Induced catalytic oxidation and flocculation process for medical intermediate wastewater

Abstract

The invention relates to the technical field of resource and environment protection, in particular to an induced catalytic oxidation and flocculation process of medical intermediate wastewater, and aims to improve the treatment efficiency of the medical wastewater and the resource consumption in the sewage treatment process. The degradation and removal of pollutants such as organic matters, ammonia nitrogen and the like in the wastewater are realized by using a process of compounding different types of additives and performing microwave catalytic oxidation; on the basis, the modified PAM flocculant is further prepared, the modified PAM contains a large number of holes brought by a branched structure and can further adsorb and wrap a large number of guest molecules, and due to the fact that chitosan also has partial cationic property, the finally prepared modified PAM has cationic charges, and the cationic charges can be used for adsorbing and wrapping a large number of guest molecules. Therefore, the potential of impurities in the water body is neutralized, and the impurities are adsorbed.

Description

Technical Field

[0001] The invention relates to the technical field of resources and environmental protection, in particular to an induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater. Background Art

[0002] At present, with the development of my country's pharmaceutical industry, the amount of pharmaceutical industry production wastewater is increasing. Compared with general traditional industrial wastewater, the high organic matter pollution in the production of pharmaceutical intermediates is often more serious, and usually requires a multi-stage treatment method of "physical and chemical method" and "biochemical method"; these traditional methods have uneven treatment time and unstable operation, and often require more than one treatment to meet the emission standards, which seriously affects the production progress and treatment costs of the enterprise. Summary of the invention

[0003] The purpose of the present invention is to provide an induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater to solve the problems raised in the prior art.

[0004] To achieve the above object, the present invention provides the following technical solution: an induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 30-50% and a pressure of 0.4-0.6MPa. After the suspended matter in the wastewater floats to the surface of the water body, the surface suspended matter is removed to obtain the wastewater clear liquid; S2. After adding the oxidant and the additive ADD-1 to the lower supernatant, an alkali solution was added thereto to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30-45min, and the wastewater was passed into the primary oxidation tank for oxidation treatment; S3. The wastewater in the primary oxidation tank is introduced into air. After the oxidation reaction lasts for 20-40 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value is stable, the additive ADD-2 is added thereto. After the reaction lasts for 20-30 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 10.5-12, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. After the reaction lasts for 3-6 minutes, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7-7.5, add PAC and modified PAM, and after precipitation, discharge the supernatant of the wastewater, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again.

[0005] Furthermore, in step S2, the oxidant is hydrogen peroxide with a concentration of 25-30%, and the additive ADD-1 is ferric perchlorate.

[0006] Furthermore, in step S2, the amount of the oxidant added is 3-5% of the mass of the wastewater, and the amount of the additive ADD-1 added is 5-8% of the mass of the wastewater.

[0007] Furthermore, in step S3, the gas-liquid ratio of air to wastewater is (400-500):1.

[0008] Furthermore, in step S3, the additive ADD-2 is sodium persulfate, and the addition amount is 2.5-4% of the mass of the wastewater.

[0009] Furthermore, in step S3, the microwave induced catalytic oxidation main reactor has a wave energy power of 1-1.5 KVA / m 3 Wastewater.

[0010] Furthermore, in step S4, the amount of PAC added is 10-20 mg / L, and the amount of modified PAM added is 8-12 mg / L.

[0011] Furthermore, in step S4, the preparation method of the modified PAM is: After nitrogen is introduced into deionized water for 30-45 minutes, acetic acid is added thereto to prepare a 1wt% acetic acid solution, glycerol is added thereto and mixed evenly, chitosan and acryloyloxyethyl trimethyl ammonium chloride are added thereto, mixing is continued for 15-30 minutes, the temperature is raised to 45-50° C., 1 / 2 of cerium nitrate is added thereto dropwise, stirring and reacting for 15-30 minutes, the mixture is slowly dropped into the acrylamide aqueous solution, the remaining 1 / 2 of cerium nitrate is added after the addition is completed, the temperature is raised to 50-55° C., the reaction is continued for 2-3 hours, the reaction is stopped, excess solvent is removed by rotary evaporation, the remaining reaction product is washed with acetone for 2-3 times, and vacuum dried to constant weight to obtain modified PAM.

[0012] Furthermore, the mass ratio of the glycerol, chitosan and acryloyloxyethyltrimethylammonium chloride is 0.5:(1-3):(1.5-2).

