Method for treating high-chlorophenol cyanide wastewater

Abstract

The application relates to the technical field of wastewater treatment, and discloses a high-chlorophenol cyanogen wastewater treatment method, which comprises the following steps: adjusting the pH of high-chlorophenol cyanogen wastewater by using an alkaline substance, standing to form a precipitate, skimming the precipitate, filtering, and collecting pretreated high-chlorophenol cyanogen wastewater; adding a composite adsorbent to the pretreated high-chlorophenol cyanogen wastewater, carrying out adsorption treatment, filtering, collecting the wastewater and the precipitate after adsorption, mixing the wastewater and a microbial agent, carrying out biochemical treatment, standing to precipitate, filtering, collecting the wastewater after biochemical treatment, and carrying out detection and discharge. The high-chlorophenol cyanogen wastewater is subjected to adsorption treatment by using the composite adsorbent, most of the organic pollutant in the wastewater is effectively removed, the content of chloride ions is reduced, and a suitable environment is provided for biochemical treatment of the wastewater; then the wastewater is subjected to biochemical treatment by mixing the microbial agent, the organic pollutants which are difficult to remove by adsorption in the wastewater are deeply removed, the treated wastewater meets the water outlet indexes, and can be directly discharged.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically a method for treating high-chlorine phenol-cyanide wastewater. Background Technology

[0002] Coking wastewater (perchlorinated phenol-cyanide wastewater) is generated during the coking, coal gas purification, and chemical product refining processes. Its main pollutants include phenols, cyanides, polycyclic aromatic compounds, and heterocyclic compounds containing nitrogen, oxygen, and sulfur. It is a typical industrial wastewater containing recalcitrant organic compounds. Because this wastewater contains high concentrations of various pollutants with multiple components, such as a high COD (chemical oxygen demand), primarily the oxygen equivalent consumed by polar organic compounds, and also high concentrations of volatile phenols and cyanides, direct discharge would cause significant pollution and harm to the environment. Therefore, this wastewater must be treated to meet standards before it can be discharged or recycled.

[0003] Using microbial strains for biochemical treatment of high-chlorinated phenol and cyanide wastewater can effectively decompose the organic matter in the wastewater and reduce the concentration of COD, volatile phenols, and cyanide, enabling the wastewater to meet effluent standards. However, microbial strains are easily affected by the pH and temperature of the wastewater, leading to the inactivation of microbial agents and affecting the wastewater treatment efficiency. Furthermore, microorganisms are prone to poisoning and inactivation when directly exposed to high concentrations of pollutants. Therefore, physical adsorption treatment of high-chlorinated phenol and cyanide wastewater is necessary during biochemical treatment. Summary of the Invention

[0004] This invention provides a method for treating high-chlorinated phenol-cyanide wastewater, which solves the problem that during the biochemical treatment of high-chlorinated phenol-cyanide wastewater, microbial strains are easily affected by the pH and temperature of the wastewater, leading to the inactivation of microbial strains and affecting the wastewater treatment efficiency.

[0005] The technical solution of the present invention:

[0006] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0007] S1. The pH of the perchloric phenol-cyanide wastewater is adjusted to 6-8 using alkaline substances, and the sediment is allowed to stand to form. After skimming and filtration, the pretreated perchloric phenol-cyanide wastewater is collected.

[0008] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 1-2 hours. After filtration, collect the adsorbed wastewater and precipitate.

[0009] S3. The adsorbed wastewater and microbial agent are mixed, biochemically treated, allowed to settle, filtered, and the biochemically treated wastewater is collected for testing and discharge.

[0010] The composite adsorbent is obtained by reacting N,N-diethylaminoethyl methacrylate and 1,3-propanesulfonyl lactone to form an amphoteric monomer, then surface-modifying zeolite with KH570, and finally mixing and reacting it with the amphoteric monomer and crosslinking monomer.

[0011] The microbial agent is obtained by treating rice husk powder with sodium hydroxide solution and aluminum sulfate, loading it with a composite bacterial solution, and then reacting it with tannic acid and polyethyleneimine.

[0012] Furthermore, in step S1, the alkaline substance is selected from lime or sodium hydroxide.

