Resin adsorbent, its preparation process, use and treatment method of phenol-containing wastewater

Abstract

The resin adsorbent, its preparation process, application and treatment method of phenol-containing wastewater relate to the technical field of industrial wastewater treatment. The present application first takes a proper amount of tetrabutyl titanate, vinyl ferrocene, p-hydroxy styrene, divinyl benzene and methyl methacrylate as monomers, adds a proper amount of n-butyllithium as an initiator and n-heptane as a pore-forming agent, stirs and uniformly mixes in a THF system to form an oil phase, then suspends the oil phase in a dispersion medium to carry out suspension polymerization, shapes the oil phase to obtain spherical resin particles, separates the spherical resin particles, removes the pore-forming agent and then vacuum dries to obtain a granular product. The resin adsorbent prepared by the present application can not only achieve ideal treatment effects under acidic and alkaline conditions, but also has shorter phenol removal reaction time, higher efficiency and higher practical application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of industrial wastewater treatment, in particular to a resin adsorbent, a preparation process thereof and a method for treating phenol-containing wastewater by using the resin adsorbent. BACKGROUND

[0002] Among the industrial wastewater containing phenol, the content of phenol is the highest and the toxicity is the largest. At present, the treatment processes for phenol in industrial wastewater mainly include physical separation, chemical oxidation and biological conversion. The chemical oxidation process is concerned because of its high treatment efficiency and easy industrial implementation.

[0003] In the document“[1] Zhou L. Adsorption, oxidation and combined treatment process of phenol-containing wastewater[D]. Central South University, 2013.”, a method for treating phenol-containing wastewater by using adsorption-oxidation combined process is disclosed. H-103 macroporous resin is used as an adsorbent and Fenton reagent is used as an oxidant. The three-phase fluidized bed is used to make the resin particles completely fluidized to strengthen the phenol removal effect of the combined process. Under the conditions of initial concentration of phenol solution 100 mg / L, solution pH 4, reaction temperature 25C°, air flow rate 0.12 m 3 / h, resin solid content 1%, Fe 2+ concentration 3 mmol / L, H2O2 and Fe 2+ molar ratio 20:1, the phenol removal rate of 99.6% in the simulated wastewater is achieved. In the actual application of the above treatment process, it is difficult to accurately control the pH value. For example, when the pH value is greater than 8, the adsorption performance of H-103 resin will decrease significantly, resulting in poor treatment effect. Therefore, it is necessary to develop a new adsorbent with better adaptability to ensure the stability of the fluidized combined process. SUMMARY

[0004] One of the purposes of the present application is to provide a resin adsorbent which can ensure the phenol removal effect of the adsorption-oxidation combined process under acidic and alkaline conditions.

[0005] In order to achieve the above purpose, the following technical scheme is adopted in the present application: a resin adsorbent is prepared by the following process:

[0006] Firstly, a proper amount of tetrabutyl titanate, vinyl ferrocene, p-hydroxystyrene, di-vinyl benzene and methyl methacrylate are used as monomers, a proper amount of n-butyllithium is added as an initiator, n-heptane is used as a pore-forming agent, and the mixture is stirred in THF system to form an oil phase;

[0007] Secondly, the oil phase is added to a dispersion medium for suspension polymerization, and spherical resin particles are obtained after shaping;

[0008] Afterwards, the spherical resin particles are separated, dried in vacuum after removing the pore-forming agent, and a granular product is obtained.

[0009] One preferred solution further comprises: swelling the obtained granular product with 1,2-dichloroethane, adding an appropriate amount of catalyst FeCl3, and reacting at 50-60 C° until the reaction is completed, after which the obtained solid product is separated.

[0010] The molar ratio of tetrabutyl titanate, vinyl ferrocene, p-hydroxystyrene, divinylbenzene and methyl methacrylate is (2-3):(1-1.5):(50-65):(7-9):(4-5), the amount of the pore-forming agent is 1.5-2 times the total mass of all monomers, and the amount of the initiator is 0.3%-0.7% of the total mass of all monomers.

