Phenolic resin gas-solid integrated treatment method, its by-products and applications

Abstract

This invention discloses an integrated gas-solid treatment method for phenolic resin, its byproducts, and applications, belonging to the field of resource and environmental protection technology. The method includes the following steps: S1, absorbing and reacting the waste gas generated during phenolic resin production with an alkaline solution to obtain an absorbent; S2, subjecting the absorbent to anaerobic acidification treatment to obtain spherical phenolic resin particles. Through gas-to-water and water-to-solid conversion, harmful substances in the waste gas generated during phenolic resin production can be effectively removed, achieving efficient and low-cost treatment of phenolic resin waste gas. Simultaneously, the obtained byproduct, spherical phenolic resin particles, realize the high-value, green, and resource-based treatment of waste gas. This product can be used in phenolic molding compounds, electrode materials, adsorbent materials, and catalyst carriers, exhibiting excellent performance.

Description

Technical Field

[0001] This invention relates to the field of resources and environmental protection technology, and in particular to a method for integrated gas-solid treatment of phenolic resin, its byproducts, and applications. Background Technology

[0002] Phenolic resin is an important chemical raw material, prepared from phenols and aldehydes through a condensation reaction. It possesses numerous advantages such as heat resistance, flame retardancy, and insulation, making it a crucial raw material for phenolic molding compounds, refractory materials, coated sand, and coatings. Furthermore, due to its high residual carbon content, phenolic resin is an ideal precursor for the preparation of carbon materials. The production process of phenolic resin generates a certain amount of harmful gases, such as volatiles from raw material storage tanks, motor valve joints, and weighing and feeding processes. These gases contain large amounts of phenols, aldehydes, and small-molecule phenolic resins, requiring collection and treatment. Existing treatment methods mainly include spray absorption, activated carbon adsorption, combustion, and plasma methods. Among these, spray absorption primarily uses a solvent to spray the waste gas, dissolving the substances in the waste gas in the solvent, followed by treatment of the resulting waste liquid. The waste gas generated during the production of phenolic resin mainly consists of phenols, aldehydes, and small-molecule resins, which are highly water-soluble. Therefore, water is primarily used as a solvent, making the method simple, low-cost, and highly safe and environmentally friendly. For example, Chinese utility model patent CN203090710U discloses a waste gas collection and treatment device for the phenolic resin production process, which uses a spray absorption tower to ensure the waste gas meets emission standards. However, the wastewater generated by this method is difficult to treat and has high treatment costs. Activated carbon adsorption utilizes the porosity of activated carbon to absorb waste gas. It is simple to operate, but the treatment effect is poor and cannot achieve stable treatment results. The generated activated carbon waste needs to be treated separately, which is costly and not suitable for treating phenolic resin waste gas alone. Combustion involves oxidizing the waste gas at high temperatures with the assistance of fuel gas or oil, converting it into non-toxic and harmless gases such as silica and water. This method is effective, but it consumes a lot of energy, has high treatment costs, and requires strict risk management, making it unsuitable for small and medium-sized enterprises. The plasma method utilizes high-energy electrons and free radicals generated by plasma equipment to activate, ionize, and crack the components in industrial waste gas, causing them to undergo a series of complex chemical reactions such as decomposition and oxidation. After multi-stage purification, odorous and foul-smelling pollutants emitted from various pollution sources are eliminated, and toxic and harmful gases are reduced in toxicity or rendered non-toxic, thus protecting the human living environment. However, the industrial application of this method still has certain shortcomings, and the treatment effect is unstable.

[0003] The waste gas generated during the production of phenolic resin contains a large amount of phenol, aldehyde, and small molecule resins, which have recycling value. Direct treatment of this waste gas is not only costly but also wasteful of resources. Achieving efficient, low-cost, and resource-based treatment of phenolic resin waste gas remains a huge challenge. Successfully overcoming this challenge is of great significance to the green and sustainable development of the phenolic resin industry. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, the technical problem to be solved by the present invention is to provide a low-cost and effective gas-solid integrated treatment method for phenolic resin, its by-products, and the utilization of the by-products.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a phenolic resin gas-solid integrated treatment method, comprising the following steps:

[0006] S1. The waste gas generated during the production of phenolic resin is absorbed and reacted with alkaline solution to obtain an absorbent liquid.