[0013] Furthermore, in step S2, the mass ratio of the pretreated high-chlorine phenol cyanide wastewater to the composite adsorbent is 100:(1-2).

[0014] Furthermore, in step S3, the mass ratio of the adsorbed wastewater to the microbial agent is 100:(10-20).

[0015] Furthermore, in step S3, during the biochemical treatment, the dissolved oxygen concentration is 5-10 mg / L, the treatment time is 10-12 h, and the treatment temperature is 20-30 °C.

[0016] Furthermore, the composite adsorbent is prepared by the following steps:

[0017] A1. Add 1,3-propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate to acetonitrile, stir until homogeneous, and reflux at 80-85℃ for 15-17h. After removing acetonitrile by distillation until a viscous liquid is formed, add methyl acetate to precipitate a white solid. After filtration and drying, the amphoteric monomer is obtained.

[0018] A2. Add KH570 to ethanol and deionized water, stir until homogeneous, add zeolite, stir the reaction, cool to room temperature, filter, wash, and dry to obtain functionalized zeolite.

[0019] A3. Add the crosslinking monomer and the amphoteric monomer to deionized water, stir until homogeneous, add potassium persulfate and functionalized zeolite, stir to react, filter, wash and dry to obtain the composite adsorbent.

[0020] Furthermore, in the above A1 reaction process, acetonitrile is used as a solvent, and N,N-diethylaminoethyl methacrylate and 1,3-propanesulfonyl lactone are used as raw materials. After a homogeneous reaction, acetonitrile is removed by distillation until a viscous liquid is formed. Methyl acetate is added to precipitate a white solid. The white solid is washed with acetone to remove a very small amount of unreacted raw materials, acetonitrile and methyl acetate, to obtain an amphoteric monomer.

[0021] The synthesis steps are as follows:

[0022]

[0023] Furthermore, during the A2 reaction process described above, the silanol groups generated by the hydrolysis of KH570 can combine with the hydroxyl groups on the zeolite surface through chemical bonds, thereby grafting KH570 onto the zeolite surface and obtaining functionalized zeolite.

[0024] Furthermore, in the A3 reaction process described above, potassium persulfate acts as an initiator, enabling the double bonds carried by N,N-diethylaminoethyl methacrylate in the amphoteric monomer to copolymerize with the double bonds on the surface of the functionalized zeolite. The double bonds contained in the crosslinking monomer can also participate in the copolymerization process, thereby forming a porous crosslinked network structure on the zeolite surface, which serves as a composite adsorbent.

[0025] Further, in step A1, the mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile is (2-2.4):(3-3.4):(10-15).

[0026] Further, in step A2, the mass ratio of KH570, ethanol, deionized water and zeolite is (0.6-1):(25-30):(8-15):(1-2).

[0027] Further, in step A3, the mass ratio of crosslinking monomer, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is (1-1.2):(3-3.2):(45-55):(0.5-0.7):(2-2.2).

[0028] Furthermore, the crosslinking monomer is selected from any one of acrylic acid, methacrylic acid, and itaconic acid.

[0029] Furthermore, the microbial inoculant is prepared through the following steps:

[0030] B1. Place rice husk powder in sodium hydroxide solution, stir and react, add aluminum sulfate, stir evenly, add hydrochloric acid to adjust pH, stir and react again, after aging, filtering, washing and drying, to obtain modified rice husk powder.

[0031] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains.

[0032] B3. Mix rice husk powder loaded with compound microbial strains, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir and react, filter, dry at room temperature overnight to obtain microbial inoculant.

[0033] Furthermore, in the above-mentioned B1 reaction process, the rice husk powder is treated with sodium hydroxide solution, so that the silicon dioxide in the rice husk powder can react with the sodium hydroxide solution to form water-soluble sodium silicate in the rice husk powder. The formed water-soluble sodium silicate can react with aluminum sulfate to form aluminum silicate. After aging and gelation, a network structure with silicon-oxygen-aluminum bonds is formed in the pores of the rice husk powder, thus obtaining modified rice husk powder.

[0034] Furthermore, during the B2 reaction process described above, the modified rice husk powder has a high porosity structure, which enables the composite bacterial solution to be adsorbed into the modified rice husk powder, resulting in rice husk powder loaded with composite bacterial strains.