[0011] In particular, when the oil phase system is prepared, tetrabutyl titanate, vinyl ferrocene, an initiator, a part of p-hydroxystyrene and a part of methyl methacrylate are stirred uniformly in a THF system, and after being kept at 35-45 C° for 10-15 min, divinylbenzene, a pore-forming agent and the remaining p-hydroxystyrene and methyl methacrylate are added to the THF system; wherein the amount of p-hydroxystyrene initially added to the THF system accounts for 30%-40% of the total amount, and the amount of methyl methacrylate initially added to the THF system accounts for 35%-45% of the total amount.

[0012] The temperature condition for the suspension polymerization reaction is preferably: first, the mixed system is heated to 50-55 C° and kept for 0.5-1 h, and then heated to 75-80 C° and kept for 1.5-2 h.

[0013] In one preferred solution of the present application, the dispersion medium is an aqueous system, and the volume ratio of the aqueous system to the oil phase is (4-5):1; the aqueous system uses deionized water as the medium, sodium chloride as the stabilizer and gelatin as the dispersant, the mass fraction of the stabilizer is 5%-8%, and the mass fraction of the dispersant is 0.5%-1.5%.

[0014] In addition, the present application also relates to the application of the resin adsorbent in wastewater treatment.

[0015] Specifically, the present application relates to a treatment method for phenol-containing wastewater, which comprises the following steps: first, the wastewater is subjected to sedimentation and filtration treatment, and then an adsorption-oxidation combined process is used in a gas-liquid-solid three-phase fluidized bed to remove phenol in the wastewater, wherein the adsorption-oxidation combined process uses the resin adsorbent described above.

[0016] The adsorption-oxidation combined process comprises the following steps: adding FeSO 4·7H 2 O, H 2 O 2 and The resin adsorbent controls the Fe content in the reaction system. 2+ The concentration is 2-4 mmol / L, and the resin solid content is 0.5%-2%. H 2 O 2 with Fe 2+ The concentration ratio is (18-20):1, and the aeration rate is adjusted to keep the bed in a fully fluidized state. The reaction is carried out at room temperature for 3-5 minutes.

[0017] When the resin adsorbent prepared according to this invention was used in an adsorption-oxidation combined process for phenol removal at room temperature, it achieved relatively ideal treatment results under different acidic and alkaline conditions. Within a pH range of 4-10 (with other conditions remaining the same), the phenol removal rate fluctuation did not exceed 3%, effectively ensuring the stability of the phenol removal effect. When applied to a fluidized bed enhanced adsorption-oxidation combined process, compared with the prior art, it can remove phenol from wastewater in a shorter time, improving the phenol removal efficiency and making it more valuable for application. Attached Figure Description

[0018] Figure 1 The adsorbent particles prepared in Example 4.

[0019] Figure 2 This study compares the phenol removal efficiency of Examples 1-6 in the adsorption-oxidation combined process, with pH as a variable and other reaction conditions as constants.

[0020] Figure 3 In the adsorption-oxidation combined process, Fe 2+ The concentration is a variable, and other reaction conditions are constants. Comparison of phenol removal effects in Examples 1-6.

[0021] Figure 4 In the adsorption-oxidation combined process, with H 2 O 2 The concentration is a variable, and other reaction conditions are constants. Comparison of phenol removal effects in Examples 1-6.

[0022] Figure 5 In the adsorption-oxidation combined process, with resin solids content The phenol removal effects of Examples 1-6 are compared, with phenol as the variable and other reaction conditions as constants.

[0023] Figure 6This study compares the phenol removal efficiency of Examples 7-12 in the adsorption-oxidation combined process, with pH as a variable and other reaction conditions as constants.

[0024] Figure 7 In the adsorption-oxidation combined process, Fe 2+ The concentration was a variable, while other reaction conditions were constants. Comparison of phenol removal effects in Examples 7-12.