[0007] S2. The absorbent is subjected to anaerobic acidification to obtain spherical phenolic resin particles.

[0008] Phenolic resin spherical particles prepared by the above-mentioned gas-solid integrated treatment method for phenolic resin.

[0009] Applications of spherical phenolic resin particles in phenolic molding compounds, electrode materials, adsorbent materials, and catalyst supports.

[0010] The beneficial effects of this invention are as follows: by converting gas to water and water to solid, harmful substances in the waste gas generated during the production of phenolic resin can be effectively removed, and efficient and low-cost treatment of phenolic resin waste gas can be achieved. At the same time, the by-product phenolic resin spherical particles obtained realize the high-value, green and resource-based treatment of waste gas. This product can be used in phenolic molding compounds, electrode materials, adsorbent materials and catalyst carriers, showing good performance. Attached Figure Description

[0011] Figure 1 The image shown is a SEM image of the spherical phenolic resin particles of Example 1 of the present invention. Detailed Implementation

[0012] To explain in detail the technical content, objectives, and effects of the present invention, the following description is provided in conjunction with the embodiments and accompanying drawings.

[0013] The most crucial concept of this invention lies in providing an efficient and resource-efficient gas-solid integrated treatment method for phenolic resin, as well as spherical phenolic resin particles prepared by this method and the applications of these spherical phenolic resin particles.

[0014] The phenolic resin gas-solid integrated treatment method of the present invention includes the following steps:

[0015] S1. The waste gas generated during the production of phenolic resin is absorbed and reacted with alkaline solution to obtain an absorbent liquid.

[0016] S2. The absorbent is subjected to anaerobic acidification to obtain spherical phenolic resin particles.

[0017] As can be seen from the above description, the beneficial effects of the present invention are as follows: the main components of phenolic resin waste gas are phenols, aldehydes, and small molecule resins, as well as a small amount of catalysts and their decomposition products. These components have good solubility in alkaline solutions. By absorbing the waste gas with alkaline solutions, it is converted into wastewater. Under the action of alkaline catalysts, the above components in the wastewater undergo simultaneous condensation reactions, which further increase their molecular weight. The resulting phenolic resin solution with a certain molecular weight and distribution, i.e., the absorbent, during the anaerobic acidification process, as the pH of the system gradually decreases, the solubility of the phenolic resin decreases and a certain degree of cross-linking occurs. The phenolic resin with a higher molecular weight eventually precipitates out of the system. As a good dilute solution system, the absorbent creates favorable conditions for the spheroidization of phenolic resin, so that the phenolic resin eventually precipitates out in the form of spherical particles.

[0018] Furthermore, S1 specifically refers to:

[0019] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and an absorbent is obtained by spraying with alkaline solution. The pH of the alkaline solution is 9-12 and the temperature is 60-85℃.

[0020] S1.2. The pH of the absorption solution is adjusted to 9-12 using an alkaline solution.

[0021] Furthermore, the absorbent liquid is reused for spraying phenolic resin waste gas.

[0022] Furthermore, the alkaline solution is an aqueous solution of sodium hydroxide, potassium hydroxide, or magnesium hydroxide.

[0023] Furthermore, the spray tower is connected to the biochemical pool.

[0024] As described above, the pH value of the alkaline solution affects the absorption of waste gas. A higher pH value is beneficial for the dissolution of phenols, aldehydes, and small molecule resins. Conversely, a higher pH value also affects the condensation of phenols, aldehydes, and small molecule resins, accelerating the condensation reaction and allowing the system to form larger molecular weight phenolic resins in a shorter time. However, excessively high pH values ​​increase treatment costs and are detrimental to subsequent biochemical treatment and particle precipitation.