[0035] Furthermore, in the above-mentioned B3 reaction process, tannic acid acts as a binder, which can adhere to the surface of the rice husk powder loaded with bacteria. The phenolic hydroxyl groups contained in tannic acid can combine with the primary, secondary, and tertiary amine functional groups in polyethyleneimine through hydrogen bonds, so that polyethyleneimine is coated on the surface of the rice husk powder loaded with bacteria by tannic acid, thus serving as a microbial agent.

[0036] Further, in step B1, the mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate is (3-5):(60-70):(0.3-0.7).

[0037] Furthermore, in step B2, the mass ratio of modified rice husk powder to compound bacterial solution is (2-5):1.

[0038] Further, in step B3, the mass ratio of rice husk powder, tannic acid, deionized water and polyethyleneimine loaded with the compound microbial strain is (2-3):(0.6-1):(20-25):(1-1.2).

[0039] Further, in step B2, the compound bacterial solution is prepared by the following steps: After sterilizing the culture medium at 120℃ for 20 min, it is cooled to room temperature. Bacillus subtilis and Bacillus pumilus are inoculated into the culture medium separately, and cultured with shaking at 25-30℃ and 150-200 r / min until the bacterial concentration in each culture medium reaches (1×10⁻⁶). 8 -1.5×10 8 After the culture was completed, two bacterial solutions were obtained. The two bacterial solutions were mixed at a volume ratio of 1:(1-1.2) to obtain a compound bacterial solution.

[0040] Furthermore, the culture medium composition is as follows: yeast extract 1-2%, peptone 1.5-2%, glucose 0.5-1%, ammonium chloride 0.5-21%, and the remainder is water.

[0041] The present invention has the following beneficial effects:

[0042] (1) In the technical solution of the present invention, N,N-diethylaminoethyl methacrylate and 1,3-propanesulfonyl lactone react to form an amphoteric monomer. The positive charge it carries can adsorb volatile phenols (phenolic hydroxyl groups), cyanides (free cyanide CN-) and chloride ions in the pretreated high-chlorine phenol cyanide wastewater through electrostatic bonding. The negative charge it carries can adsorb and remove positively charged ammonia nitrogen, thereby effectively removing pollutants in the high-chlorine phenol cyanide wastewater and reducing the chloride ion concentration in the pretreated high-chlorine phenol cyanide wastewater. This avoids the high chloride ion concentration in the wastewater, which can easily destroy the cell structure of the microbial agents through oxidation and inhibit microbial activity, thus providing a suitable environment for the biochemical treatment of high-chlorine phenol cyanide wastewater and improving the removal efficiency of organic pollutants in high-chlorine phenol cyanide wastewater.

[0043] (2) In the technical solution of the present invention, functionalized zeolite, amphoteric monomer and crosslinking monomer undergo copolymerization and crosslinking reaction to form a porous crosslinking network structure on the surface of zeolite. On the one hand, the porous structure of zeolite provides a high adsorption capacity for pollutants such as volatile phenols, cyanides and chloride ions in high chlorine phenol cyanide wastewater. It forms a double adsorption structure with amphoteric monomer to improve the adsorption of pollutants in wastewater. On the other hand, the porous crosslinking network structure formed on the surface of zeolite has high adsorption performance and adsorption capacity, thereby improving the removal efficiency of pollutants in wastewater. Moreover, the carboxyl groups carried by the crosslinking monomer give the composite adsorbent more adsorption sites, improving the removal efficiency of cationic pollutants in wastewater. In addition, the composite adsorbent contains a large number of active functional groups, which can be uniformly dispersed in wastewater to avoid the aggregation and precipitation of the composite adsorbent.

[0044] (3) In the technical solution of the present invention, after forming a network structure with silicon-oxygen-aluminum bonding in the pores of rice husk powder, the composite bacterial liquid is loaded. On the one hand, the network structure with silicon-oxygen-aluminum bonding forms a supporting skeleton structure for rice husk powder, which can improve the impact strength of rice husk powder and prevent rice husk powder from being crushed due to hydraulic shearing during the biochemical treatment of wastewater, thus losing its loading effect on microbial strains and affecting the biochemical treatment of wastewater. On the other hand, rice husk powder serves as a carrier for the composite bacterial liquid, which improves the activity of the composite bacterial strains and prevents the microbial agents from being easily affected by the pH and temperature in the wastewater, leading to the failure of the microbial agents and affecting the wastewater treatment efficiency. In addition, the composite bacterial strains include Bacillus subtilis and Bacillus pumilus, which have a good degradation effect on ammonia nitrogen, organic matter and other pollutants in wastewater.

