product yield, easy industrial production and the like, and the polyhydroxy phenolic crosslinking agent can controllably introduce oxygen-containing functional groups into the resin to prepare condensed polycyclic polynuclear aromatic resins with different oxygen contents, and the utilization value of the condensed polycyclic polynuclear aromatic resins is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of heavy oil processing, in particular to a multi-hydroxyl phenolic crosslinking agent and a preparation method and application method thereof. BACKGROUND

[0002] With the development of petrochemical industry, the positions of ethylene cracking process and catalytic cracking process in petrochemical industry are becoming more and more important. These two types of processes will produce ethylene tar (about 15% of ethylene production capacity) and catalytic cracking diesel (about 30% of diesel production capacity) as by-products during operation. At present, the refining industry generally uses ethylene tar as heavy fuel, which not only causes environmental problems such as greenhouse effect and air pollution, but also is a serious waste of aromatic resources in it. Catalytic cracking diesel is mainly converted into light aromatic hydrocarbons and benzene-toluene-xylene mixture through hydrogenation process for utilization, but these processes are high in energy consumption and low in economic benefit. Whether it is ethylene tar or catalytic cracking diesel, it is urgent to find a way to efficiently convert the aromatic components in it into high value-added chemical products to improve the economic benefit of the petroleum refining industry and perfect the process of petroleum processing.

[0003] Ethylene tar and catalytic cracking diesel both belong to aromatic-rich oil, which has strong electrophilic substitution reactivity, and can be converted into condensed polymers aromatic (COPNA) resin by electrophilic substitution reaction with the help of crosslinking agent. This resin was discovered by Japanese scientist Tatsuo Ohtani in the mid-1980s, and has good processability, good carbon material infiltration and self-lubricity, and is considered to be an excellent precursor of carbon material. As one of the most critical factors in the preparation process of COPNA resin, the commonly used crosslinking agents include p-xylyleneglycol, trioxane, benzaldehyde, p-tolualdehyde, divinylbenzene, among which p-xylyleneglycol has better crosslinking effect than the other four crosslinking agents, and can obtain COPNA resin with higher yield and good heat resistance; however, p-xylyleneglycol as a crosslinking agent also has many shortcomings, including high cost, difficulty in modification of the obtained COPNA resin due to lack of polar functional groups, and disadvantageous storage of sodium ions due to low interlayer spacing of the synthesized resin-based carbon material, etc.

[0004] Therefore, it is urgent to develop a crosslinking agent with low cost, rich in polar functional groups and capable of improving the structure and performance of the corresponding resin-based carbon material, so as to improve the utilization value of COPNA resin. SUMMARY

[0005] The present application aims to provide a multi-hydroxyl phenolic crosslinking agent and a preparation method and application method thereof, so as to provide a crosslinking agent with low cost, rich in polar functional groups and capable of improving the structure and performance of the corresponding resin-based carbon material, thereby improving the utilization value of COPNA resin.

[0006] The embodiment of the present application provides a preparation method of a multi-hydroxy phenolic crosslinking agent, which comprises: completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution; continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain the multi-hydroxy phenolic crosslinking agent.

[0007] The phenol comprises one or more of phenol, o-dihydroxybenzene, p-dihydroxybenzene, m-dihydroxybenzene, m-trihydroxybenzene, p-tert-butyl phenol, p-t-octyl phenol, p-methyl phenol, gallic acid, hydrolyzed tannin and condensed tannin.

[0008] The mass ratio of the paraformaldehyde, the phenol and the alkaline solution is (5-20):(10-30):(50-85).

[0009] The predetermined temperature is 25-70 DEG C, and the predetermined time is 1-48 h.

[0010] The alkaline solution is an aqueous solution of any one or a combination of multiple of ammonia, sodium hydroxide and potassium hydroxide, and the mass concentration of the alkaline solution is 2%-40%.

[0011] The completely dissolving the paraformaldehyde and the phenol in the alkaline solution to form the mixed solution comprises: adding the paraformaldehyde and the phenol into the alkaline solution, heating to the predetermined temperature until the paraformaldehyde and the phenol are completely dissolved to form the mixed solution.

