Targeted adsorption catalyst, its preparation method and application

Abstract

The application discloses a targeted adsorption catalyst, which comprises a carrier and a molecular imprinting polymer loaded on the carrier, the carrier is manganese oxide loaded activated carbon, and the molecular imprinting polymer is a molecular imprinting polymer capable of selectively adsorbing sulfonamidopyridine; and the application also discloses a preparation method of the catalyst and application of the catalyst in degrading and treating wastewater containing sulfonamidopyridine. The targeted adsorption catalyst of the application plays the roles of an adsorbent and a catalyst simultaneously, directly carries out a catalytic oxidation reaction after adsorbing target molecules, degrades and treats the adsorbed pollutants, and completes the adsorption and degradation steps in one step, so that the treatment efficiency is improved; and after the catalyst is adsorbed and degraded, the catalyst can be directly recycled, and thus the catalyst does not need to pass through a desorption step, and the use efficiency of the catalyst is improved.

Description

[0001] ABSTRACT

[0002] The application discloses a MnOx-GAC / MIP catalyst and a preparation method and application thereof. The catalyst is prepared from activated carbon, saturated KMnO4 solution and dilute nitric acid as raw materials, through water bath heating, drying, calcination to form a granular carrier; then the granular carrier is mixed with a template molecule and a functional monomer, and further mixed with a crosslinking agent, an initiator and a reactant to perform a heating polymerization reaction, and the template molecule is extracted by Soxhlet extraction, and the MnOx-GAC / MIP catalyst is obtained through drying, grinding, screening and drying. The catalyst prepared by the application has high adsorption and degradation efficiency, can realize precise selective adsorption and catalytic degradation of target organic matters, and has strong controllability in the preparation process, and the prepared catalyst has good activity and high strength. TECHNICAL FIELD

[0003] The application relates to a targeted adsorption catalyst and a preparation method thereof, and can be used for adsorbing and catalytically oxidizing sulfapyridine. BACKGROUND

[0004] Sulfapyridine (SPY) is a common antibiotic pollutant in water bodies, mainly from pharmaceutical, breeding, medical and other industrial wastewater, and enters the surface and underground water through the discharge of domestic sewage, industrial wastewater, sewage plant, output of landfill leachate, agricultural livestock and aquaculture, etc. Antibiotics in the water environment have endocrine disrupting activity, toxicity effect, teratogenic and mutagenic effect on aquatic organisms due to their exogenous and high biological activity, and can induce the generation and spread of a large number of drug-resistant strains and antibiotic resistance genes.

[0005] Water treatment can generally use various adsorbents such as molecularly imprinted polymers to adsorb pollutants in water bodies, but adsorption is only a physical process, and the pollutants are not degraded and need to be desorbed, and the desorbed pollutants are then treated by degradation. The steps are complicated, and the degradation method is complex.

[0006] If SPY is directly degraded in water, SPY has the characteristics of low concentration ratio, high toxicity and difficult biodegradation in wastewater, so that the wastewater containing SPY presents the characteristics of coexistence of high toxicity, low concentration and low toxicity, and high concentration of other pollutants. The traditional wastewater treatment process such as the treatment method of oxidizing organic matters cannot concentrate on the pollutants with low concentration ratio due to the broad spectrum of active free radicals, and even preferentially attacks easily degradable organic matters, so that the free radicals cannot quickly contact with SPY, a large number of free radicals are directly quenched without use, and the free radicals cannot play an effective oxidation effect on SPY, so that the advanced oxidation technology (AOPs) has high cost and low degradation efficiency for SPY in water.

[0007] Therefore, the prior art is difficult to effectively remove SPY, cannot completely degrade and mineralize it, and makes the effluent difficult to meet the requirements, causing a series of environmental and human health problems.

