Polyhydroxy phenol cross-linking agent and preparation method and application method thereof

Abstract

The invention relates to a polyhydroxy phenol crosslinking agent as well as a preparation method and an application method thereof. The preparation method comprises the following steps: completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution; and continuously stirring the mixed solution at a preset temperature to react for a preset time, so as to obtain the polyhydroxy phenol cross-linking agent. According to the invention, hydroxymethyl is introduced into the molecular structure of phenol through paraformaldehyde, so that the phenol molecule has a plurality of crosslinkable active groups, and the polyhydroxy phenol cross-linking agent is obtained, thereby providing the polyhydroxy phenol cross-linking agent for converting petrochemical aromatic hydrocarbon-rich oil into condensed polycyclic polynuclear aromatic hydrocarbon resin with high added value; the polyhydroxy phenol cross-linking agent can be synthesized by a one-pot method, the preparation process has the advantages of low raw material cost, mild reaction conditions, high product yield, easiness in industrial production and the like, and oxygen-containing functional groups can be controllably introduced into resin to prepare condensed polycyclic polynuclear aromatic resins with different oxygen contents; the utilization value of the condensed polycyclic polynuclear aromatic resin is improved.

Description

Technical Field

[0001] The present application relates to the technical field of heavy oil processing, and in particular to a polyhydroxyphenol crosslinking agent and a preparation method and an application method thereof. Background Art

[0002] With the development of the petrochemical industry, the position of ethylene cracking process and catalytic cracking process in the petrochemical industry is becoming more and more important. These two types of processes will produce two kinds of aromatic-rich oils, ethylene tar (accounting for about 15% of ethylene production capacity) and catalytic cracking diesel (accounting for about 30% of diesel production capacity) 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; catalytic cracking diesel is mainly converted into light aromatics and benzene-toluene-xylene mixtures through hydrogenation process, but these processes are energy-intensive and have low economic benefits. Whether it is ethylene tar or catalytic cracking diesel, it is urgent to find a way to efficiently convert the aromatic components into high-value-added chemical products to improve the economic benefits of the petroleum refining industry and improve the process technology of petroleum processing.

[0003] Ethylene tar and catalytic diesel are both aromatic-rich oils with strong electrophilic substitution reaction activity. They can be converted into condensed polycyclic polynuclear aromatic hydrocarbons (COPNA) resins through electrophilic substitution reactions with the help of crosslinkers. The resin was discovered by Japanese scientist Otani Sugiro in the mid-1980s. It has good processability, good carbon material wettability and self-lubricating properties, and is considered to be an excellent carbon material precursor. As one of the most critical factors in the preparation process of COPNA resin, the commonly used crosslinkers include terephthalic acid, trioxymethylene, benzaldehyde, terephthalic acid, and divinylbenzene. Among them, terephthalic acid has a better crosslinking effect than the other four crosslinkers, and can obtain COPNA resins with higher yields and good heat resistance; despite this, terephthalic acid as a crosslinker also has many disadvantages, including high cost, difficulty in modifying the obtained COPNA resin due to the lack of polar functional groups, and low interlayer spacing of the synthesized resin-based carbon material, which makes it unfavorable for the storage of sodium ions, etc.

[0004] Therefore, there is an urgent need to develop a cross-linking agent that is low-cost, rich in polar functional groups and can improve the structural properties of the corresponding resin-based carbon materials, so as to enhance the utilization value of COPNA resin. Summary of the invention

[0005] The purpose of the present application is to provide a polyhydroxyphenol cross-linking agent and a preparation method and an application method thereof, so as to provide a cross-linking agent with low cost, rich polar functional groups and the ability to improve the structural properties of the corresponding resin-based carbon material, thereby enhancing the utilization value of COPNA resin.

[0006] The embodiment of the present application provides a method for preparing a polyhydroxyphenol cross-linking agent, which comprises: completely dissolving polyformaldehyde and phenol in an alkaline solution to form a mixed solution; and continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain the polyhydroxyphenol cross-linking agent.

[0007] The phenol includes one or more of phenol, catechol, hydroquinone, resorcinol, phloroglucinol, p-tert-butylphenol, p-tert-octylphenol, p-methylphenol, gallic acid, hydrolyzed tannin and condensed tannin.

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

[0009] Among them, the predetermined temperature is 25 to 70°C; the predetermined time is 1 to 48 hours.

[0010] The alkaline solution is an aqueous solution of any one or more combinations of ammonia water, sodium hydroxide and potassium hydroxide, and the mass concentration of the alkaline solution is 2% to 40%.