[0045] (4) In the technical solution of the present invention, polyethyleneimine is coated on the surface of rice husk powder loaded with bacteria by tannic acid as a microbial agent. On the one hand, the molecular structure of polyethyleneimine contains a large number of primary amine, secondary amine and tertiary amine functional groups, which carry positive charges and have a good adsorption effect on the remaining volatile phenols (phenolic hydroxyl groups), cyanides (free cyanide CN-) and chloride ions in the high chlorine phenol cyanide wastewater after adsorption, thereby improving the removal efficiency. In addition, it works synergistically with microbial strains to effectively improve the wastewater treatment efficiency. Furthermore, tannic acid can increase the force on the composite strains and prevent the composite strains from falling off, thus affecting the biological action of the composite strains on the wastewater. On the other hand, polyethyleneimine has high hydrophilicity, which can improve the dispersibility of rice husk powder loaded with bacteria in the wastewater and prevent the rice husk powder from being unevenly dispersed in the wastewater, affecting the biological reaction process and leading to a decrease in wastewater treatment efficiency.

[0046] (5) In the technical solution of the present invention, the high-chlorine phenol cyanide wastewater is treated by adsorption with a composite adsorbent, which effectively removes most of the organic pollutants in the wastewater and reduces the chloride ion content in the high-chlorine phenol cyanide wastewater, providing a suitable environment for the biochemical treatment of the high-chlorine phenol cyanide wastewater; then, a mixture of microbial agents is used for biochemical treatment to deeply remove the organic pollutants in the high-chlorine phenol cyanide wastewater that are difficult to adsorb and remove, so that the treated wastewater meets the effluent standards and can be directly discharged. Detailed Implementation

[0047] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0049] Among them, Bacillus subtilis is disclosed in patent application number CN202410524438.3, accession number CGMCCNo.28443, and is deposited at the China General Microbiological Culture Collection Center.

[0050] Bacillus pumilus: accession number CGMCC No.1.10291, purchased from the China General Microbiological Culture Collection Center.

[0051] The zeolite is natural clinoptilolite with a particle size of 5 mm; the rice husk powder has a particle size of 0.5 mm and a pore size of 30 μm.

[0052] The alkaline substance is selected from lime.

[0053] The crosslinking monomer is acrylic acid.

[0054] Polyethyleneimine with a molecular weight of 300 was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0055] The compound bacterial solution is prepared by the following steps:

[0056] After sterilizing the culture medium at 120℃ for 20 min, and cooling it to room temperature, Bacillus subtilis and Bacillus pumilus were inoculated into the culture medium separately, and cultured with shaking at 26℃ and 180 r / min until the bacterial concentration in each culture medium reached 1.3 × 10⁻⁶. 8 The bacterial culture was carried out at a concentration of 100 cells / mL. After the culture was completed, two bacterial solutions were obtained. The two bacterial solutions were mixed at a volume ratio of 1:1.1 to obtain a compound bacterial solution.

[0057] Furthermore, the culture medium composition is as follows: yeast extract 1.5%, peptone 1.8%, glucose 0.8%, ammonium chloride 20.8%, and the remainder is water.

[0058] Example 1

[0059] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0060] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 6 with lime, and after standing, a precipitate was formed. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0061] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 1 hour. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:1.

[0062] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:10. During the biochemical treatment, the dissolved oxygen concentration is 5 mg / L, the treatment time is 10 h, and the treatment temperature is 20℃.

[0063] The composite adsorbent is prepared by the following steps:

[0064] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 80°C for 15 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2:3:10.

[0065] A2. KH570 was added to ethanol and deionized water, stirred until homogeneous, zeolite was added, and the mixture was stirred at 70°C for 1.5 h. After cooling to room temperature, the mixture was filtered, washed three times with ethanol and three times with deionized water, and dried in an oven at 70°C for 10 min to obtain functionalized zeolite. The mass ratio of KH570, ethanol, deionized water and zeolite was 0.6:25:8:1.