[0013] Furthermore, the mass ratio of chitosan to cerium nitrate and acrylamide is (1-3): (0.003-0.005): 15 Compared with the prior art, the present invention has the following beneficial effects: In order to improve the treatment efficiency of pharmaceutical wastewater and the resource consumption in the sewage treatment process, the present invention uses MICO, i.e., multifunctional induced catalytic oxidation technology, to treat the wastewater. The present invention first performs aeration flotation treatment on the wastewater, and after the pollutants are initially removed, the wastewater is passed into a regulating tank, and the pollutants are further treated under the action of an oxidant and an additive ADD-1. After the air oxidation treatment, the additive ADD-2 is added again to further oxidize the wastewater; The additive ADD-1 used in the present invention is ferrate, and its stable valence state is +6. When the pH value is 2-4, its redox potential can reach 2.2V. In this case, the combined action of hydrogen peroxide and ferrate can produce a Fenton reaction, and the change of the hydroxyl radical OH· gives it an additional oxidation potential of 1.8-2.7V, thereby further improving the oxidative degradation ability of organic matter in the wastewater; and on this basis, the present invention also adds an additive ADD-2, which is a persulfate. When added to the wastewater, under the action of the additive ADD-1, a new sulfate radical SO4 will be generated - , its redox potential can reach 2.5-3.1V, which greatly increases the oxidation capacity of the reaction system; The present invention also uses microwave synergistic technology to induce catalytic oxidation treatment of wastewater. Under the action of microwaves, the degradation of organic matter in the wastewater can be further enhanced. In the microwave treatment process, the activation energy of chemical reactions can be effectively reduced, the reaction kinetics can be changed, the degradation difficulty can be reduced, and the degradation efficiency can be improved. The ADD-2 added in the present invention is a persulfate, which can effectively absorb microwaves and generate active free radicals and hot spots, thereby accelerating the degradation of macromolecular organic matter. On this basis, the present invention further prepares a modified PAM flocculant, using chitosan as a raw material and glycerol as a branching agent, which are mixed with acrylamide to prepare a modified PAM with biodegradable properties. The modified PAM contains a large number of holes due to the branching structure, which can further adsorb and encapsulate a large number of guest molecules. In addition, since chitosan itself also has partial cationicity, the finally prepared modified PAM can have a cationic charge, thereby neutralizing the potential of impurities in the water body and adsorbing them. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings: Figure 1 It is a process flow diagram of the present invention. DETAILED DESCRIPTION

[0015] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] Example 1. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 5% ferric perchlorate by mass of the wastewater to the supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the gas-liquid ratio of air to wastewater being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate of 2.5% of the wastewater mass is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 8 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0017] Example 2. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 1, this embodiment increases the amount of ferric perchlorate added in step S2; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the gas-liquid ratio of air to wastewater being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate of 2.5% of the wastewater mass is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 8 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0018] Example 3. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 2, this example increases the amount of sodium persulfate added in step S3; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the air-to-wastewater gas-liquid ratio being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate (4% of the wastewater mass) is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 8 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0019] Example 4. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 3, this example increases the power of the microwave-induced catalytic oxidation main reactor in step S3; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the gas-liquid ratio of air to wastewater being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate of 4% of the wastewater mass is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1.5KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 8 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0020] Example 5. A multifunctional induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 3, this example increases the amount of modified PAM added in step S4; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, and the gas-liquid ratio of air to wastewater is 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate of 4% of the wastewater mass is added, and sodium hydroxide is added. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 12 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0021] Example 6. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 5, this example increases the amount of chitosan added in step S4; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the air-to-wastewater gas-liquid ratio being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate (4% of the wastewater mass) is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 12 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 3 parts of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0022] Example 7. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 6, this example increases the amount of acryloyloxyethyl trimethyl ammonium chloride added in step S4; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 8% ferric perchlorate by mass of the wastewater to the lower supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, with the air-to-wastewater gas-liquid ratio being 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate (4% of the wastewater mass) is added thereto. After the reaction for 25 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 11, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. The wave energy power of the microwave-induced catalytic oxidation main reactor is 1KVA / m3 per cubic meter. 3 After 5 minutes of reaction, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 12 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol was added thereto and mixed evenly, 3 parts of chitosan and 2 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0023] Comparative Example 1. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, comprising the following steps: Compared with Example 1, this comparative example does not use a microwave-induced catalytic oxidation main reactor to treat wastewater; S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 40% and a pressure of 0.5MPa. After the suspended solids in the wastewater float to the surface of the water body, the surface suspended solids are removed to obtain the wastewater clear liquid; S2. After adding 3% hydrogen peroxide and 5% ferric perchlorate by mass of the wastewater to the supernatant, an alkali solution was added to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30 minutes, and the wastewater was passed into the primary oxidation tank for oxidation treatment; Wherein, the concentration of hydrogen peroxide is 30%; S3. Air is introduced into the wastewater in the primary oxidation tank, and the gas-liquid ratio of air to wastewater is 500:1. After the oxidation reaction for 30 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value stabilizes, sodium persulfate of 2.5% of the wastewater mass is added thereto. After the reaction for 25 minutes, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7, add 10 mg / L PAC and 8 mg / L modified PAM, and after precipitation, discharge the wastewater supernatant, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again; Wherein, the preparation method of the modified PAM is: By weight, after nitrogen was introduced into deionized water for 45 minutes, acetic acid was added thereto to prepare a 1wt% acetic acid solution, 0.5 parts of glycerol were added thereto and mixed evenly, 1 part of chitosan and 1.5 parts of acryloyloxyethyl trimethyl ammonium chloride were added thereto, and mixing was continued for 15 minutes, and the temperature was raised to 45°C, 0.0015 parts of cerium nitrate were added thereto dropwise, and after stirring and reacting for 30 minutes, the mixture was slowly added dropwise to an acrylamide aqueous solution containing 15 parts of acrylamide, and after the addition was completed, 0.0015 parts of cerium nitrate were continued to be added, and after the addition was completed, the temperature was raised to 50°C, and the reaction was continued for 2.5 hours, the reaction was stopped, and the excess solvent was removed by rotary evaporation, and the remaining reaction product was washed 3 times with acetone, and then vacuum dried to constant weight to obtain modified PAM.