[0012] The embodiment of the present application further provides a multi-hydroxy phenolic crosslinking agent, which is prepared by any one of the preparation methods of the multi-hydroxy phenolic crosslinking agent.

[0013] The embodiment of the present application further provides a use method of the multi-hydroxy phenolic crosslinking agent, which comprises: performing a condensation reaction on the multi-hydroxy phenolic crosslinking agent and aromatic hydrocarbon-rich oil under the action of a catalyst to obtain a condensed polycyclic polynuclear aromatic resin.

[0014] The performing the condensation reaction on the multi-hydroxy phenolic crosslinking agent and the aromatic hydrocarbon-rich oil under the action of the catalyst to obtain the condensed polycyclic polynuclear aromatic resin comprises: stirring and mixing the multi-hydroxy phenolic crosslinking agent, the aromatic hydrocarbon-rich oil and the catalyst uniformly at a first predetermined temperature, then heating to a second predetermined temperature under stirring, the second predetermined temperature is higher than the first predetermined temperature, continuously stirring and reacting at the second predetermined temperature for a first predetermined time to obtain the condensed polycyclic polynuclear aromatic resin.

[0015] The aromatic hydrocarbon-rich oil comprises at least one of ethylene tar, ethylene tar heavy component, ethylene tar light component, coated pitch residual material and catalytic cracking diesel oil; and the catalyst comprises at least one of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid and perchloric acid.

[0016] The polyhydroxyphenol crosslinking agent, its preparation method, and its application method provided in this application involve completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution, and then continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain the polyhydroxyphenol crosslinking agent. This achieves the introduction of hydroxymethyl groups into the molecular structure of phenol through paraformaldehyde, giving the phenol molecule multiple crosslinkable active groups, thus obtaining a polyhydroxyphenol crosslinking agent. This provides a polyhydroxyphenol crosslinking agent suitable for converting petrochemical aromatic oils such as ethylene tar and catalytic cracking diesel into condensed polycyclic aromatic hydrocarbon resins. Furthermore, this polyhydroxyphenol crosslinking agent can be synthesized in a one-pot process, and its preparation process has advantages such as low raw material cost, mild reaction conditions, high product yield, and ease of industrial production. Furthermore, oxygen-containing functional groups can be controllably introduced into the resin to prepare condensed polycyclic aromatic hydrocarbon resins with different oxygen contents, which can effectively improve the metal ion storage capacity of condensed polycyclic aromatic hydrocarbon resin-based carbon materials. Therefore, the condensed polycyclic aromatic hydrocarbon resin can be used as a high-quality precursor for electrode materials, thus enhancing the utilization value of condensed polycyclic aromatic hydrocarbon resins. Attached Figure Description

[0017] The technical solution and other beneficial effects of this application will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.

[0018] Figure 1 This is a schematic flowchart of the preparation method of the polyhydroxyphenol crosslinking agent provided in the embodiments of this application;

[0019] Figure 2 This is a schematic flowchart illustrating the application method of the polyhydroxyphenol crosslinking agent provided in the embodiments of this application. Detailed Implementation

[0020] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are for illustrative purposes only and do not limit the scope of the application. Similarly, the following embodiments are only some, not all, embodiments of the present application, and all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of the present application.

[0021] In the following description of this application, "some embodiments" are referred to, which describe a subset of all possible embodiments. However, it is understood that "some embodiments" may be the same subset or different subset of all possible embodiments, and may be combined with each other without conflict.

[0022] In the following description of this application, the terms "first, second, third" are used merely to distinguish similar objects and do not represent a specific ordering of objects. It is understood that "first, second, third" may be interchanged in a specific order or sequence where permitted, so that the embodiments of this application described herein can be implemented in an order other than that illustrated or described herein.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In the event of any conflict, this specification shall prevail. The terminology used herein is for the purpose of describing embodiments of this application only and is not intended to limit this application.