[0025] Increasing the temperature enhances absorption and accelerates condensation. The phenolic resin waste gas is pumped into a spray tower and absorbed using an alkaline solution with a pH of 9–12 and a temperature of 60–85°C. During this process, phenols, aldehydes, and small-molecule resins are captured by the alkaline solution. In the alkaline solution, these components undergo further condensation reactions to form larger molecular weight phenolic resins. Because the pH of the system is maintained between 9 and 12, the phenolic resins retain good solubility and do not precipitate. The liquid level in the spray tower changes during absorption and condensation. An automatic control valve regulates the liquid level, maintaining it at 4–10% of the tower height. Absorbent liquid exceeding the level is discharged into a biological treatment tank for anaerobic acidification.

[0026] Furthermore, S2 specifically refers to:

[0027] S2.1 Under anaerobic conditions, adjust the pH of the absorption solution to 5-7;

[0028] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0029] S2.3. The supernatant is subjected to aerobic treatment, and the solid is dried to obtain spherical phenolic resin particles.

[0030] As can be seen from the above description, after the supernatant enters the aerobic tank for aerobic treatment, the pollutant concentration decreases significantly, the wastewater can be recycled, and the absorbent, as a good dilute solution system, creates favorable conditions for the spheroidization of phenolic resin, so that the phenolic resin is finally precipitated in the form of spherical particles.

[0031] Furthermore, in S2.2, the phenol content of the supernatant is ≤100ppm, the aldehyde content is ≤50ppm, the COD is ≤10000ppm, and the pH is 5-7.

[0032] Furthermore, in S2.2, the supernatant has a phenol content ≤50ppm, an aldehyde content ≤40ppm, a COD ≤8000ppm, and a pH of 5.8–6.8.

[0033] As can be seen from the above description, during the anaerobic acidification process, low molecular weight substances are consumed by bacteria, while high molecular weight substances precipitate out. Therefore, the organic matter content in the supernatant is greatly reduced, achieving efficient treatment of waste gas.

[0034] Furthermore, it also includes S2.4, where the wastewater obtained after aerobic treatment of the supernatant is used to produce formaldehyde solution.

[0035] As described above, after the supernatant enters the aerobic tank for aerobic treatment, the pollutant concentration decreases significantly, and the wastewater can be recycled. The wastewater can be used to produce formaldehyde solution, and is also used for spray absorption in the absorption tower during formaldehyde production. The produced formaldehyde meets the requirements for phenolic resin preparation and can be used in the next stage of phenolic resin production, achieving low or zero wastewater discharge.

[0036] Further, in S1, the phenol content of the absorbent is 200–2000 ppm, the aldehyde content is 100–1000 ppm, and the COD is 5000–50000 ppm. Preferably, in S1, the phenol content of the absorbent is 200–1000 ppm, the aldehyde content is 100–800 ppm, the COD is 5000–20000 ppm, and the pH is 9–11.

[0037] As can be seen from the above description, excessively high levels of phenol, aldehyde, and COD will reduce the absorption effect of waste gas and affect the precipitation and size of particles during the acidification process. The concentration of the absorbent can be controlled by discharging the absorbent or adding alkaline solution. Preferably, the absorbent can be temporarily stored before the next stage of treatment. Preferably, a collection tank is used to temporarily store the absorbent.

[0038] Furthermore, in S1, a surfactant is added to the absorbent liquid.

[0039] Furthermore, the surfactants include F127, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride.

[0040] Furthermore, the surfactant is added during the spray absorption process, or in the absorbent solution after spray absorption, or during the anaerobic acidification treatment. Preferably, the surfactant is added to the absorbent solution before the anaerobic acidification treatment.

[0041] As can be seen from the above description, adding a surfactant to the absorbent liquid coats the surface of the particles, reduces the surface energy of the particles, causes them to precipitate out of the system, increases the precipitation of precipitates in the biochemical system, further promotes the precipitation of phenolic resin particles, and regulates the particle size.

[0042] Furthermore, in S2, the feed load for anaerobic acidification treatment is 0.4–5 kg COD / d / m³. 3 .

[0043] Furthermore, in S2, the feed load for anaerobic acidification treatment is 0.7–3 kg COD / d / m³. 3 .