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

[0012] The embodiment of the present application further provides a polyhydroxyphenol cross-linking agent, which is prepared by any of the above-mentioned preparation methods of the polyhydroxyphenol cross-linking agent.

[0013] The embodiment of the present application also provides an application method of a polyhydroxyphenol crosslinking agent, which comprises: subjecting the polyhydroxyphenol crosslinking agent to a condensation reaction with aromatic-rich oil under the action of a catalyst to obtain a condensed polycyclic polynuclear aromatic resin.

[0014] The method comprises: uniformly stirring and mixing the polyhydroxyphenol crosslinking agent, the aromatic-rich oil and the catalyst at a first predetermined temperature, and then heating and heating the mixture to a second predetermined temperature under stirring, wherein the second predetermined temperature is higher than the first predetermined temperature, and continuously stirring and reacting at the second predetermined temperature for a first predetermined time to obtain the condensed polycyclic polynuclear aromatic resin.

[0015] The aromatics-rich oil includes at least one of ethylene tar, ethylene tar heavy components, ethylene tar light components, coated asphalt residues and catalytic cracking diesel; the catalyst includes at least one of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid and perchloric acid.

[0016] The polyhydroxyphenol crosslinking agent provided in the present application and its preparation method and application method are obtained by completely dissolving polyformaldehyde 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 react, thereby obtaining the polyhydroxyphenol crosslinking agent. In this way, the hydroxymethyl group is introduced into the molecular structure of phenol by polyformaldehyde, so that the phenol molecule has multiple crosslinkable active groups, that is, the polyhydroxyphenol crosslinking agent is obtained, thereby providing a polyhydroxyphenol crosslinking agent that can be used to convert petrochemical rich aromatic oils such as ethylene tar and catalytic cracking diesel into condensed polycyclic polynuclear aromatic resins, and the polyhydroxyphenol crosslinking agent can be synthesized by a one-pot method, and its preparation process has the advantages of low raw material cost, mild reaction conditions, high product yield, and easy industrial production. Moreover, oxygen-containing functional groups can be controllably introduced into the resin to obtain condensed polycyclic polynuclear aromatic hydrocarbon resins with different oxygen contents, which can effectively improve the metal ion storage capacity of the condensed polycyclic polynuclear aromatic hydrocarbon resin-based carbon material, thereby making the condensed polycyclic polynuclear aromatic hydrocarbon resin a high-quality precursor for electrode materials, thereby improving the utilization value of the condensed polycyclic polynuclear aromatic hydrocarbon resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.

[0018] Figure 1 1 is a schematic flow chart of a method for preparing a polyhydroxyphenol cross-linking agent provided in an embodiment of the present application;

[0019] Figure 2 It is a schematic flow chart of the application method of the polyhydroxyphenol cross-linking agent provided in the embodiments of the present application. DETAILED DESCRIPTION

[0020] The present application is further described in detail below in conjunction with the accompanying drawings and examples. It is particularly noted that the following examples are only used to illustrate the present application, but are not intended to limit the scope of the present application. Similarly, the following examples are only some embodiments of the present application rather than all embodiments, and all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of this application.

[0021] In the following description of the present application, reference is made to “some embodiments”, which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

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

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. If there is any conflict, this specification takes precedence. The terms used herein are only for the purpose of describing the embodiments of this application and are not intended to limit this application.

[0024] Unless otherwise specified, various 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 examples, the properties of the raw oils such as ethylene tar and catalytic cracking diesel used can be shown in Table 1 below.

[0026] Table 1

[0027]

[0028] The following is a detailed description with reference to specific embodiments. It should be noted that the serial numbers of the following embodiments are not intended to limit the preferred order of the embodiments.

[0029] See also Figure 1 , Figure 1 : is a schematic diagram of a process for preparing a polyhydroxyphenol cross-linking agent provided in an embodiment of the present application. The specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

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

[0031] Among them, phenol can include one or more of phenol, catechol, hydroquinone, resorcinol, phloroglucinol, p-tert-butylphenol, p-tert-octylphenol, p-methylphenol, gallic acid, hydrolyzed tannin and condensed tannin, for example, it can be p-tert-butylphenol, resorcinol, gallic acid or phenol.

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

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

[0034] Step S12: continuously stirring the mixed solution at a predetermined temperature for a predetermined time to obtain a polyhydroxyphenol cross-linking agent.