[0024] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0025] In the following embodiments, the properties of the feedstock oils such as ethylene tar and catalytic cracked diesel oil used can be as shown in Table 1 below.

[0026] Table 1

[0027]

[0028] The following detailed description is based on specific embodiments. It should be noted that the sequence numbers of the embodiments are not intended to limit the preferred order of the embodiments.

[0029] Please see Figure 1 , Figure 1 This is a schematic flowchart of the preparation method of the polyhydroxyphenol crosslinking agent provided in the embodiments of this application. The specific process of the preparation method of the polyhydroxyphenol crosslinking agent can be as follows:

[0030] Step S11. Completely dissolve paraformaldehyde and phenol in an alkaline solution to form a mixed solution.

[0031] The phenol may include one or more of the following: phenol, catechol, hydroquinone, resorcinol, phloroglucinol, p-tert-butylphenol, p-tert-octylphenol, p-methylphenol, gallic acid, hydrolyzed tannin, and condensed tannin. For example, it may specifically be p-tert-butylphenol, resorcinol, gallic acid, or phenol.

[0032] The alkaline solution can be an aqueous solution of any one or more combinations of ammonia, sodium hydroxide, and potassium hydroxide, specifically, an aqueous solution of ammonia, sodium hydroxide, or potassium hydroxide. Furthermore, the mass concentration of the alkaline solution can be from 2% to 40%, specifically, 2%, 5%, 15%, 20%, 25%, 30%, 35%, or 38%. In some specific examples, the alkaline solution can be a 5% sodium hydroxide aqueous solution, or a 20% potassium hydroxide aqueous solution, or a 30% ammonia aqueous solution, or a 38% sodium hydroxide aqueous solution, or a 25% potassium hydroxide aqueous solution, or a 15% sodium hydroxide aqueous solution.

[0033] In some embodiments, in step S11 above, the mass ratio of paraformaldehyde, phenol, and alkaline solution can be (5-20):(10-30):(50-85), wherein the mass ratio of paraformaldehyde to alkaline solution can be (4.17-23.75):50, and the mass ratio of phenol to alkaline solution can be (8.950-37.495):50.

[0034] Step S12. The mixed solution is continuously stirred at a predetermined temperature for a predetermined time to obtain a polyhydroxyphenol crosslinking agent.

[0035] Specifically, after completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution, the resulting mixed solution can be continuously stirred and reacted at a predetermined temperature for a predetermined time to obtain a polyhydroxyphenolic crosslinking agent. The predetermined temperature can be 25–70°C, for example, 25°C, 30°C, 40°C, 45°C, 50°C, or 60°C. The predetermined time can be 1–48 hours, for example, 5 hours, 8 hours, 12 hours, 18 hours, 24 hours, or 48 hours.

[0036] In some embodiments, step S11 may specifically include: adding paraformaldehyde and phenol to an alkaline solution, heating to a predetermined temperature, until paraformaldehyde and phenol are completely dissolved to form a mixed solution.

[0037] Furthermore, in specific implementation, an alkaline solution can be prepared and added to a three-necked flask equipped with a thermometer, a stirring device, and a reflux device. Then, paraformaldehyde and phenol are weighed and added to the three-necked flask. The mixture is heated to a predetermined temperature while stirring. Once the reaction raw materials (i.e., paraformaldehyde and phenol) have been completely dissolved, the timer is started. The mixture is stirred under reflux and reacted at a constant temperature for a predetermined time. After the reaction is completed, the reactants are cooled to room temperature to obtain a polyhydroxyphenol crosslinking agent.

[0038] It should be noted that the polyhydroxyphenolic crosslinking agent obtained after step S12 is prepared by attaching hydroxymethyl groups to phenol with paraformaldehyde, thereby giving the phenol molecule multiple crosslinkable active groups (i.e., hydroxyl groups). In other words, the polyhydroxyphenolic crosslinking agent obtained after step S12 is a phenolic compound containing multiple crosslinking functional groups (i.e., hydroxyl groups), and this phenolic compound is a polyol, which allows it to act on aromatic hydrocarbon-rich oil molecules such as ethylene tar and catalytic cracking diesel to synthesize condensed polycyclic and polynuclear aromatic hydrocarbon resins containing oxygen-containing functional groups.