[0025] Figure 8 In the adsorption-oxidation combined process, with H 2 O 2 The concentration was a variable, while other reaction conditions were constants. Comparison of phenol removal effects in Examples 7-12.

[0026] Figure 9 In the adsorption-oxidation combined process, with resin solids content The phenol removal effects of Examples 7-12 are compared, with phenol as the variable and other reaction conditions as constants.

[0027] Figure 10 Examples 1-6 compare the removal efficiency of phenol from actual industrial wastewater in the fluidized bed enhanced adsorption-oxidation combined process.

[0028] Figure 11 Examples 7-12 compare the removal efficiency of phenol from actual industrial wastewater in the fluidized bed enhanced adsorption-oxidation combined process. Detailed Implementation

[0029] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to specific embodiments and accompanying drawings.

[0030] The main reagents and instruments used in the following experiments are:

[0031] Main reagents: p-hydroxystyrene (99.9%, Jinjinle Hunan Chemical Co., Ltd.); divinylbenzene (50%, Sinopharm Chemical Reagent); methyl methacrylate (99.5%, Jilin Petrochemical); vinyl ferrocene (98%, Sinopharm Chemical Reagent); tetrabutyl titanate (98%, Sinopharm Chemical Reagent); n-butyllithium (20%, cyclohexane, Baling Petrochemical); n-heptane (99%, Sinopharm Chemical Reagent); THF (AR, Shanghai Aladdin); anhydrous ethanol (AR, Sinopharm Chemical Reagent); 1,2-dichloroethane (99.5%, Sinopharm Chemical Reagent); anhydrous FeCl3 (98%, Yurui Chemical); gelatin (AR, Sinopharm Chemical Reagent); sodium chloride (AR, Sinopharm Chemical Reagent). FeSO 4 ·7H2 O (99%, Shanghai Aladdin); 30% H 2 O 2 (AR, Yonghua Chemical); Phenol (99%, Sinopharm Chemical Reagent); H2SO4 (95%, Sinopharm Chemical Reagent); Ammonia (28%, Sinopharm Chemical Reagent).

[0032] Main instruments and equipment: OS40-S electric stirrer (Kexing Instruments); HZ010t constant temperature water bath (Shanghai Experimental Instruments); ZK-82A vacuum drying oven (Shanghai Experimental Instruments); PHS-3C digital display pH meter (Hangzhou Qiwei Instruments); NAI-ST-6A Soxhlet extractor (Shanghai Nai Experimental Instruments); S22 visible spectrophotometer (Shanghai Lingguang Technology). Example 1

[0033] 1.1 Preparation of the oil phase system: Take 6.9g tetrabutyl titanate (about 0.02mol), 2.2g vinyl ferrocene (about 0.01mol), 53g p-hydroxystyrene (about 0.5mol), 9.3g divinylbenzene (about 0.07mol), 4g methyl methacrylate (about 0.04mol), 0.2g n-butyllithium, and 112g n-heptane and add them to the THF system. Stir in a stirrer to form the oil phase.

[0034] 1.2 Preparation of aqueous phase system (dispersion medium): Take 1000ml of deionized water, add appropriate amounts of sodium chloride and gelatin to it in sequence under stirring, slowly heat to 38°C, stir and mix well to obtain an aqueous phase system with a sodium chloride mass fraction of about 5% and a gelatin mass fraction of about 0.5%.

[0035] 1.3 The oil phase obtained in 1.1 was added to the aqueous phase system obtained in 1.2 for suspension polymerization. The volume ratio of the aqueous phase to the oil phase was controlled at 4:1. The mixture was heated to 50°C and held for 1 hour under stirring. Then it was heated to 80°C and held for 1.5 hours. After setting, spherical resin particles were obtained.