[0008] In view of the low concentration of SPY, effective identification and efficient enrichment are key steps. Improving the accurate identification of target pollutants is one of the effective methods for efficient degradation of low-concentration SPY in water. The molecular imprinting technology can specifically capture antibiotics and realize efficient enrichment of antibiotics, and combined with the strong oxidation of AOPs, efficient degradation of low-concentration antibiotics can be realized. SUMMARY

[0009] In order to overcome the problems of low removal efficiency and difficult degradation of sulfapyridine in the prior art, the application provides a targeted adsorption catalyst (MnO x -GAC / MIP) and a preparation method and application thereof, so as to solve the problems of low efficiency and high cost of conventional degradation process of refractory pollutants SPY in wastewater.

[0010] The technical scheme adopted by the application is:

[0011] A targeted adsorption catalyst, the catalyst comprises a carrier and a molecular imprinting polymer loaded on the carrier, the carrier is manganese oxide loaded activated carbon, and the molecular imprinting polymer is a molecular imprinting polymer selectively adsorbing sulfapyridine.

[0012] Further, the manganese oxide loaded activated carbon is prepared by calcining activated carbon and potassium permanganate at high temperature.

[0013] The molecular imprinting polymer selectively adsorbing sulfapyridine is prepared by polymerization reaction using methyl acrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent, azobisisobutyronitrile as an initiator, and sulfapyridine as a template molecule, and then eluting the template molecule.

[0014] Further, in the manganese oxide loaded activated carbon, the mass ratio of activated carbon to manganese oxide is 1:0.01-0.1, preferably 1:0.04-0.08.

[0015] Further, in the targeted adsorption catalyst, the mass ratio of activated carbon to molecular imprinting polymer is 1:0.05-0.2, preferably 1:0.1-0.15.

[0016] The molar ratio of sulfapyridine, methyl acrylic acid, ethylene glycol dimethacrylate and azobisisobutyronitrile is 1:0.5-1:1-6:0.01-0.05.

[0017] Further, the preparation method of the targeted adsorption catalyst comprises the following steps:

[0018] (1) The activated carbon is dispersed in water, and saturated KMnO4 solution and dilute nitric acid are added dropwise under heating and stirring. After reaction for 2-4 hours, cooling is performed, and a pre-synthetic carrier is separated and washed and dried. High-temperature calcination is performed in an air environment for 2-4 hours to prepare the activated carbon loaded with manganese oxide;

[0019] The heating and stirring is generally performed at a temperature of 60-80°C and a rotation speed of 200-300 r / min for 5-10 min.

[0020] The concentration of the dilute nitric acid is generally 0.1-0.5 mol / L, and preferably 0.2 mol / L.

[0021] The volume ratio of the saturated KMnO4 solution to the dilute nitric acid is generally 1:0.5-2, and preferably 1:1.

[0022] The volume of the saturated KMnO4 solution is generally 10-30 mL / g of the activated carbon, and preferably 15-20 mL / g.

[0023] The volume of the water used for dispersing the activated carbon is generally 10-30 mL / g of the activated carbon.

[0024] The washing can be performed with water and methanol until the washing liquid is neutral.

[0025] The drying is generally performed at 100-110°C for 8-10 hours.

[0026] The high-temperature calcination is generally performed at a temperature of 200-300°C for 2-4 hours.

[0027] The calcination temperature is preferably 250°C, and the calcination time is preferably 3 hours.

[0028] (2) The template molecule sulfonamidopyridine, the functional monomer methacrylic acid, the first part of acetonitrile, ultrasonic mixing, cooling and pre-polymerization, the obtained mixture is added with the activated carbon loaded with manganese oxide, the crosslinking agent ethylene glycol dimethacrylate, the initiator azobisisobutyronitrile, and the second part of acetonitrile is added, ultrasonic mixing, deoxygenation, and closed heating and stirring, and polymerization is performed. The obtained solid product is washed to remove the template molecule, and the targeted adsorption catalyst loaded with the molecularly imprinted polymer is prepared.

[0029] The mass ratio of the template molecule sulfonamidopyridine to the functional monomer methacrylic acid is 1:0.5-1, and preferably 1:0.5-0.8.

[0030] The amount of substance of the template molecule sulfonamide pyridine is 0.3-1.5 mmol / g, preferably 0.5-1.2 mmol / g, and more preferably 0.8-1.2 mmol / g, based on the mass of the manganese oxide-loaded activated carbon.