[0039] Furthermore, in the embodiments of this application, the content of oxygen-containing functional groups in the prepared polyhydroxyphenol crosslinking agent can be controlled by adjusting the reaction conditions (e.g., reaction raw materials, alkaline solution, predetermined temperature, predetermined time, etc.), thereby enabling the control of the content of oxygen-containing functional groups in the condensed polycyclic polynuclear aromatic hydrocarbon resin prepared by the polyhydroxyphenol crosslinking agent. This effectively enhances the metal ion storage capacity of the resin-based carbon material, making the obtained resin product a high-quality precursor for electrode materials.

[0040] In addition, this application can utilize a one-pot method to synthesize polyhydroxyphenol crosslinking agents, thereby enabling the preparation process of polyhydroxyphenol crosslinking agents to have advantages such as low raw material cost, mild reaction conditions, high product yield, and ease of industrial production.

[0041] It should be noted that among the existing technologies for preparing COPNA resin using polycyclic aromatic hydrocarbons:

[0042] Chinese patent document (CN110283341B) discloses a method for converting polycyclic aromatic hydrocarbons in petroleum asphalt and / or FCC slurry into COPNA resin using plant starches such as corn starch and potato starch as crosslinking agents and protic acid as a catalyst. The resulting B-stage COPNA resin has a high β-resin content and high viscosity, while the C-stage petroleum-based COPNA resin has a high carbon residue value. The plant starches used are rich in hydroxyl functional groups, resulting in good crosslinking effect. This method can significantly reduce the preparation cost of COPNA resin and expand the application range of COPNA resin.

[0043] Chinese patent document (CN106565938A) discloses the preparation of a high-carbon-residue heat-resistant resin by using ethylene tar recalcification fraction as raw material, dialdehyde starch as crosslinking agent, and lignin sulfonic acid as catalyst.

[0044] Chinese patent document (CN105419726B) discloses the preparation of COPNA resin using coal tar pitch powder as raw material, terephthalic acid as crosslinking agent and p-toluenesulfonic acid as catalyst, and the preparation of COPNA resin binder by mixing boron carbide powder and chopped carbon fiber as modified fillers with COPNA resin.

[0045] Chinese patent document (CN102942769A) discloses the preparation of high-strength COPNA resin-based polystyrene composite material by using aromatic hydrocarbon-rich substances as raw materials, poly-alkaloids (terephthalaldehyde or paraformaldehyde) or polyols (terephthalic acid) as crosslinking agents, p-toluenesulfonic acid as catalyst, synthesizing COPNA resin as matrix, and polystyrene as reinforcing component.

[0046] Chinese patent document (CN102453227B) discloses the preparation of COPNA resin using heavy aromatic oil as raw material and one or more of the following compounds having an ethylene structure (at least one of polyethylene, ethylene urea and ethyleneimine and their derivatives), phenol (naphthol and its derivatives) and aldehyde (formaldehyde, acetaldehyde and their derivatives) as crosslinking agents, under the action of an acidic catalyst (hydrochloric acid, sulfuric acid, p-toluenesulfonic acid).

[0047] The crosslinking agents used in the aforementioned patent documents for preparing COPNA resin include terephthalic acid, terephthalaldehyde, trioxymethylene, formaldehyde, polystyrene, acetaldehyde, and starch. However, none of these patent documents involve the use of phenols and biomass phenols converted into polyols for converting petrochemical aromatic oils such as ethylene tar (including light and heavy fractions) and catalytic cracking diesel into COPNA resin. Therefore, compared with existing technologies for preparing COPNA resin using polycyclic aromatic hydrocarbons, this application provides a new crosslinking agent (i.e., the aforementioned polyhydroxyphenolic crosslinking agent) that can be used to convert petrochemical aromatic oils such as ethylene tar (including light and heavy fractions) and catalytic cracking diesel into COPNA resin. This new crosslinking agent is inexpensive, rich in polar functional groups, and can improve the structural properties of the corresponding resin-based carbon materials. This solves the technical problem of insufficient metal ion storage capacity in existing COPNA resin-based carbon materials, thereby enhancing the utilization value of COPNA resin.