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

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

[0037] Furthermore, in a specific implementation, an alkaline solution can be prepared, and the prepared alkaline solution is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then polyformaldehyde and phenol are weighed and added to the three-necked flask, and heated to a predetermined temperature under stirring, and after observing that the reaction raw materials (i.e., polyformaldehyde and phenol) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for a predetermined time. After the reaction is completed, the reactants are cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0038] It should be noted that the polyhydroxyphenol crosslinking agent obtained after the completion of the above step S12 is obtained by connecting hydroxymethyl to phenol through paraformaldehyde, so that the phenol molecule has multiple crosslinkable active groups (i.e., hydroxyl groups). In other words, the polyhydroxyphenol crosslinking agent obtained after the completion of the above step S12 is a phenol compound containing multiple crosslinking functional groups (i.e., hydroxyl groups), and the phenol compound is a polyol, so that it can act on aromatic oil molecules such as ethylene tar and catalytic cracking diesel to synthesize condensed polycyclic polynuclear aromatic resins containing oxygen-containing functional groups.

[0039] Moreover, in the embodiments of the present application, the content of oxygen-containing functional groups in the prepared polyhydroxyphenol cross-linking agent can be regulated by controlling the reaction conditions (for example, reaction raw materials, alkaline solution, predetermined temperature, predetermined time, etc.), and then the content of oxygen-containing functional groups in the condensed polycyclic polynuclear aromatic hydrocarbon resin prepared by the polyhydroxyphenol cross-linking agent can be regulated, thereby effectively improving the metal ion storage capacity of the resin-based carbon material, so that the obtained resin product can be used as a high-quality precursor of the electrode material.

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

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

[0042] Chinese patent document (CN110283341B) discloses that plant starch such as corn starch and potato starch is used as a crosslinking agent and protonic acid is used as a catalyst to convert polycyclic aromatic hydrocarbons in petroleum asphalt and / or FCC slurry into COPNA resin. The obtained B-stage COPNA resin has a high β resin content and high viscosity, and the C-stage petroleum-based COPNA resin has a high carbon residue value. The plant starch used is rich in hydroxyl functional groups and has a good crosslinking effect, which can significantly reduce the preparation cost of COPNA resin and expand the application range of COPNA resin.

[0043] Chinese patent document (CN106565938A) discloses that high carbon residue heat-resistant resin is prepared by using heavy fraction of ethylene tar as raw material, dialdehyde starch as cross-linking agent and lignin sulfonic acid as catalyst;

[0044] Chinese patent document (CN105419726B) discloses the preparation of COPNA resin using coal tar powder as raw material, terephthalic acid as crosslinking agent, and p-toluenesulfonic acid as catalyst, and the preparation of COPNA resin binder by mixing carbonized boron 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 materials using aromatic hydrocarbon-rich substances as raw materials, polyaldehydes (terephthalaldehyde or polyformaldehyde) or polyols (terephthalic alcohol) as crosslinking agents, p-toluenesulfonic acid as catalysts, synthetic COPNA resin as matrix, and polystyrene as reinforcing components;

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

[0047] In the above patent documents, the cross-linking agents used to prepare COPNA resins include terephthalic alcohol, terephthalaldehyde, trioxymethylene, formaldehyde, polystyrene, acetaldehyde, and starch, but none of the above patent documents involve the use of phenols and biomass phenols converted into polyols as cross-linking agents for converting petrochemical rich aromatic oils such as ethylene tar (including light fractions and heavy fractions) and catalytic cracking diesel into COPNA resins. Therefore, compared to the existing related technologies for preparing COPNA resins using polycyclic aromatic hydrocarbons, the embodiments of the present application provide a new cross-linking agent (i.e., the above polyhydroxyphenol cross-linking agent) that can be used to convert petrochemical rich aromatic oils such as ethylene tar (including light fractions and heavy fractions) and catalytic cracking diesel into COPNA resins, and the new cross-linking agent has low cost, rich polar functional groups, and can improve the structural properties of the corresponding resin-based carbon material, thereby solving the technical problem of insufficient metal ion storage capacity of existing COPNA resin-based carbon materials, so as to enhance the utilization value of COPNA resins.

[0048] Furthermore, for ease of understanding, the present application is further described in detail below through six specific embodiments (ie, Embodiment 1, Embodiment 2, Embodiment 3, Embodiment 4, Embodiment 5 and Embodiment 6).