[0031] The volume of the first part of acetonitrile is 0.5-5 mL / mmol, preferably 1-2 mL / mmol, based on the amount of substance of sulfonamide pyridine.

[0032] The temperature of the prepolymerization reaction is generally 3-5°C, preferably 4°C.

[0033] The time of the prepolymerization reaction is generally 0.5-2 h, preferably 1 h.

[0034] The amount-of-substance ratio of the template molecule to the initiator is 2-4:0.05, preferably 2.5-3.5:0.05.

[0035] The amount-of-substance ratio of the crosslinking agent to the initiator is 5-15:0.05, preferably 10:0.05.

[0036] The volume of the second part of acetonitrile is 1-10 mL / g, preferably 2.5-5 mL / g, based on the mass of the manganese oxide-loaded activated carbon.

[0037] The oxygen removal is generally performed by blowing nitrogen for 10-20 min.

[0038] The temperature of the polymerization reaction is generally 50-90°C, preferably 70°C. The reaction time of the polymerization reaction is 10-15 h, preferably 12 h.

[0039] The obtained solid product is washed to remove the template molecule. The washing is generally performed using acetonitrile and distilled water.

[0040] The template molecule is removed by stirring in a mixed solution of methanol and acetic acid in a volume ratio of 7:3 for 5-10 h, followed by Soxhlet extraction in a mixed solution of methanol and acetic acid in a volume ratio of 9:1 heated to 85°C to elute the template molecule.

[0041] After the template molecule is removed, the product is washed with methanol and distilled water multiple times and dried under vacuum to obtain a targeted adsorption catalyst loaded with a molecularly imprinted polymer.

[0042] The application also provides the use of the targeted adsorption catalyst in the degradation treatment of wastewater containing sulfonamide pyridine.

[0043] Further, the method of the use is as follows: the targeted adsorption catalyst is added to wastewater containing sulfonamide pyridine, the target compound is adsorbed, and then an oxidizing agent is added to perform a catalytic oxidation reaction at room temperature to obtain wastewater after sulfonamide pyridine degradation treatment.

[0044] The oxidant is hydrogen peroxide or potassium persulfate.

[0045] The adsorption time is generally 4-6 hours. The oxidation reaction time is generally 1-2 hours.

[0046] The removal rate of sulfapyridine can reach more than 90%.

[0047] The present application can treat sulfapyridine wastewater with a concentration as low as 0.5 mg / L, and has good treatment effect on low-concentration wastewater.

[0048] Moreover, the present application can precisely target and treat low-concentration sulfapyridine in high-concentration organic wastewater, and is not affected by high-concentration other organic pollutants.

[0049] When the wastewater containing sulfapyridine contains other organic pollutants with a concentration of 100-1000 mg / L, the removal rate of low-concentration (10-50 mg / L) sulfapyridine by the targeted adsorption catalyst can also reach more than 90%.

[0050] Further, the amount of the targeted adsorption catalyst used is 1-5 g per liter of wastewater.

[0051] The amount of the oxidant used is 3-10 g per liter of wastewater.

[0052] The adsorption reaction time is generally 4-6 hours.

[0053] The catalytic oxidation reaction time is generally 1-2 hours.

[0054] The present application first uses activated carbon and potassium permanganate to prepare MnOx-GAC catalyst by high-temperature calcination, uses MnOx-GAC as a carrier, and loads molecularly imprinted polymers (MIPs) with targeted recognition on the surface by a hydrothermal method. MIPs achieve targeted recognition of target molecules by constructing selective recognition sites of target molecules (SPY), and realize efficient enrichment of pollutants; MnOx-GAC has catalytic active sites that can catalyze active oxidants, so as to produce free radicals with strong oxidation effect to degrade target pollutants, thereby realizing targeted degradation of pollutants. Since the catalytic active sites and the targeted recognition sites of MnOx-GAC / MIP are both distributed on the surface of activated carbon (GAC), the mass transfer efficiency of free radicals and target pollutants (SPY) is greatly improved, and the degradation efficiency of SPY is improved.