[0048] Furthermore, for ease of understanding, this application will be further described in detail below through six specific embodiments (i.e., Embodiment 1, Embodiment 2, Embodiment 3, Embodiment 4, Embodiment 5 and Embodiment 6).

[0049] Example 1

[0050] In Example 1, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0051] Prepare a 5% sodium hydroxide aqueous solution and add 100g of the prepared 5% sodium hydroxide aqueous solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux evaporator. Then weigh 8.333g of paraformaldehyde and 41.667g of p-tert-butylphenol and add them to the three-necked flask. Heat the mixture to 60°C with stirring. After observing that the reaction raw materials (i.e., paraformaldehyde and p-tert-butylphenol) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 5 hours. After the reaction is completed, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0052] Example 2

[0053] In Example 2, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0054] Prepare a 20% potassium hydroxide aqueous solution and add 50g of the prepared solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux evaporator. Then, weigh 7.692g of paraformaldehyde and 18.795g of resorcinol and add them to the flask. Heat the mixture to 40°C with stirring. Once the reactants (paraformaldehyde and resorcinol) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 12 hours. After the reaction is complete, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0055] Example 3

[0056] In Example 3, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0057] Prepare a 30% ammonia solution and add 50g of the prepared 30% ammonia solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux evaporator. Then weigh 22.500g of paraformaldehyde and 37.495g of p-tert-butylphenol and add them to the three-necked flask. Heat the mixture to 50°C with stirring. After observing that the reactants (i.e., paraformaldehyde and p-tert-butylphenol) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 18 hours. After the reaction is completed, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0058] Example 4

[0059] In Example 4, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0060] Prepare a 38% sodium hydroxide aqueous solution and add 50g of the prepared 38% sodium hydroxide aqueous solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux reflux device. Then weigh 23.75g of paraformaldehyde and 26.897g of gallic acid and add them to the three-necked flask. Heat the mixture to 45°C with stirring. After observing that the reaction raw materials (i.e., paraformaldehyde and gallic acid) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 8 hours. After the reaction is completed, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0061] Example 5

[0062] In Example 5, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0063] Prepare a 25% potassium hydroxide aqueous solution and add 50g of the prepared solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux evaporator. Then, weigh 21.429g of paraformaldehyde and 8.950g of phenol and add them to the flask. Heat the mixture to 25°C with stirring. Once the reactants (paraformaldehyde and phenol) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 48 hours. After the reaction is complete, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0064] Example 6

[0065] In Example 6, the specific process for preparing the polyhydroxyphenolic crosslinking agent can be as follows:

[0066] Prepare a 15% sodium hydroxide aqueous solution and add 50g of the prepared 15% sodium hydroxide aqueous solution to a three-necked flask equipped with a thermometer, a stirrer, and a reflux evaporator. Then weigh 22.222g of paraformaldehyde and 27.778g of p-tert-butylphenol and add them to the three-necked flask. Heat the mixture to 30°C with stirring. After observing that the reaction raw materials (i.e., paraformaldehyde and p-tert-butylphenol) have completely dissolved, start timing. Keep stirring under reflux and react at a constant temperature for 24 hours. After the reaction is completed, cool the reactants to room temperature to obtain the polyhydroxyphenol crosslinking agent.