[0049] Example 1

[0050] In Example 1, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0051] A sodium hydroxide aqueous solution with a mass concentration of 5% is prepared, and 100 g of the prepared sodium hydroxide aqueous solution with a mass concentration of 5% is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then 8.333 g of polyformaldehyde and 41.667 g of p-tert-butylphenol are weighed and added to the three-necked flask, and heated to 60° C. with stirring. After observing that the reaction raw materials (i.e., polyformaldehyde and p-tert-butylphenol) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for 5 hours. After the reaction is completed, the reactant is cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0052] Example 2

[0053] In Example 2, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0054] A potassium hydroxide aqueous solution with a mass concentration of 20% is prepared, and 50 g of the prepared potassium hydroxide aqueous solution with a mass concentration of 20% is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then 7.692 g of polyformaldehyde and 18.795 g of resorcinol are weighed and added to the three-necked flask, and heated to 40° C. under stirring. After observing that the reaction raw materials (i.e., polyformaldehyde and resorcinol) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for 12 hours. After the reaction is completed, the reactant is cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0055] Example 3

[0056] In Example 3, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0057] Prepare an ammonia solution with a mass concentration of 30%, and add 50g of the prepared ammonia solution with a mass concentration of 30% into a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then weigh 22.500g of polyformaldehyde and 37.495g of p-tert-butylphenol and add them into the three-necked flask, heat to 50°C with stirring, and start timing after observing that the reaction raw materials (i.e., polyformaldehyde and p-tert-butylphenol) are completely dissolved, keep stirring under reflux, and react at a constant temperature for 18h. After the reaction is completed, cool the reactant to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0058] Example 4

[0059] In Example 4, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0060] A sodium hydroxide aqueous solution with a mass concentration of 38% is prepared, and 50 g of the prepared sodium hydroxide aqueous solution with a mass concentration of 38% is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then 23.75 g of polyformaldehyde and 26.897 g of gallic acid are weighed and added to the three-necked flask, and heated to 45° C. under stirring. After observing that the reaction raw materials (i.e., polyformaldehyde and gallic acid) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for 8 hours. After the reaction is completed, the reactant is cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0061] Example 5

[0062] In Example 5, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0063] A potassium hydroxide aqueous solution with a mass concentration of 25% is prepared, and 50 g of the prepared potassium hydroxide aqueous solution with a mass concentration of 25% is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then 21.429 g of polyformaldehyde and 8.950 g of phenol are weighed and added to the three-necked flask, and heated to 25° C. under stirring. After observing that the reaction raw materials (i.e., polyformaldehyde and phenol) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for 48 hours. After the reaction is completed, the reactant is cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0064] Example 6

[0065] In Example 6, the specific process of the preparation method of the polyhydroxyphenol cross-linking agent can be as follows:

[0066] A sodium hydroxide aqueous solution with a mass concentration of 15% is prepared, and 50 g of the prepared sodium hydroxide aqueous solution with a mass concentration of 15% is added to a three-necked flask equipped with a thermometer, a stirring device and a reflux device, then 22.222 g of polyformaldehyde and 27.778 g of p-tert-butylphenol are weighed and added to the three-necked flask, and heated to 30° C. with stirring. After observing that the reaction raw materials (i.e., polyformaldehyde and p-tert-butylphenol) are completely dissolved, the timing is started, stirring is maintained under reflux, and the reaction is carried out at a constant temperature for 24 hours. After the reaction is completed, the reactant is cooled to room temperature to obtain a polyhydroxyphenol cross-linking agent.

[0067] As can be seen from the above, the method for preparing the polyhydroxyphenol crosslinking agent provided in this embodiment is to obtain the polyhydroxyphenol crosslinking agent by completely dissolving polyformaldehyde 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. In this way, hydroxymethyl groups are introduced into the molecular structure of phenol by means of polyformaldehyde, so that the phenol molecule has multiple cross-linkable active groups, that is, a polyhydroxyphenol cross-linking agent is obtained, thereby providing a polyhydroxyphenol cross-linking agent for the transformation of petrochemical aromatic-rich oil into high-value-added condensed polycyclic polynuclear aromatic resins. The polyhydroxyphenol cross-linking agent can be synthesized by a one-pot method, and its preparation process has the advantages of low raw material cost, mild reaction conditions, high product yield, and easy industrial production. In addition, oxygen-containing functional groups can be controllably introduced into the resin to obtain condensed polycyclic polynuclear aromatic resins with different oxygen contents, which can effectively improve the metal ion storage capacity of the condensed polycyclic polynuclear aromatic resin-based carbon material, so that the condensed polycyclic polynuclear aromatic resin can be used as a high-quality precursor of the electrode material, thereby improving the utilization value of the condensed polycyclic polynuclear aromatic resin.