[0055] The removal rate of sulfapyridine can reach 96.2% according to the present application, the targeted adsorption catalyst of the present application simultaneously plays the roles of an adsorbent and a catalyst, directly performs a catalytic oxidation reaction after adsorption, and the targeted adsorbent of the prior art only has an adsorption effect, and cannot play a catalytic role, so that after adsorbing pollutants, desorption is needed, and the desorbed pollutants need to be further treated and degraded, which is complicated and high in cost. The present application directly performs an oxidation reaction after adsorption, degrades and treats the adsorbed pollutants, does not need desorption and further degradation, completes the adsorption and degradation steps in one step, improves the treatment efficiency, and after adsorption and degradation of the catalyst, the catalyst can be directly recycled further, without the need of a desorption step, and the use efficiency of the catalyst is also improved. BRIEF DESCRIPTION OF DRAWINGS

[0056] Figure 1 XRD patterns of MnOx-GAC / MIP, MnOx-GAC and GAC. DETAILED DESCRIPTION

[0057] The technical solutions of the present application are further described below with specific examples, but the protection scope of the present application is not limited thereto.

[0058] Example 1

[0059] Preparation of manganese oxide loaded activated carbon MnOx-GAC:

[0060] 2-4 g of granular activated carbon was added into a conical flask containing 50 mL of deionized water, and stirred at 60-80℃ and 200 r / min in a water bath for 5 min. Then, saturated KMnO4 solution and 0.2 mol / L dilute nitric acid with a volume ratio of 1:2-2:1 were added dropwise, and reacted for 2-4 h. After cooling to room temperature, separation was performed to obtain a pre-synthesized carrier, which was washed with water and methanol until the solution was neutral, and then dried in an oven at 101.2℃ for 8 h. Finally, it was placed in a tube furnace at 200-300℃ and calcined in an air environment for 2-4 h to obtain the MnOx-GAC catalyst, which was placed in a dry dish for use.

[0061] The raw material amount, reaction temperature and time for preparing the pre-synthesized carrier are shown in Table 1.

[0062] Table 1:

[0063]

[0064] The six pre-synthesized carriers Pre-MnOx-GAC-1-Pre-MnOx-GAC-6 prepared in Table 1 were calcined in a tube furnace at 250℃ in an air environment for 3 h to obtain six manganese oxide loaded activated carbons MnOx-GAC, and the particle size and specific surface area are shown in Table 2.

[0065] Table 2

[0066]

[0067]

[0068] Pre-MnOx-GAC-3 was selected as the pre-synthesized carrier by comparing the particle size and the specific surface area. Then, the pre-synthesized carrier was calcined in a tube furnace at different calcination temperatures for different calcination times. The calcination temperatures and the calcination times are shown in Table 3.

[0069] Table 3

[0070] Calcination temperature (°C) Calcination time (h) MnOx-GAC-1 200 2 MnOx-GAC-2 250 3 MnOx-GAC-3 250 3 MnOx-GAC-4 300 4 MnOx-GAC-5 200 2 MnOx-GAC-6 250 3

[0071] 0.1 g of the prepared six kinds of MnOx-GAC was put into 1 L of SPY wastewater with a concentration of 20 mg / L, and then stirred uniformly. After 4 hours of adsorption, the removal rate was shown in Table 4.

[0072] Table 4

[0073]

[0074] The results in Table 4 show that MnOx-GAC-3 has the best adsorption effect on SPY. The weight of the calcined MnOx-GAC-3 is 3.174 g, the weight gain is 0.174 g, and the loading of manganese oxide is 5.8%.

[0075] Example 2

[0076] MnOx-GAC / MIP was prepared by hydrothermal method: the functional monomer (MAA), the crosslinking agent ethylene glycol dimethacrylate (EGDMA), and the initiator azobisisobutyronitrile (AIBN) were mixed with MnOx-GAC-3 uniformly, and then the polymerization reaction was carried out by water bath heating.