[0036] 1.4 The spherical resin particles obtained in 1.3 were separated and extracted with anhydrous ethanol in a Soxhlet extractor for 8 hours to remove the porogen. After removing the porogen, they were vacuum dried at a temperature not exceeding 80°C to obtain spherical resin adsorbent microspheres with a water content of about 15%. Example 2

[0037] Compared to Example 1, this embodiment adds a post-crosslinking reaction treatment to the resin microspheres during the preparation of spherical resin adsorbent particles. Specifically, after step 1.4, the following operation is also included:

[0038] 1.5 Take the dried spherical resin particles from 1.4, swell them with an appropriate amount of 1,2-dichloroethane, add the catalyst FeCl3, the mass ratio of spherical resin particles to catalyst is about 5:1, and react fully under the condition of keeping warm at 50-60°C. After the reaction is completed, separate the resin adsorbent particles. Example 3

[0039] In this embodiment, the process for preparing spherical resin adsorbent particles differs from that in Example 1 mainly in the different operation methods for preparing the oil phase system. Specifically, when preparing the oil phase system, tetrabutyl titanate, vinyl ferrocene, initiator, 30% of p-hydroxystyrene and 45% of methyl methacrylate are first stirred evenly in a THF system and kept at 35°C for 10 minutes. Then, divinylbenzene, porogen, and the remaining p-hydroxystyrene and methyl methacrylate are added to the THF system. Other conditions are the same as in Example 1. Example 4

[0040] Compared to Example 3, this embodiment adds a post-crosslinking reaction process to the resin microspheres during the preparation of spherical resin adsorbent particles, namely, the following operations are also included:

[0041] Take dried spherical resin particles, swell them with an appropriate amount of 1,2-dichloroethane, add FeCl3 catalyst (mass ratio of spherical resin particles to catalyst approximately 5:1), and react fully at 50-60°C. After the reaction is complete, separate the resin adsorbent particles, clean them, and then vacuum dry them to obtain the following product: Figure 1 The image shows grayish-brown microsphere-shaped adsorbent particles. Example 5

[0042] 1.1 Preparation of the oil phase system: Take 10.4g tetrabutyl titanate (about 0.03mol), 3.2g vinyl ferrocene (about 0.015mol), 69g p-hydroxystyrene (about 0.65mol), 11.9g divinylbenzene (about 0.09mol), 5g methyl methacrylate (about 0.05mol), 0.7g n-butyllithium, and 199g n-heptane and add them to the THF system. Stir in a stirrer to form the oil phase.

[0043] 1.2 Preparation of aqueous phase system (dispersion medium): Take 1000ml of deionized water, add sodium chloride and gelatin to it in sequence under stirring, and slowly heat to about 38°C to prepare an aqueous phase system with a sodium chloride mass fraction of about 8% and a gelatin mass fraction of about 1.5%.

[0044] 1.3 The oil phase obtained in 1.1 was added to the aqueous phase system obtained in 1.2 for suspension polymerization. The volume ratio of the aqueous phase to the oil phase was controlled at 5:1. The mixture was heated to 55°C and held for 0.5 h under stirring. Then it was heated to 75°C and held for 2 h. After setting, spherical resin particles were obtained.

[0045] 1.4 Separate the spherical resin particles obtained in 1.3, extract them with anhydrous ethanol in a Soxhlet extractor for about 8 hours to remove the pore-forming agent, and then vacuum dry them at a temperature not exceeding 80°C to obtain spherical resin adsorbent microspheres with a water content of about 15%. Example 6

[0046] Compared to Example 5, this embodiment adds a post-crosslinking reaction treatment to the resin microspheres during the preparation of spherical resin adsorbent particles. Specifically, after step 1.4, the following operation is also included:

[0047] 1.5 Take the dried spherical resin particles from 1.4, swell them with an appropriate amount of 1,2-dichloroethane, add the catalyst FeCl3, the mass ratio of spherical resin particles to catalyst is about 5:1, and react fully under the condition of keeping warm at 50-60°C. After the reaction is completed, separate the resin adsorbent particles. Example 7