[0044] As described above, under anaerobic conditions, the absorbent liquid undergoes acid production and methanogenesis stages. By controlling the load, the acid-producing bacteria are provided with sufficient nutrients, and the amount of organic acids produced exceeds the absorption capacity of the methanogenic bacteria. This leads to the accumulation of organic acids in the system and a drop in the pH of the solution to below 7. As the pH decreases, the solubility of the phenolic resin in the system decreases, and cross-linking occurs to a certain extent, further increasing its molecular weight. Higher molecular weight phenolic resins eventually precipitate from the system. The absorbent liquid, as a good dilute solution, creates favorable conditions for the spheroidization of phenolic resins, causing them to precipitate as spherical particles. The phenolic resins in the absorbent liquid have a certain molecular weight distribution. Smaller molecular weight phenolic resins, as well as phenols and aldehydes, have better degradation capabilities during anaerobic treatment. They can serve as carbon sources for bacteria, supplementing their nutrition and undergoing acidic fermentation to lower the pH of the solution. Higher molecular weight phenolic resins are more difficult to degrade and precipitate as the pH decreases, forming a solid precipitate. After solid-liquid separation and drying, a solid substance is obtained. In other words, controlling the load has a significant impact on acidification and precipitation. Low load will reduce the acidification effect and cause the degradation of high molecular weight phenolic resin, which is not conducive to precipitation. Excessive load will also affect the stability of the biochemical system.

[0045] Phenolic resin spherical particles prepared by the above-mentioned gas-solid integrated treatment method for phenolic resin.

[0046] As can be seen from the above description, when absorbents with different compositions, molecular weights and their distributions are subjected to anaerobic treatment, low molecular weight substances provide nutrients for bacteria and produce acid, causing high molecular weight phenolic resin to precipitate. Combined with a biochemical system with a certain load, i.e. a good dilute solution system, good conditions are provided for particle precipitation and spheroidization. In the dilute solution system, the consumption of precipitated spherical substances is the lowest and the stability is the most.

[0047] This invention also provides a method for continuous gas-solid integrated treatment of phenolic resin, specifically: the absorbent is fed into an anaerobic tank for acidification treatment via continuous feeding, and after anaerobic acidification treatment, it enters a sedimentation tank for sedimentation, and is then discharged through a pipe at the bottom of the sedimentation tank. Solid-liquid separation is then achieved by plate and frame filter press and vacuum filtration. After the solid precipitate is dried, spherical phenolic resin particles are obtained. The drying is carried out by methods such as baking or spray drying, and the supernatant flows into the next stage of treatment.

[0048] This invention also provides a phenolic molding compound comprising the above-mentioned phenolic resin spherical particles and its preparation method. The preparation method specifically comprises: mixing 2-20 parts by weight of phenolic resin spherical particles, 25-45 parts of phenolic resin, 20-40 parts of filler, 10-20 parts of curing agent, and 5-10 parts of additives uniformly; and obtaining the phenolic molding compound after melt blending, cooling, and pulverizing. The curing agent is hexamethylenetetramine, and the filler is one or more of the following: wood fiber, bamboo fiber, glass fiber, carbon fiber, basalt fiber, polyester fiber, alumina fiber, carbon nanotubes, graphene, graphite, calcium carbonate, talc powder, mica powder, silica fume, silica, magnesium oxide, calcium oxide, and asbestos powder.

[0049] As described above, the phenolic resin prepared by this invention consists of spherical particles with low density. When used as a filler in modified phenolic molding compounds, it can significantly reduce the density of the molding compounds, achieving a lightweight effect. Furthermore, by controlling the processing conditions or adding surfactants, nano-sized spherical particles can be obtained. When used as fillers in modified phenolic molding compounds, these particles exhibit unique nano-effects, improving the mechanical properties of the material and reducing its deformation. The prepared molding compounds can be used to manufacture electronic frameworks, separators for new energy power batteries, and large-size electrical components.

[0050] Applications of spherical phenolic resin particles in phenolic molding compounds, electrode materials, adsorbent materials, and catalyst supports.