[0067] As can be seen from the above, the preparation method of the polyhydroxyphenol crosslinking agent provided in this embodiment involves completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution, and then continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain the polyhydroxyphenol crosslinking agent. Thus, by introducing hydroxymethyl groups into the molecular structure of phenol through paraformaldehyde, the phenol molecule acquires multiple crosslinkable active groups, resulting in a polyhydroxyphenol crosslinking agent. This provides a polyhydroxyphenol crosslinking agent for the transformation of petrochemical aromatic oils into high-value-added condensed polycyclic and polynuclear aromatic resins. This polyhydroxyphenol crosslinking agent can be synthesized in a one-pot process, which has advantages such as low raw material cost, mild reaction conditions, high product yield, and ease of industrial production. Furthermore, it allows for the controllable introduction of oxygen-containing functional groups into the resin to obtain condensed polycyclic and polynuclear aromatic resins with different oxygen contents. This effectively enhances the metal ion storage capacity of condensed polycyclic and polynuclear aromatic resin-based carbon materials, making this condensed polycyclic and polynuclear aromatic resin a high-quality precursor for electrode materials and increasing its utilization value.

[0068] To better implement the preparation method of the polyhydroxyphenol crosslinking agent provided in the embodiments of this application, the embodiments of this application also provide a polyhydroxyphenol crosslinking agent, which is prepared by the preparation method of the polyhydroxyphenol crosslinking agent provided in any of the above embodiments.

[0069] Specifically, the polyhydroxyphenolic crosslinking agent is a phenolic compound containing multiple crosslinkable active groups (e.g., hydroxyl groups), and the phenolic compound can be specifically a polyol, thereby enabling it to act on aromatic oil molecules such as ethylene tar and catalytic cracked diesel to synthesize condensed polycyclic and polynuclear aromatic resins with high oxygen-containing functional group content.

[0070] Furthermore, it should be noted that the polyhydroxyphenol crosslinking agent in this embodiment is prepared using the preparation method of the polyhydroxyphenol crosslinking agent provided in any of the above embodiments, and therefore has all the same beneficial effects, which will not be repeated here.

[0071] Based on the polyhydroxyphenol crosslinking agent described in the above embodiments, this embodiment will further describe the application method of the polyhydroxyphenol crosslinking agent.

[0072] Please see Figure 2 , Figure 2 This is a schematic flowchart illustrating the application method of the polyhydroxyphenolic crosslinking agent provided in this application embodiment. This application method of the polyhydroxyphenolic crosslinking agent can be applied to scenarios where petrochemical aromatic oils such as ethylene tar and catalytic cracking diesel are converted into condensed polycyclic aromatic hydrocarbon resins. For example... Figure 2 As shown, the specific application process of this polyhydroxyphenol crosslinking agent can be as follows:

[0073] Step S21: The polyhydroxyphenol crosslinking agent and the aromatic oil are subjected to a condensation reaction under the action of a catalyst to obtain a condensed polycyclic and polynuclear aromatic resin.

[0074] Specifically, the polyhydroxyphenolic crosslinking agent described in any of the above embodiments of this application can be condensed with aromatic oil under the action of a catalyst to obtain a condensed polycyclic aromatic hydrocarbon resin. The aromatic oil may include at least one of ethylene tar, heavy components of ethylene tar, light components of ethylene tar, coated asphalt residues, and catalytic cracking diesel oil; for example, it may specifically be ethylene tar or catalytic cracking diesel oil. The catalyst may include at least one of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid, and perchloric acid; for example, it may specifically be p-toluenesulfonic acid.

[0075] Furthermore, in specific implementation, the polyhydroxyphenolic crosslinking agent described in any of the above embodiments can be stirred and mixed evenly with the aromatic oil and catalyst at a first predetermined temperature, and then heated to a second predetermined temperature while stirring. The second predetermined temperature is higher than the first predetermined temperature, and the reaction is continued at the second predetermined temperature for a first predetermined time to obtain a condensed polycyclic aromatic hydrocarbon resin. The first predetermined temperature can be 90°C. The second predetermined temperature can be 180°C or 200°C. The first predetermined time can be 5 hours or 10 hours.

[0076] In some embodiments, such as Figure 2 As shown, after step S21 above, the application method of the above-mentioned polyhydroxyphenolic crosslinking agent may further include:

[0077] Step S22. Under a protective gas atmosphere, the condensed polycyclic aromatic hydrocarbon resin is carbonized to obtain a condensed polycyclic aromatic hydrocarbon resin-based carbon material.

[0078] The protective gas can be nitrogen or argon, specifically nitrogen.