[0066] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1:3:45:0.5:2.

[0067] Microbial inoculants are prepared through the following steps:

[0068] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 3:60:0.3.

[0069] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 2:1.

[0070] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 2:0.6:20:1.

[0071] Example 2

[0072] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0073] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 7 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0074] S2. Add composite adsorbent to the pretreated high-chlorine phenol-cyanide wastewater and perform adsorption treatment for 1.5 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol-cyanide wastewater to composite adsorbent is 100:1.5.

[0075] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:15. During the biochemical treatment, the dissolved oxygen concentration is 8 mg / L, the treatment time is 11 h, and the treatment temperature is 25℃.

[0076] The composite adsorbent is prepared by the following steps:

[0077] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 83°C for 16 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.2:3.2:13.

[0078] A2. KH570 was added to ethanol and deionized water, stirred until homogeneous, zeolite was added, and the mixture was stirred at 70°C for 1.5 h. After cooling to room temperature, the mixture was filtered, washed three times with ethanol and three times with deionized water, and dried in an oven at 70°C for 10 min to obtain functionalized zeolite. The mass ratio of KH570, ethanol, deionized water and zeolite was 0.8:28:12:1.5.

[0079] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1.1:3.1:50:0.6:2.1.

[0080] Microbial inoculants are prepared through the following steps:

[0081] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 4:65:0.5.

[0082] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 3.5:1.

[0083] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 2.5:0.8:23:1.1.

[0084] Example 3

[0085] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0086] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0087] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0088] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0089] The composite adsorbent is prepared by the following steps:

[0090] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0091] A2. Add KH570 to ethanol and deionized water, stir well, add zeolite, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain functionalized zeolite; the mass ratio of KH570, ethanol, deionized water and zeolite is 1:30:15:2.

[0092] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1.2:3.2:55:0.7:2.2.

[0093] Microbial inoculants are prepared through the following steps:

[0094] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0095] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0096] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 3:1:25:1.2.

[0097] Comparative Example 1

[0098] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0099] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0100] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0101] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0102] The composite adsorbent is prepared by the following steps:

[0103] A1. KH570 was added to ethanol and deionized water and stirred until homogeneous. Zeolite was added and the mixture was stirred at 70°C for 1.5 h. After cooling to room temperature, the mixture was filtered, washed three times with ethanol and three times with deionized water, and dried in an oven at 70°C for 10 min to obtain functionalized zeolite. The mass ratio of KH570, ethanol, deionized water and zeolite was 1:30:15:2.

[0104] A2. Acrylic acid and N,N-diethylaminoethyl methacrylate were added to deionized water and stirred until homogeneous. Potassium persulfate and functionalized zeolite were added, and the mixture was stirred and reacted at 80°C for 2 hours. After filtration, the mixture was washed three times with deionized water and dried in an oven at 80°C for 10 minutes to obtain a composite adsorbent. The mass ratio of acrylic acid, N,N-diethylaminoethyl methacrylate, deionized water, potassium persulfate, and functionalized zeolite was 1.2:3.2:55:0.7:2.2.

[0105] Microbial inoculants are prepared through the following steps:

[0106] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0107] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0108] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 3:1:25:1.2.

[0109] Comparative Example 2

[0110] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0111] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0112] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0113] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0114] The composite adsorbent is prepared by the following steps:

[0115] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0116] A2. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and zeolite is 1.2:3.2:55:0.7:2.2.

[0117] Microbial inoculants are prepared through the following steps:

[0118] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0119] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0120] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 3:1:25:1.2.

[0121] Comparative Example 3

[0122] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0123] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0124] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0125] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0126] The composite adsorbent is prepared by the following steps:

[0127] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0128] A2. Add KH570 to ethanol and deionized water, stir well, add zeolite, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain functionalized zeolite; the mass ratio of KH570, ethanol, deionized water and zeolite is 1:30:15:2.

[0129] A3. Add the amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain the composite adsorbent; the mass ratio of amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 4.4:55:0.7:2.2.

[0130] Microbial inoculants are prepared through the following steps:

[0131] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0132] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0133] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 3:1:25:1.2.