[0048] In this embodiment, the process for preparing spherical resin adsorbent particles differs from that in Example 5 mainly in the different operation methods for preparing the oil phase system. Specifically, when preparing the oil phase system, tetrabutyl titanate, vinyl ferrocene, initiator, 40% of the total amount of p-hydroxystyrene, and 35% of the total amount of methyl methacrylate are first stirred evenly in a THF system and kept at 45°C for 10 minutes. Then, divinylbenzene, porogen, and the remaining p-hydroxystyrene and methyl methacrylate are added to the THF system. Other conditions are the same as in Example 5. Example 8

[0049] Compared to Example 7, this embodiment adds a post-crosslinking reaction process for the resin microspheres. That is, based on Example 7, it also includes the following operations: take the dried spherical resin particles, swell them with an appropriate amount of 1,2-dichloroethane, add the catalyst FeCl3, the mass ratio of spherical resin particles to catalyst is about 5:1, and react fully under the condition of keeping warm at 50-60°C. After the reaction is completed, separate the resin adsorbent particles, clean them, and then vacuum dry them to finally obtain gray-brown microspherical adsorbent particles. Example 9

[0050] 1.1 Preparation of the oil phase system: Take 8.5g tetrabutyl titanate, 2.8g vinyl ferrocene, 60g p-hydroxystyrene, 10.5g divinylbenzene, 4.5g methyl methacrylate, 0.5g n-butyllithium, and 150g n-heptane and add them to the THF system. Stir in a stirrer to form the oil phase.

[0051] 1.2 Preparation of aqueous phase system (dispersion medium): Take 1000ml of deionized water, add sodium chloride and gelatin to it in sequence under stirring, and slowly heat to about 38°C to prepare an aqueous phase system with a sodium chloride mass fraction of about 7% and a gelatin mass fraction of about 1%.

[0052] 1.3 The oil phase obtained in 1.1 was added to the aqueous phase system obtained in 1.2 for suspension polymerization. The volume ratio of the aqueous phase to the oil phase was controlled at 5:1. The mixture was heated to 53°C and held for 1 hour under stirring. Then it was heated to 77°C and held for 1.5 hours. After setting, spherical resin particles were obtained.

[0053] 1.4 Separate the spherical resin particles obtained in 1.3, extract them with anhydrous ethanol in a Soxhlet extractor for about 8 hours to remove the pore-forming agent, and then vacuum dry them at a temperature not exceeding 80°C to obtain spherical resin adsorbent microspheres with a water content of about 15%. Example 10

[0054] Compared to Example 9, this embodiment adds a post-crosslinking reaction treatment on the resin microspheres. The operation method of the post-crosslinking reaction is as follows: take the dried spherical resin particles, swell them with an appropriate amount of 1,2-dichloroethane, add the catalyst FeCl3, the mass ratio of spherical resin particles to catalyst is about 5:1, and react fully under the heat preservation condition of 50-60°C. After the reaction is completed, the resin adsorbent particles are separated. Example 11

[0055] The main difference between this embodiment and Example 9 in the preparation of the spherical resin adsorbent particles lies in the different operation method for preparing the oil phase system. In preparing the oil phase system, tetrabutyl titanate, vinyl ferrocene, initiator, 35% p-hydroxystyrene, and 40% methyl methacrylate are first stirred evenly in a THF system and kept at 40°C for 15 minutes. Then, divinylbenzene, porogen, and the remaining p-hydroxystyrene and methyl methacrylate are added to the THF system. Other conditions are the same as in Example 9. Example 12

[0056] Compared to Example 11, this embodiment adds a post-crosslinking reaction process to the resin microspheres. Specifically, based on Example 11, the following operations were performed: dried spherical resin particles were taken, swollen with an appropriate amount of 1,2-dichloroethane, and FeCl3 catalyst was added. The mass ratio of spherical resin particles to catalyst was approximately 5:1. The reaction was carried out at a temperature of 50-60°C until the reaction was completed. The resin adsorbent particles were then separated, cleaned, and vacuum dried to finally obtain gray-brown microspherical adsorbent particles.