[0079] Specifically, under a protective gas atmosphere, the condensed polycyclic aromatic hydrocarbon resin obtained after step S21 is first treated at a third predetermined temperature for a second predetermined time, then heated to a fourth predetermined temperature, and then kept at the fourth predetermined temperature for a third predetermined time to obtain the condensed polycyclic aromatic hydrocarbon resin-based carbon material. The fourth predetermined temperature is higher than the third predetermined temperature; for example, the third predetermined temperature can be 300℃, and the fourth predetermined temperature can be 1200℃ or 1400℃. The second predetermined time can be 2 hours, and the third predetermined time can be 2 hours.

[0080] In some specific embodiments, such as Figure 2 As shown, after step S22 above, the application method of the above-mentioned polyhydroxyphenolic crosslinking agent may further include:

[0081] Step S23. Mix the condensed polycyclic aromatic hydrocarbon resin-based carbon material with a conductive agent and a binder, and add a solvent to obtain a slurry. Then, apply the slurry to a substrate and dry it to obtain an electrode sheet.

[0082] Specifically, the conductive agent can be a super p conductive agent (i.e., small-particle conductive carbon black). The binder can be PVDF (i.e., polyvinylidene fluoride). The solvent can be NMP (i.e., N-methylpyrrolidone). The substrate can be copper foil or aluminum foil.

[0083] Specifically, a condensed polycyclic aromatic hydrocarbon resin-based carbon material, a conductive agent, and a binder can be mixed in a mass ratio of 8:1:1 and a solvent can be added to obtain a slurry. The slurry is then uniformly coated onto a substrate and dried in a vacuum oven at 120°C for 12 hours to obtain a carbon-coated substrate. The carbon-coated substrate is then cut into negative electrode sheets with a diameter of 12 mm. The loading of the negative electrode sheet can be approximately 1–2.5 mg / cm³. 2 .

[0084] Furthermore, for ease of understanding, this application will be further explained in detail below through two specific application examples (i.e., application example 1 and application example 2).

[0085] Application Example 1

[0086] In Application Example 1, the specific procedure for applying the polyhydroxyphenolic crosslinking agent can be as follows:

[0087] Weigh 20g of the polyhydroxyphenolic crosslinking agent prepared in Example 3 above, mix it with 20g of catalytic cracking diesel oil and 1.2g of p-toluenesulfonic acid at 90°C, and then heat it to 180°C under stirring. Start timing and keep stirring under reflux. React at a constant temperature for 5 hours to obtain condensed polycyclic aromatic hydrocarbon resin.

[0088] Next, under a nitrogen atmosphere, the obtained condensed polycyclic aromatic hydrocarbon resin can be treated at 300°C for 2 hours, then heated to 1400°C and kept at 1400°C for 2 hours to obtain condensed polycyclic aromatic hydrocarbon resin-based carbon materials.

[0089] Subsequently, the obtained condensed polycyclic aromatic hydrocarbon resin-based carbon material, super p conductive agent, and PVDF are mixed in a mass ratio of 8:1:1, and NMP is added as a solvent to obtain a slurry. The slurry is then uniformly coated onto copper foil and dried in a vacuum oven at 120°C for 12 hours to obtain carbon-coated copper foil. The carbon-coated copper foil is then cut into negative electrode sheets with a diameter of 12 mm. The loading of the negative electrode sheet can be approximately 1–2.5 mg / cm³. 2 .

[0090] Furthermore, after obtaining the negative electrode, a Whatman glass fiber membrane can be used as the separator, and a 1 mol / L NaPF6 solution can be used as the electrolyte to assemble a sodium-ion battery in a glove box. The discharge specific capacity of the sodium-ion battery under different current densities is tested within a test voltage range of 0.01 to 2.0 V. The results of the electrochemical performance test are shown in Table 2 below.