[0134] Comparative Example 4

[0135] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0136] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0137] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0138] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0139] The composite adsorbent is prepared by the following steps:

[0140] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0141] A2. Add KH570 to ethanol and deionized water, stir well, add zeolite, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain functionalized zeolite; the mass ratio of KH570, ethanol, deionized water and zeolite is 1:30:15:2.

[0142] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1.2:3.2:55:0.7:2.2.

[0143] Microbial inoculants are prepared through the following steps:

[0144] B1. Mix rice husk powder and compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strain; the mass ratio of rice husk powder to compound bacterial solution is 5:1.

[0145] B2. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid, deionized water and polyethyleneimine is 3:1:25:1.2.

[0146] Comparative Example 5

[0147] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0148] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0149] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0150] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0151] The composite adsorbent is prepared by the following steps:

[0152] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0153] A2. Add KH570 to ethanol and deionized water, stir well, add zeolite, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain functionalized zeolite; the mass ratio of KH570, ethanol, deionized water and zeolite is 1:30:15:2.

[0154] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1.2:3.2:55:0.7:2.2.

[0155] Microbial inoculants are prepared through the following steps:

[0156] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0157] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0158] B3. Mix rice husk powder loaded with compound microorganisms and deionized water, stir evenly, add polyethyleneimine, stir at 25℃ for 30 min, filter, dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, deionized water and polyethyleneimine is 3:26:1.2.

[0159] Comparative Example 6

[0160] A method for treating high-chlorinated phenol-cyanide wastewater includes the following steps:

[0161] S1. The pH of the high-chlorine phenol-cyanide wastewater was adjusted to 8 with lime, and the sediment was allowed to stand to form. After skimming and filtration, the pretreated high-chlorine phenol-cyanide wastewater was collected.

[0162] S2. Add composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater and perform adsorption treatment for 2 hours. After filtration, collect the adsorbed wastewater and precipitate. The mass ratio of pretreated high-chlorine phenol cyanide wastewater to composite adsorbent is 100:2.

[0163] S3. The adsorbed wastewater and microbial agent are mixed, and after biochemical treatment, the mixture is allowed to settle and filtered. The biochemically treated wastewater is then collected, tested, and discharged. The mass ratio of the adsorbed wastewater to the microbial agent is 100:20. During the biochemical treatment, the dissolved oxygen concentration is 10 mg / L, the treatment time is 12 h, and the treatment temperature is 30℃.

[0164] The composite adsorbent is prepared by the following steps:

[0165] A1. 1,3-Propanesulfonyl lactone and N,N-diethylaminoethyl methacrylate were added to acetonitrile, stirred until homogeneous, and refluxed at 85°C for 17 h. The acetonitrile was removed by rotary evaporation until a viscous liquid was formed. Methyl acetate was added to precipitate a white solid. The white solid was collected by filtration and dried in an oven at 50°C for 15 min to obtain an amphoteric monomer. The mass ratio of 1,3-propanesulfonyl lactone, N,N-diethylaminoethyl methacrylate, and acetonitrile was 2.4:3.4:15.

[0166] A2. Add KH570 to ethanol and deionized water, stir well, add zeolite, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain functionalized zeolite; the mass ratio of KH570, ethanol, deionized water and zeolite is 1:30:15:2.

[0167] A3. Add acrylic acid and amphoteric monomer to deionized water, stir evenly, add potassium persulfate and functionalized zeolite, stir and react at 80℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain composite adsorbent; the mass ratio of acrylic acid, amphoteric monomer, deionized water, potassium persulfate and functionalized zeolite is 1.2:3.2:55:0.7:2.2.

[0168] Microbial inoculants are prepared through the following steps:

[0169] B1. Rice husk powder was placed in a 2.5 mol / L sodium hydroxide solution and stirred at 90℃ and 180 r / min for 2 h. Aluminum sulfate was then added and stirred until homogeneous. 2 mol / L hydrochloric acid was added to adjust the pH to 4.5, and the mixture was stirred at 60℃ for 1 h. After aging, filtration, washing three times with deionized water, and drying in a 110℃ oven for 10 min, modified rice husk powder was obtained. The mass ratio of rice husk powder, sodium hydroxide solution, and aluminum sulfate was 5:70:0.7.