[0057] In Examples 1-12 above, tetrabutyl titanate, vinyl ferrocene, p-hydroxystyrene, divinylbenzene, and methyl methacrylate are used as monomers participating in the reaction. n-Heptane is used as a pore-forming agent that does not participate in the polymerization reaction and can be removed from the resin particles by extraction. In the THF system with n-butyllithium as the initiator, vinyl ferrocene can copolymerize with p-hydroxystyrene, tetrabutyl titanate and methyl methacrylate undergo an addition reaction to form hydroxyethyl acrylate titanate, and the crosslinking agent divinylbenzene can copolymerize with p-hydroxystyrene and methyl methacrylate at the same time, so that the polymer chains form a crosslinked network structure, thereby realizing the copolymerization of each monomer to form spherical resin particle products. In an aqueous system, sodium chloride acts as a stabilizer, and gelatin acts as a dispersant. When the oil phase and the aqueous phase are mixed, they separate into layers. Under the shear force generated by stirring, the oil phase disperses into droplets in the aqueous phase. Due to the interfacial tension between the oil and aqueous phases, the dispersed droplets are spherical. Under stirring, the small droplets collide and aggregate into larger droplets, eventually forming spherical resin particles. The size of the formed spherical resin particles can be controlled by changing the stirring intensity, dispersant concentration, and stirring time.

[0058] 1. Simulated wastewater phenol removal test based on adsorption-oxidation combined process:

[0059] 1.1 Prepare an aqueous solution of phenol with a mass concentration of 1000 mg / L, and prepare an H2SO4 solution with a mass fraction of 50%.

[0060] 1.2 Take the prepared phenol aqueous solution, adjust its pH value with H2SO4 solution or ammonia water respectively, and then add an appropriate amount of FeSO 4 ·7H 2 O, H 2 O 2 and spherical particles prepared in Examples 1-12 The removal rate of phenol from simulated wastewater was tested using resin adsorbent granules under the following initial conditions, with a reaction time of 10 min for all conditions:

[0061]

[0062] The experimental results corresponding to Examples 1-6 are shown below. Figures 2-5 As shown, the experimental results corresponding to Examples 7-12 are as follows: Figures 6-9 As shown.

[0063] 2. Actual wastewater phenol removal test based on fluidized bed enhanced adsorption-oxidation combined process:

[0064] The actual wastewater to be treated was supplied by a coking plant of a steel company in Xiangtan, Hunan Province. After sedimentation, filtration, and pH adjustment with concentrated ammonia (pretreatment), the wastewater parameters are as follows (unit: mg / L):

[0065]

[0066] Using a three-phase fluidized bed with the same structure as in the background literature, at room temperature, the resin solids content in the reaction system is controlled at 1%, and Fe... 2+ The concentration is 3 mmol / L. H 2 O 2 content of The concentration was 60 mmol / L. The ventilation rate was adjusted to achieve a fully fluidized bed. The reaction time was set to 2-8 min, and the experimental results under different time conditions were recorded. The experimental results corresponding to Examples 1-6 are shown below. Figure 10 As shown, the experimental results corresponding to Examples 7-12 are as follows: Figure 11 As shown.

[0067] This invention modifies the resin polymer by introducing ferrocene and tetravalent titanium into the THF system, thereby improving the resin's adsorption capacity for phenol under alkaline conditions. The altered polymer structure increases reactive sites, enhances the synergistic effect with the oxidant, and improves phenol removal efficiency. Statistical experimental results show that the resin adsorbent particles prepared in the above embodiments, when applied to the adsorption-oxidation combined process, achieve ideal treatment effects under both acidic and alkaline conditions. Within a pH range of 4-10, the phenol removal rate fluctuation is within 3%, demonstrating stable phenol removal performance. Results from actual wastewater phenol removal tests using a fluidized bed enhanced adsorption-oxidation combined process show that this invention can still achieve the goal of phenol non-detectability under alkaline conditions. Particularly noteworthy is that, compared to the prior art, this invention can remove phenol from wastewater in a shorter time under conditions of lower resin solids content, significantly improving phenol removal efficiency and demonstrating greater practical application value.