[0051] As described above, converting waste gas into spherical phenolic resin particles and applying them to phenolic molding compounds, electrode materials, adsorbent materials, catalyst supports, and other fields not only achieves excellent treatment results but also realizes the high-value utilization of waste, demonstrating a good green and environmentally friendly effect. The spherical phenolic resin particles prepared by this invention possess high thermal stability and low residual carbon content. The carbon microspheres obtained after carbonization have a rich porous structure, providing ample space for ion enrichment and making them suitable as electrode materials for supercapacitors, lithium-ion batteries, etc. Their abundant porous structure also provides conditions for their application in adsorbent materials, catalyst supports, and other fields.

[0052] Embodiment 1 of the present invention is as follows:

[0053] A method for integrated gas-solid treatment of phenolic resin includes the following steps:

[0054] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and sprayed with a sodium hydroxide aqueous solution at 65°C and pH 10 to obtain an absorbent.

[0055] S1.2. Adjust the pH of the absorbent using sodium hydroxide aqueous solution to maintain it between 9 and 11; monitor the COD value of the absorbent; when the COD value of the absorbent exceeds 20,000 ppm, discharge part of the absorbent into the collection tank for storage, and replenish part of the sodium hydroxide aqueous solution to the spray tower to maintain liquid level balance.

[0056] S2.1. The absorbent is pumped into the anaerobic tank for anaerobic acidification treatment. The pH of the absorbent is adjusted to 5-7, and the feed load is 1 kg COD / d / m³. 3 ;

[0057] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0058] S2.3 The supernatant enters the aerobic tank for aerobic treatment, and the solids enter the sedimentation tank. The solids are then filtered through a plate and frame filter press and spray-dried through the pipes at the bottom of the sedimentation tank to obtain phenolic resin spherical particles.

[0059] The test results showed that the phenol content of the absorbent in S1.2 was 358 ppm, the aldehyde content was 196 ppm, the COD was 21540 ppm, and the pH was 10.5; the phenol content of the supernatant was 45 ppm, the aldehyde content was 36 ppm, the COD was 7595 ppm, and the pH was 6.2.

[0060] Embodiment 2 of the present invention is as follows:

[0061] A method for integrated gas-solid treatment of phenolic resin includes the following steps:

[0062] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and sprayed with a sodium hydroxide aqueous solution at 65°C and pH 11 to obtain an absorbent.

[0063] S1.2 Adjust the pH of the absorbent using sodium hydroxide aqueous solution to maintain it between 9 and 11; monitor the COD value of the absorbent; when the COD value of the absorbent exceeds 25,000 ppm, discharge part of the absorbent into the collection tank for storage, and replenish the spray tower with part of sodium hydroxide aqueous solution to maintain liquid level balance.

[0064] S2.1. The absorbent is pumped into the anaerobic tank for anaerobic acidification treatment, and the pH of the absorbent is adjusted to 5-7. The feed load is 0.8 kg COD / d / m³. 3 ;

[0065] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0066] S2.3 The supernatant enters the aerobic tank for aerobic treatment, and the solids enter the sedimentation tank. The solids are then filtered through a plate and frame filter press and spray-dried through the pipes at the bottom of the sedimentation tank to obtain phenolic resin spherical particles.

[0067] The test results showed that the phenol content of the absorbent in S1.2 was 258 ppm, the aldehyde content was 251 ppm, the COD was 26423 ppm, and the pH was 10.8; the phenol content of the supernatant was 32 ppm, the aldehyde content was 25 ppm, the COD was 6211 ppm, and the pH was 6.5.

[0068] Embodiment 3 of the present invention is as follows:

[0069] A method for integrated gas-solid treatment of phenolic resin includes the following steps:

[0070] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and sprayed with a sodium hydroxide aqueous solution at 65°C and pH 11 to obtain an absorbent.

[0071] S1.2 Adjust the pH of the absorbent using sodium hydroxide aqueous solution to maintain it between 9 and 11; monitor the COD value of the absorbent; when the COD value of the absorbent exceeds 25,000 ppm, discharge part of the absorbent into the collection tank for storage, and replenish the spray tower with part of sodium hydroxide aqueous solution to maintain liquid level balance.