[0068] In order to better implement the preparation method of the polyhydroxyphenol cross-linking agent provided in the embodiments of the present application, the embodiments of the present application also provide a polyhydroxyphenol cross-linking agent, which is prepared by the preparation method of the polyhydroxyphenol cross-linking agent provided in any of the above embodiments.

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

[0070] Furthermore, it should be noted that the polyhydroxyphenol cross-linking agent in the embodiment of the present application is prepared by the preparation method of the polyhydroxyphenol cross-linking agent provided by any of the above embodiments, and therefore has all the same beneficial effects, which will not be described in detail in this embodiment.

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

[0072] See also Figure 2 , Figure 2 : is a schematic flow diagram of the application method of the polyhydroxyphenol crosslinking agent provided in the embodiment of the present application. The application method of the polyhydroxyphenol crosslinking agent can be applied to the scene of converting petrochemical aromatic oils such as ethylene tar and catalytic cracking diesel into condensed polycyclic polynuclear aromatic resins. Figure 2 As shown, the specific process of the application method of the polyhydroxyphenol cross-linking agent can be as follows:

[0073] Step S21: condensing the polyhydroxyphenol crosslinking agent and the aromatic-rich oil under the action of a catalyst to obtain a condensed polycyclic polynuclear aromatic resin.

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

[0075] Furthermore, in a specific implementation, the polyhydroxyphenol crosslinking agent described in any of the above embodiments can be stirred and mixed with the aromatic-rich oil and the catalyst at a first predetermined temperature, and then heated to a second predetermined temperature under stirring, the second predetermined temperature being higher than the first predetermined temperature, and stirred and reacted for a first predetermined time at the second predetermined temperature to obtain a condensed polycyclic polynuclear aromatic 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 h or 10 h.

[0076] In some embodiments, Figure 2 As shown, after the above step S21, the application method of the above polyhydroxyphenol cross-linking agent may further include:

[0077] Step S22. In a protective gas atmosphere, carbonizing the condensed polycyclic polynuclear aromatic hydrocarbon resin to obtain a condensed polycyclic polynuclear aromatic hydrocarbon resin-based carbon material.

[0078] The protective gas may be nitrogen or argon, for example, specifically nitrogen.

[0079] Specifically, the condensed polycyclic polynuclear aromatic hydrocarbon resin obtained after the completion of the above step S21 can be treated at a third predetermined temperature for a second predetermined time and then heated to a fourth predetermined temperature under a protective gas atmosphere, and treated at a constant temperature at the fourth predetermined temperature for a third predetermined time to obtain a condensed polycyclic polynuclear 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°C, and the fourth predetermined temperature can be 1200°C or 1400°C. The second predetermined time can be 2h, and the third predetermined time can be 2h.

[0080] In some specific embodiments, Figure 2 As shown, after the above step S22, the application method of the above polyhydroxyphenol cross-linking agent may further include:

[0081] Step S23: Mix the condensed polycyclic polynuclear 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 on a substrate and dry it to obtain an electrode plate.

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

[0083] Specifically, the condensed polycyclic polynuclear aromatic resin-based carbon material, the conductive agent and the binder can be mixed in a mass ratio of 8:1:1 and a solvent can be added to obtain a slurry, and then the slurry can be evenly coated on the substrate and placed in a vacuum oven at 120°C for 12 hours to obtain a carbon-coated substrate, and then the carbon-coated substrate can be cut into a negative electrode sheet with a diameter of 12 mm. The loading amount of the negative electrode sheet can be about 1 to 2.5 mg / cm 2 .

[0084] Furthermore, for ease of understanding, the present application is further described in detail below through two specific application examples (ie, application example 1 and application example 2).

[0085] Application Example 1

[0086] In Application Example 1, the specific process of the application method of the polyhydroxyphenol cross-linking agent can be as follows:

[0087] Weigh 20 g of the polyhydroxyphenol crosslinking agent prepared in Example 3 above, 20 g of catalytic cracking diesel and 1.2 g of p-toluenesulfonic acid, stir and mix them evenly at 90° C., then heat to 180° C. while stirring, start timing, keep stirring under reflux, and react at a constant temperature for 5 hours to obtain a condensed polycyclic polynuclear aromatic resin.