[0077] The functional monomer (MAA) and the template molecule (SPY) with a molar ratio of 1:1 to 1:3 were added to a 50 mL centrifuge tube, 4 mL of acetonitrile was added, and then ultrasonic treatment was carried out to mix uniformly. Then, the pre-polymerization reaction was carried out at a temperature of 3-5℃ for 1 h.

[0078] The raw materials and the reaction temperature are shown in Table 5

[0079] Table 5

[0080]

[0081] The crosslinking agent and initiator were added to the cooled mixture, the amount-of-substance ratio of the crosslinking agent and initiator was 5-15:0.05, 3 g of MnOx-GAC-3 and 10 mL of acetonitrile were added, ultrasonic dissolution was performed for 30 min, oxygen was removed by blowing nitrogen for 10 min, the mixture was sealed, and the sealed mixture was added to a water bath at 50-90°C to perform a polymerization reaction, and stirring was performed for 12 h.

[0082] The amount of the crosslinking agent and initiator and the reaction temperature are shown in Table 6.

[0083] Table 6

[0084]

[0085]

[0086] The obtained solid product was washed with acetonitrile and distilled water in sequence, then was stirred in a mixed solution (V methanol:V acetic acid = 7:3) for 6 h to remove the imprinted SPY in the polymer network, Soxhlet extraction was performed using a methanol / acetic acid mixture (9:1, v / v) at 85°C to elute the template molecule SPY, finally, the methanol and distilled water were repeatedly washed, and the product was dried under vacuum at 65°C overnight and was used, to obtain the MnOx-GAC / MIP catalyst with specific recognition sites, which were respectively recorded as MnOx-GAC / MIP-1-MnOx-GAC / MIP-6.

[0087] Example 3

[0088] Application of the MnOx-GAC / MIP:

[0089] 0.1 g of the MnOx-GAC / MIP was put into 1 L of SPY wastewater with a concentration of 20 mg / L, and after being fully stirred and uniformly mixed, 4 g / L of the potassium persulfate catalyst was added to start the reaction, and samples were taken at 0, 5, 10, 15, 20, 30 and 60 min.

[0090]

[0091] C t Ct is the concentration of SPY after the reaction for t minutes, and C0 is the initial concentration of SPY

[0092] The removal rates of different MnOx-GAC / MIPs on SPY are shown in Table 7.

[0093] Table 7

[0094]

[0095]

[0096] According to the experimental results, the MnOx-GAC / MIP-3 catalyst has the best effect on the removal of SPY, and therefore the final preparation scheme is determined as follows:

[0097] Take 3 g of granular activated carbon and add it to a conical flask containing 50 mL of deionized water, and stir for 5 min under the condition of 70°C and 200 r / min water bath heating. Then add 50 mL of saturated KMnO4 solution drop by drop, and after 15 min, add 50 mL of 0.2 mol / L dilute nitric acid drop by drop. React for 3 h, then cool to room temperature, and separate by standing. Wash with water and methanol until the solution is neutral, then dry in an oven at 101.2°C for 8 h. Finally, place in a tube furnace at 250°C and calcine for 3 h in an air environment to obtain the MnOx-GAC catalyst, which is placed in a dry dish for use.

[0098] Add 3.35 mmol of template molecule SPY and 2 mmol of functional monomer MAA to a 50 mL centrifuge tube, add 4 mL of acetonitrile, and ultrasonically treat to mix uniformly, then cool in a 4°C environment for 1 h.

[0099] Add 3 g of MnOx-GAC catalyst, 10 mmol of crosslinking agent EDGMA, 0.05 mmol of initiator AIBN, and 10 mL of acetonitrile to the cooled mixture, ultrasonically dissolve for 30 min, and blow off oxygen with nitrogen for 10 min. Seal, and place the sealed mixture in a 70°C water bath and stir for 12 h, then wash and remove the template molecule to obtain the target adsorption catalyst.

[0100] The X-ray crystal diffraction pattern of MnOx-GAC / MIP-3 is shown in Figure 1 Figure 1 MnOx-GAC / MIP is MnOx-GAC / MIP-3, and MnOx-GAC is MnOx-GAC-3.