[0091] Application Example 2

[0092] In Application Example 2, the specific procedure for applying the polyhydroxyphenolic crosslinking agent can be as follows:

[0093] Weigh 20g of the polyhydroxyphenolic crosslinking agent prepared in Example 6 above, mix it with 25g of ethylene tar and 0.9g of p-toluenesulfonic acid at 90°C, and then heat it to 200°C while stirring. Start timing and keep stirring under reflux. React at a constant temperature for 10h to obtain condensed polycyclic aromatic hydrocarbon resin.

[0094] Next, under a nitrogen atmosphere, the obtained condensed polycyclic aromatic hydrocarbon resin can be treated at 300°C for 2 hours, then heated to 1200°C and kept at 1200°C for 2 hours to obtain condensed polycyclic aromatic hydrocarbon resin-based carbon materials.

[0095] Subsequently, the obtained condensed polycyclic aromatic hydrocarbon resin-based carbon material, super p conductive agent, and PVDF are mixed in a mass ratio of 8:1:1, and NMP is added as a solvent to obtain a slurry. The slurry is then uniformly coated onto copper foil and dried in a vacuum oven at 120°C for 12 hours to obtain carbon-coated copper foil. The carbon-coated copper foil is then cut into negative electrode sheets with a diameter of 12 mm. The loading of the negative electrode sheet can be approximately 1–2.5 mg / cm³. 2 .

[0096] Furthermore, after obtaining the negative electrode, a Whatman glass fiber membrane can be used as the separator, and a 1 mol / L NaPF6 solution can be used as the electrolyte to assemble a sodium-ion battery in a glove box. The discharge specific capacity of the sodium-ion battery under different current densities is tested within a test voltage range of 0.01 to 2.0 V. The results of the electrochemical performance test are shown in Table 2 below.

[0097] Table 2

[0098]

[0099] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0100] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for applying a polyhydroxyphenolic crosslinking agent, characterized in that, include: A condensation reaction is carried out between a polyhydroxyphenolic crosslinking agent and an aromatic oil rich in aromatic hydrocarbons under the action of a catalyst to obtain a condensed polycyclic polynuclear aromatic hydrocarbon resin. in, The preparation method of the polyhydroxyphenol crosslinking agent includes: Paraformaldehyde and phenol are completely dissolved in an alkaline solution to form a mixed solution; The mixed solution is continuously stirred at a predetermined temperature for a predetermined time to obtain a polyhydroxyphenol crosslinking agent; The phenols include one or more of phenol, catechol, hydroquinone, resorcinol, phloroglucinol, p-tert-butylphenol, p-tert-octylphenol, p-methylphenol, gallic acid, hydrolyzed tannins, and condensed tannins. The mass ratio of the paraformaldehyde, the phenol, and the alkaline solution is (5~20):(10~30):(50~85); The predetermined temperature is 25~70℃; the predetermined time is 1~48h.

2. The application method according to claim 1, characterized in that, The alkaline solution is an aqueous solution of any one or more combinations of ammonia, sodium hydroxide, and potassium hydroxide, and the mass concentration of the alkaline solution is 2% to 40%.

3. The application method according to claim 1, characterized in that, The process of completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution includes: Paraformaldehyde and phenol are added to an alkaline solution, and the temperature is raised to the predetermined temperature until the paraformaldehyde and phenol are completely dissolved to form a mixed solution.

4. The application method according to claim 1, characterized in that, The step of condensing a polyhydroxyphenolic crosslinking agent with an aromatic oil under the action of a catalyst to obtain a condensed polycyclic aromatic hydrocarbon resin includes: The polyhydroxyphenol crosslinking agent, aromatic oil, and catalyst are stirred and mixed evenly at a first predetermined temperature. Then, the mixture is heated to a second predetermined temperature while stirring. The second predetermined temperature is higher than the first predetermined temperature. The mixture is stirred and reacted at the second predetermined temperature for a first predetermined time to obtain a condensed polycyclic aromatic hydrocarbon resin.

5. The application method according to claim 1, characterized in that, The aromatic oil includes at least one of ethylene tar, heavy ethylene tar components, light ethylene tar components, coated asphalt residues, and catalytic cracked diesel oil; the catalyst includes at least one of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid, and perchloric acid.

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