[0072] S2.1. Add cetyltrimethylammonium bromide (0.1% of the absorbent mass) to the absorbent solution. Pump the absorbent solution into the anaerobic tank for anaerobic acidification treatment, adjusting the pH of the absorbent solution to 5-7. The feed load is 1.2 kg COD / d / m³. 3 ;

[0073] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0074] S2.3 The supernatant enters the aerobic tank for aerobic treatment, and the solids enter the sedimentation tank. The solids are then filtered through a plate and frame filter press and spray-dried through the pipes at the bottom of the sedimentation tank to obtain phenolic resin spherical particles.

[0075] The test results showed that the phenol content of the absorbent in S1.2 was 226 ppm, the aldehyde content was 189 ppm, the COD was 25453 ppm, and the pH was 10.6; the phenol content of the supernatant was 28 ppm, the aldehyde content was 22 ppm, the COD was 5012 ppm, and the pH was 6.1.

[0076] Embodiment four of the present invention is as follows:

[0077] A method for integrated gas-solid treatment of phenolic resin includes the following steps:

[0078] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and sprayed with a sodium hydroxide aqueous solution at 60°C and pH 9 to obtain an absorbent liquid.

[0079] S1.2. Adjust the pH of the absorbent using sodium hydroxide aqueous solution to maintain it between 9 and 12; monitor the COD value of the absorbent; when the COD value of the absorbent exceeds 20,000 ppm, discharge part of the absorbent into the collection tank for storage, and replenish part of the sodium hydroxide aqueous solution to the spray tower to maintain liquid level balance.

[0080] S2.1. The absorbent is pumped into the anaerobic tank for anaerobic acidification treatment. The pH of the absorbent is adjusted to 5-7, and the feed load is 0.4 kg COD / d / m³. 3 ;

[0081] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0082] S2.3 The supernatant enters the aerobic tank for aerobic treatment, and the solids enter the sedimentation tank. The solids are then filtered through a plate and frame filter press and spray-dried through the pipes at the bottom of the sedimentation tank to obtain phenolic resin spherical particles.

[0083] The test results showed that the phenol content of the absorbent in S1.2 was 269 ppm, the aldehyde content was 302 ppm, the COD was 22346 ppm, and the pH was 9.56; the phenol content of the supernatant was 33 ppm, the aldehyde content was 28 ppm, the COD was 5783 ppm, and the pH was 6.8.

[0084] Embodiment five of the present invention is as follows:

[0085] A method for integrated gas-solid treatment of phenolic resin includes the following steps:

[0086] S1.1 The waste gas generated during the production of phenolic resin is passed into a spray tower and sprayed with an aqueous sodium hydroxide solution at 85°C and pH 12 to obtain an absorbent liquid.

[0087] S1.2. Adjust the pH of the absorbent using sodium hydroxide aqueous solution to maintain it between 9 and 12; monitor the COD value of the absorbent; when the COD value of the absorbent exceeds 25,000 ppm, discharge part of the absorbent into the collection tank for storage, and replenish part of the sodium hydroxide aqueous solution to the spray tower to maintain liquid level balance.

[0088] S2.1. The absorbent is pumped into the anaerobic tank for anaerobic acidification treatment, and the pH of the absorbent is adjusted to 5-7. The feed load is 5 kg COD / d / m³. 3 ;

[0089] S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid;

[0090] S2.3 The supernatant enters the aerobic tank for aerobic treatment, and the solids enter the sedimentation tank. The solids are then filtered through a plate and frame filter press and spray-dried through the pipes at the bottom of the sedimentation tank to obtain phenolic resin spherical particles.

[0091] The test results showed that the phenol content of the absorbent in S1.2 was 246 ppm, the aldehyde content was 152 ppm, the COD was 22055 ppm, and the pH was 11.3; the phenol content of the supernatant was 48 ppm, the aldehyde content was 35 ppm, the COD was 7634 ppm, and the pH was 6.4.

[0092] Embodiment six of the present invention is as follows:

[0093] The spherical phenolic resin particles prepared in Example 1 were used to prepare phenolic molding compound. The specific preparation method was as follows: by weight, 10 parts of spherical phenolic resin particles, 37 parts of phenolic resin, 15 parts of wood fiber, 6 parts of calcium carbonate, 7 parts of talc, 5 parts of magnesium oxide, 15 parts of hexamethylenetetramine, 2 parts of EBS, 2 parts of calcium stearate, and 1 part of oil black were mixed evenly. After melt blending, cooling, and pulverizing, phenolic molding compound was obtained.