[0024] Detection: According to the methods of Examples 1-7 and Comparative Example 1, the pharmaceutical wastewater was treated, and the test results are shown in the following table;

[0025] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater, characterized in that: The following steps are involved: S1. The pharmaceutical intermediate wastewater is discharged into the regulating tank and aerated under pressure. During the aeration process, the dissolved air water is refluxed at a reflux ratio of 30-50% and a pressure of 0.4-0.6MPa. After the suspended matter in the wastewater floats to the surface of the water body, the surface suspended matter is removed to obtain the wastewater clear liquid; S2. After adding the oxidant and the additive ADD-1 to the lower supernatant, an alkali solution was added thereto to control the pH value of the supernatant system to 2-4, and the reaction was stirred for 30-45min, and the wastewater was passed into the primary oxidation tank for oxidation treatment; S3. The wastewater in the primary oxidation tank is introduced into air. After the oxidation reaction lasts for 20-40 minutes, the wastewater is introduced into the secondary oxidation tank, and the pH value is adjusted to 2-4 again. After the pH value is stable, the additive ADD-2 is added thereto. After the reaction lasts for 20-30 minutes, sodium hydroxide is added thereto. After the pH value is adjusted to 10.5-12, the wastewater is discharged into the microwave-induced catalytic oxidation main reactor. After the reaction lasts for 3-6 minutes, the wastewater is discharged into the flocculation tank; S4. Add ferrous sulfate solution to the wastewater in the flocculation tank, adjust the pH value of the wastewater to 7-7.5, add PAC and modified PAM, and after precipitation, discharge the supernatant of the wastewater, collect the sludge, filter press, transport the sludge, and discharge the sludge filtrate into the primary oxidation tank again.

2. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S2, the oxidant is hydrogen peroxide with a concentration of 25-30%, and the additive ADD-1 is ferric perchlorate.

3. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S2, the amount of the oxidant added is 3-5% of the mass of the wastewater, and the amount of the additive ADD-1 added is 5-8% of the mass of the wastewater.

4. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S3, the gas-liquid ratio of air to wastewater is (400-500):

1.

5. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S3, the additive ADD-2 is sodium persulfate, and the addition amount is 2.5-4% of the mass of the wastewater.

6. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S3, the microwave induced catalytic oxidation main reactor has a wave energy power of 1-1.5 KVA / m3. 3 Wastewater.

7. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S4, the amount of PAC added is 10-20 mg / L, and the amount of modified PAM added is 8-12 mg / L.

8. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 1, characterized in that: In step S4, the preparation method of the modified PAM is: After nitrogen is introduced into deionized water for 30-45 minutes, acetic acid is added thereto to prepare a 1wt% acetic acid solution, glycerol is added thereto and mixed evenly, chitosan and acryloyloxyethyl trimethyl ammonium chloride are added thereto, mixing is continued for 15-30 minutes, the temperature is raised to 45-50° C., 1 / 2 of cerium nitrate is added thereto dropwise, stirring and reacting for 15-30 minutes, the mixture is slowly dropped into the acrylamide aqueous solution, the remaining 1 / 2 of cerium nitrate is added after the addition is completed, the temperature is raised to 50-55° C., the reaction is continued for 2-3 hours, the reaction is stopped, excess solvent is removed by rotary evaporation, the remaining reaction product is washed with acetone for 2-3 times, and vacuum dried to constant weight to obtain modified PAM.

9. The multifunctional induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 8, characterized in that: The mass ratio of the glycerol, chitosan and acryloyloxyethyl trimethyl ammonium chloride is 0.5: (1-3): (1.5-2).

10. The induced catalytic oxidation and flocculation process for pharmaceutical intermediate wastewater according to claim 8, characterized in that: The mass ratio of chitosan to cerium nitrate and acrylamide is (1-3): (0.003-0.005):15.

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