[0101] Figure 1 MnOx-GAC / MIP-3 has strong diffraction at 2θ = 32.9°, 38.1°, 55.2°, and 65.8°, indicating that Mn mainly exists in the form of Mn 3+ oxide on the MnOx-GAC / MIP-3 catalyst. And all samples have similar intensity diffraction peaks between 30° and 60°, meaning that the MIP does not destroy the crystal form of MnOx-GAC. The diffraction peak intensity at 29.960° and 35.307° is enhanced, indicating that excessive Mn doping leads to an increase in Mn-O oxide structure.

[0102] ​The prepared MnOx-GAC / MIP-3 catalyst is added to the wastewater to be treated, and then stirred thoroughly to perform a specific adsorption reaction, and after the adsorption equilibrium is reached, an oxidizing agent (potassium persulfate, PDS) is added to the system to perform targeted adsorption and degradation of the target pollutant SPY.

[0103] Example 4

[0104] After 2.4 g / L of the MnOx-GAC / MIP-3 catalyst is added to a mixed solution containing 20 mg / L of SPY and similar-structure pollutants (sulfonamides SA 20 mg / L, sulfadiazine SDZ 20 mg / L, sulfamethoxazole SMX 20 mg / L) and adsorbed for 4 hours, 5 g / L of potassium persulfate is added, and the reaction is performed for 60 minutes. The degradation effects of the MnOx-GAC / MIP-3 catalyst on the four pollutants are shown in Table 8.

[0105] Table 8 Degradation effects of MnOx-GAC / MIP-3 on four pollutants

[0106]

[0107] In Table 5, -240 min refers to the initial concentration of the pollutant before treatment.

[0108] After adsorption for 4 hours (240 min), 0 min represents the pollutant concentration after adsorption and before the addition of the persulfate oxidizing agent, and the subsequent time represents the time after the addition of the potassium persulfate oxidizing agent. The results show that the adsorption efficiencies of all the pollutants (SA, SDZ, SPY, and SMX) on the MnOx-GAC / MIP catalyst are 10.80%, 22.80%, 46.65%, and 16.55%, respectively, and the adsorption efficiency on SPY is the highest, with a concentration decrease of about half.

[0109] After adsorption, the potassium persulfate oxidizing agent is added for oxidative degradation, and the degradation efficiencies are 74.5%, 82.6%, 92.9%, and 77.4%, respectively. The total removal rate of SPY reaches 96.2%; it is shown that the MnOx-GAC / MIP catalyst prepared in the application has adsorption and removal effects on SPY and similar-structure substances, but the adsorption and degradation effects on the target substance SPY are the best, which shows that the MnOx-GAC / MIP catalyst has good targeted recognition ability for the target pollutant, and can realize precise recognition and degradation of the pollutant.

[0110] Example 5

[0111] After 2.4 g / L of MnOx-GAC / MIP-3 catalyst was added to the mixed solution containing 20 mg / L SPY and 500 mg / L glucose and adsorbed for 4 hours, 5 g / L potassium persulfate was added, and the reaction was carried out for 60 minutes. The total removal rate of SPY reached 93.54%. After 2.4 g / L of MnOx-GAC-3 catalyst was added to the mixed solution containing 20 mg / L SPY and 500 mg / L glucose and adsorbed for 4 hours, 5 g / L potassium persulfate was added, and the reaction was carried out for 60 minutes. The total removal rate of SPY was 79.11%.

[0112] It can be seen that in the wastewater containing low concentration of sulfapyridine and high concentration of organic matter (the concentration of glucose is 25 times that of SPY), the MnOx-GAC / MIP catalyst can precisely target the removal of SPY, and the removal rate reaches more than 93%, without being affected by the high concentration of other organic matters. The removal rate of SPY by the MnOx-GAC-3 catalyst without molecularly imprinted polymer is significantly reduced, which is obviously affected by the high concentration of organic matter. In high-concentration organic wastewater, the target molecule with low concentration and high toxicity cannot be precisely targeted and removed.