[0094] The phenolic molding compound was tested and found to have a tensile strength of 61 MPa and an impact strength of 7.5 kJ / m. 2 The load deformation temperature is 182℃.

[0095] Embodiment seven of the present invention is as follows:

[0096] The phenolic resin spherical particles prepared in Example 1 were applied to electrode materials. Specifically, the phenolic resin spherical particles were carbonized under nitrogen protection for 4 hours at a carbonization temperature of 800°C to obtain carbon microspheres with a specific surface area of ​​586 m². 2 / g. Weigh carbon microspheres, acetylene black and 3% SBR-CMC mixture and mix them evenly in a mass ratio of 8:1:1 to prepare a slurry (active material). Then, coat the active material slurry onto the rough part of a strip of graphite paper, put it in a vacuum oven and dry it at 100℃ for 5 hours. Then, perform a three-electrode supercapacitor test.

[0097] Tests showed that carbon microspheres at 1 Ag -1 The capacity calculated under the current density test is 215 F / g.

[0098] In summary, this invention provides an integrated gas-solid treatment method for phenolic resin. The method involves absorbing phenolic resin waste gas with an alkaline solution and simultaneously performing condensation treatment to increase the molecular weight of the phenolic resin. Following this, anaerobic acidification is performed, with the lower molecular weight substances serving primarily as a carbon source for bacterial anaerobic acidification, allowing the larger molecular weight phenolic resin to precipitate from the system. This preparation method is simple to operate, environmentally friendly, and economical. The obtained spherical phenolic resin particles can be used in phenolic molding compounds, electrode materials, adsorbent materials, catalyst carriers, etc., achieving high-value utilization of waste resources.

[0099] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for integrated gas-solid treatment of phenolic resin, characterized in that, Includes the following steps: S1. The waste gas generated during the production of phenolic resin is absorbed and reacted with an alkaline solution to obtain an absorbent liquid, which is a phenolic resin solution; the phenol content of the absorbent liquid is 200~2000ppm, the aldehyde content is 100~1000ppm, and the COD is 5000~50000ppm. S2. A surfactant is added to the absorbent liquid, and then anaerobic acidification is performed to obtain spherical phenolic resin particles.

2. The phenolic resin gas-solid integrated treatment method according to claim 1, characterized in that, S1 specifically refers to: S1.1 The waste gas generated during the production of phenolic resin is introduced into a spray tower and an absorbent is obtained by spraying with an alkaline solution. The pH of the alkaline solution is 9-12 and the temperature is 60-85℃. S1.

2. The pH of the absorption solution is adjusted to 9-12 using alkaline solution.

3. The phenolic resin gas-solid integrated treatment method according to claim 1, characterized in that, S2 specifically refers to: S2.1 Under anaerobic conditions, adjust the pH of the absorption solution to 5-7; S2.2, The absorbent after S2.1 is subjected to solid-liquid separation to obtain supernatant and solid; S2.

3. The supernatant is subjected to aerobic treatment, and the solid is dried to obtain spherical phenolic resin particles.

4. The phenolic resin gas-solid integrated treatment method according to claim 3, characterized in that, In S2.2, the supernatant has a phenol content of less than or equal to 100 ppm, an aldehyde content of less than or equal to 50 ppm, a COD of less than or equal to 10000 ppm, and a pH of 5 to 7.

5. The phenolic resin gas-solid integrated treatment method according to claim 3, characterized in that, It also includes S2.4, where the wastewater obtained after the supernatant is aerobically treated is used to produce formaldehyde solution.

6. The phenolic resin gas-solid integrated treatment method according to claim 1, characterized in that, In S2, the feed load for the anaerobic acidification treatment is 0.4~5 kg COD / d / m3.

7. Phenolic resin spherical particles prepared by the phenolic resin gas-solid integrated treatment method according to any one of claims 1 to 6.

8. The application of the phenolic resin spherical particles according to claim 7 in phenolic molding compounds, electrode materials, adsorbent materials, and catalyst supports.

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