[0068] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present technical solution are within the protection scope of the present invention.

Claims

1. A preparation process for resin adsorbents, characterized in that, Includes the following steps: 1) Using appropriate amounts of tetrabutyl titanate, vinyl ferrocene, p-hydroxystyrene, divinylbenzene and methyl methacrylate as monomers, and adding appropriate amounts of n-butyllithium as initiator and n-heptane as porogen, the mixture is stirred and mixed in a THF system to form an oil phase; the molar ratio of tetrabutyl titanate, vinyl ferrocene, p-hydroxystyrene, divinylbenzene and methyl methacrylate is (2-3):(1-1.5):(50-65):(7-9):(4-5); 2) The oil phase is added to a dispersion medium for suspension polymerization, and spherical resin particles are obtained after sizing. 3) Separate the spherical resin particles, remove the pore-forming agent, and then vacuum dry to obtain the granular product.

2. The preparation process as described in claim 1, characterized in that, Also includes: 4) Take the product obtained in step 3) and swell it with 1,2-dichloroethane. Add an appropriate amount of catalyst FeCl3 and react it fully under the condition of keeping it at 50-60℃. After the reaction is completed, separate the obtained solid product.

3. The preparation process as described in claim 1, characterized in that: In step 1), the amount of the porogen is 1.5-2 times the total mass of all monomers, and the amount of the initiator is 0.3%-0.7% of the total mass of all monomers.

4. The preparation process according to any one of claims 1-3, characterized in that: In step 1), tetrabutyl titanate, vinyl ferrocene, initiator, a portion of p-hydroxystyrene, and a portion of methyl methacrylate are first stirred evenly in a THF system and kept at 35-45℃ for 10-15 minutes. Then, divinylbenzene, porogen, and the remaining p-hydroxystyrene and methyl methacrylate are added to the THF system. The amount of p-hydroxystyrene initially added to the THF system accounts for 30%-40% of its total amount, and the amount of methyl methacrylate initially added to the THF system accounts for 35%-45% of its total amount.

5. The preparation process as described in claim 4, characterized in that: In step 2), the temperature conditions for the polymerization reaction are as follows: first, heat the mixed system to 50-55℃ and keep it at that temperature for 0.5-1h, then heat it to 75-80℃ and keep it at that temperature for 1.5-2h.

6. The preparation process according to any one of claims 1-3, characterized in that: The dispersion medium is an aqueous phase system, and its volume ratio with the oil phase is (4-5):

1. In the aqueous phase system, deionized water is used as the medium, sodium chloride is used as the stabilizer, and gelatin is used as the dispersant. The mass fraction of the stabilizer is 5%-8%, and the mass fraction of the dispersant is 0.5%-1.5%.

7. A resin adsorbent, characterized in that: It is prepared using the preparation process described in any one of claims 1-6.

8. The application of the resin adsorbent according to claim 7 in the treatment of phenol-containing wastewater.

9. A method for treating phenol-containing wastewater, characterized in that: The wastewater is first treated by sedimentation and filtration, and then phenol in the wastewater is removed by an adsorption-oxidation combined process in a gas-liquid-solid three-phase fluidized bed. The adsorption-oxidation combined process uses the resin adsorbent described in claim 7.

10. The processing method as described in claim 9, characterized in that, The adsorption-oxidation combined process includes the following steps: adding FeSO4·7H2O, H2O2, and the resin adsorbent to the wastewater, and controlling the Fe content in the reaction system. 2+ Concentration of 2-4 mmol / L, resin solid content of 0.5%-2%, H2O2 and Fe 2+ The concentration ratio was 20:1, and the aeration rate was adjusted to keep the bed in a fully fluidized state. The reaction was carried out at room temperature for 3-5 minutes.

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