[0113] Example 6

[0114] The used MnOx-GAC / MIP-3 catalyst in Example 4 was recovered by filtration and drying. The recovery rate of the catalyst can reach 86.43%. The catalyst was again put into the same wastewater to be treated, and the treatment steps were the same as in Example 3. The total removal rate of SPY was 89.65%. It can be seen that the MnOx-GAC / MIP catalyst can be recycled, and the treatment efficiency does not change significantly.

Claims

1. A targeted adsorbent catalyst characterized in that The targeted adsorption catalyst comprises a carrier and a molecular imprinting polymer loaded on the carrier, the carrier is manganese oxide loaded activated carbon, the manganese oxide loaded activated carbon is prepared by calcining activated carbon and potassium permanganate at high temperature; the molecular imprinting polymer is a molecular imprinting polymer selectively adsorbing sulfonamidopyridine; the targeted adsorption catalyst simultaneously plays the roles of an adsorbent and a catalyst. The preparation method of the targeted adsorption catalyst comprises the following steps: (1) the activated carbon is dispersed in water, and the saturated KMnO4 solution and dilute nitric acid are added dropwise under heating and stirring, the reaction is carried out for 2-4 hours, then the mixture is cooled, and the pre-synthetic carrier is separated and washed, and then dried and calcined at high temperature in air for 2-4 hours to prepare the manganese oxide loaded activated carbon; (2) the template molecule sulfonamidopyridine, the functional monomer methacrylic acid, the first part of acetonitrile, and the ultrasonic mixture are uniformly mixed, and the pre-polymerization reaction is carried out after cooling; the obtained mixture is added with the manganese oxide loaded activated carbon, the crosslinking agent ethylene glycol dimethacrylate, and the initiator azobisisobutyronitrile, and then the second part of acetonitrile is added, the ultrasonic mixture is uniformly mixed, oxygen is removed, and the polymerization reaction is carried out under heating and stirring in a closed state; the obtained solid product is washed to remove the template molecule, and the targeted adsorption catalyst loaded with the molecular imprinting polymer is prepared; the mass ratio of the sulfonamidopyridine, the methacrylic acid, the ethylene glycol dimethacrylate, and the azobisisobutyronitrile is 1:0.5-1:1-6:0.01-0.

05.

2. The targeted adsorbent catalyst of claim 1, wherein In the manganese oxide loaded activated carbon, the mass ratio of the activated carbon and the manganese oxide is 1:0.01-0.

1.

3. The targeted adsorbent catalyst of claim 1, wherein In the step (1), the concentration of the dilute nitric acid is 0.1-0.5 mol / L, and the volume ratio of the saturated KMnO4 solution and the dilute nitric acid is 1:0.5-2; the volume of the saturated KMnO4 solution is 10-30 mL / g based on the mass of the activated carbon.

4. The targeted adsorbent catalyst of claim 1, wherein In the step (2), the mass ratio of the template molecule sulfonamidopyridine and the functional monomer methacrylic acid is 1:0.5-1, the mass of the template molecule sulfonamidopyridine is 0.3-1.5 mmol / g based on the mass of the manganese oxide loaded activated carbon, the pre-polymerization reaction temperature is 3-5 ℃, and the pre-polymerization reaction time is 0.5-2 h; The mass ratio of the template molecule and the initiator is 2-4:0.05, the mass ratio of the crosslinking agent and the initiator is 5-15:0.05; the polymerization reaction temperature is 50-90 ℃, and the polymerization reaction time is 10-15 h.

5. The targeted adsorption catalyst according to any one of claims 1-4 is applied to the degradation treatment of wastewater containing sulfonamidopyridine. The application method is that the targeted adsorption catalyst is added into the wastewater containing sulfonamidopyridine, the target compound is adsorbed, then an oxidizing agent is added, and the catalytic oxidation reaction is carried out at room temperature to obtain the wastewater after the sulfonamidopyridine is degraded. ​ 6. The use according to claim 5, wherein ​

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