[0088] Next, under a nitrogen atmosphere, the obtained condensed polycyclic polynuclear aromatic resin is first treated at 300°C for 2 hours and then heated to 1400°C, and treated at a constant temperature of 1400°C for 2 hours to obtain a condensed polycyclic polynuclear aromatic resin-based carbon material.

[0089] Afterwards, the obtained condensed polycyclic polynuclear aromatic resin-based carbon material, super p conductive agent and PVDF can be mixed in a mass ratio of 8:1:1 and NMP as a solvent can be added to obtain a slurry, and then the slurry can be evenly coated on a copper foil and placed in a vacuum oven at 120°C for 12 hours to obtain a carbon-coated copper foil, and then the carbon-coated copper foil can be cut into a negative electrode sheet with a diameter of 12 mm, and the loading amount of the negative electrode sheet can be about 1 to 2.5 mg / cm 2 .

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

[0091] Application Example 2

[0092] In Application Example 2, the specific process of the application method of the polyhydroxyphenol cross-linking agent can be as follows:

[0093] Weigh 20 g of the polyhydroxyphenol crosslinking agent prepared in Example 6 above, 25 g of ethylene tar and 0.9 g of p-toluenesulfonic acid, stir and mix them evenly at 90° C., then heat to 200° C. under stirring, start timing, keep stirring under reflux, and react at a constant temperature for 10 hours to obtain a condensed polycyclic polynuclear aromatic resin.

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

[0095] Afterwards, the obtained condensed polycyclic polynuclear aromatic resin-based carbon material, super p conductive agent and PVDF can be mixed in a mass ratio of 8:1:1 and NMP as a solvent can be added to obtain a slurry, and then the slurry can be evenly coated on a copper foil and placed in a vacuum oven at 120°C for 12 hours to obtain a carbon-coated copper foil, and then the carbon-coated copper foil can be cut into a negative electrode sheet with a diameter of 12 mm, and the loading amount of the negative electrode sheet can be about 1 to 2.5 mg / cm 2 .

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

[0097] Table 2

[0098]

[0099] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

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

Claims

1. A method for preparing a polyhydroxyphenol crosslinking agent, characterized in that: include: Completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution; The mixed solution is continuously stirred and reacted at a predetermined temperature for a predetermined time to obtain a polyhydroxyphenol cross-linking agent.

2. The preparation method according to claim 1, characterized in that: The phenol includes one or more of phenol, catechol, hydroquinone, resorcinol, phloroglucinol, p-tert-butylphenol, p-tert-octylphenol, p-methylphenol, gallic acid, hydrolyzed tannin and condensed tannin.

3. The preparation method according to claim 1, characterized in that: The mass ratio of the paraformaldehyde, the phenol and the alkaline solution is (5-20):(10-30):(50-85).

4. The preparation method according to claim 1, characterized in that: The predetermined temperature is 25 to 70° C.; the predetermined time is 1 to 48 hours.

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

6. The preparation method according to claim 1, characterized in that: The method of completely dissolving paraformaldehyde and phenol in an alkaline solution to form a mixed solution comprises: Adding paraformaldehyde and phenol into an alkaline solution, heating the solution to the predetermined temperature until the paraformaldehyde and the phenol are completely dissolved to form a mixed solution.

7. A polyhydroxyphenol crosslinking agent, characterized in that: The method is prepared by the preparation method according to any one of claims 1 to 6.

8. A method for applying a polyhydroxyphenol crosslinking agent, characterized in that: include: The polyhydroxyphenol crosslinking agent described in claim 7 is subjected to a condensation reaction with aromatic-rich oil in the presence of a catalyst to obtain a condensed polycyclic polynuclear aromatic resin.

9. The application method according to claim 8, characterized in that: The polyhydroxyphenol crosslinking agent according to claim 7 is subjected to a condensation reaction with the aromatic-rich oil under the action of a catalyst to obtain a condensed polycyclic polynuclear aromatic resin, comprising: The polyhydroxyphenol cross-linking agent described in claim 7 is stirred and mixed evenly with aromatic-rich oil and a catalyst at a first predetermined temperature, and then heated to a second predetermined temperature while stirring, wherein the second predetermined temperature is higher than the first predetermined temperature, and the stirring reaction is continued at the second predetermined temperature for a first predetermined time to obtain a condensed polycyclic polynuclear aromatic resin.

10. The application method according to claim 8, characterized in that: The aromatics-rich oil includes at least one of ethylene tar, ethylene tar heavy components, ethylene tar light components, coated asphalt residues and catalytic cracking diesel; the catalyst includes at least one of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid and perchloric acid.

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