[0170] B2. Mix the modified rice husk powder and the compound bacterial solution, stir until adsorption is complete, and dry at room temperature overnight to obtain rice husk powder loaded with compound bacterial strains; the mass ratio of modified rice husk powder to compound bacterial solution is 5:1.

[0171] B3. Mix rice husk powder loaded with compound microorganisms, tannic acid and deionized water, stir at 25°C for 30 min, filter, and dry at room temperature overnight to obtain microbial inoculant; the mass ratio of rice husk powder loaded with compound microorganisms, tannic acid and deionized water is 3:2.2:25.

[0172] The wastewater collected after biochemical treatment in Examples 1-3 and Comparative Examples 1-6 was then tested.

[0173] The indicators of the high-chlorinated phenol-cyanide wastewater used in Examples 1-3 and Comparative Examples 1-6 of this invention are as follows: COD 617 mg / L, chloride ion concentration 153 mg / L, ammonia nitrogen concentration 120 mg / L, total nitrogen concentration 155 mg / L, volatile phenols 44 mg / L, and cyanide 23 mg / L.

[0174] The concentrations of COD, ammonia nitrogen, cyanide, and volatile phenols in the collected biochemically treated wastewater were determined according to the methods in GB16171-2012 "Emission Standard of Pollutants for Coking Chemical Industry"; the concentration of total nitrogen in the collected biochemically treated wastewater was determined according to national standard HJ 636-2017.

[0175] The chloride ion concentration in the collected biochemically treated wastewater was determined according to GB / T 11896-1989 standard. The industrial wastewater discharge standard stipulates that the chloride ion content shall not exceed 50 mg / L.

[0176] After measurement, the concentrations of COD, chloride ions, ammonia nitrogen, total nitrogen, volatile phenols, and cyanide in the treated wastewater were recorded.

[0177] As shown in Table 1 below.

[0178] Table 1. Various indicators of the biochemically treated wastewater collected in Examples 1-3 and Comparative Examples 1-6

[0179] project COD content (mg / L) Ammonia nitrogen content (mg / L) Total nitrogen content (mg / L) Volatile phenol content (mg / L) Cyanide content (mg / L) Chloride ion content (g / L) Example 1 52.6 6.5 11.3 0.25 0.18 11.5 Example 2 50.1 5.7 10.8 0.22 0.11 10.7 Example 3 53.7 6.8 11.9 0.31 0.20 11.9 Comparative Example 1 102.3 58.3 70.1 13.51 10.32 63.6 Comparative Example 2 127.3 66.7 82.1 15.22 13.44 70.9 Comparative Example 3 125.6 63.1 75.4 14.11 12.71 65.9 Comparative Example 4 115.6 60.1 72.9 13.98 12.04 64.7 Comparative Example 5 120.9 62.7 73.4 14.01 13.21 65.3 Comparative Example 6 123.6 63.4 74.1 14.13 12.68 65.7

[0180] As can be seen from the data in Table 1, all indicators of the high-chlorinated phenol-cyanide wastewater treated in Examples 1-3 meet the effluent standards of the "Emission Standard of Pollutants for Coking Chemical Industry GB16171-2012" and can be directly discharged.

[0181] In Comparative Example 1, the amphoteric monomer was replaced with a composite adsorbent prepared from N,N-diethylaminoethyl methacrylate for the treatment of perchloric phenol-cyanide wastewater. The wastewater collected after biochemical treatment showed a higher content of organic pollutants, demonstrating that the amphoteric monomer formed by the reaction of N,N-diethylaminoethyl methacrylate and 1,3-propanesulfonyl lactone, carrying both positive and negative charges, can effectively adsorb and remove organic pollutants from perchloric phenol-cyanide wastewater and reduce the chloride ion concentration in the wastewater. This provides a suitable environment for the biochemical treatment of perchloric phenol-cyanide wastewater and improves the removal efficiency of organic pollutants from the wastewater.

[0182] In Comparative Example 2, the functionalized zeolite was replaced with a composite adsorbent prepared from zeolite for the treatment of high-chlorine phenol-cyanide wastewater. The wastewater collected after biochemical treatment had a higher content of organic pollutants, demonstrating that KH570 grafted onto the zeolite surface is beneficial for the formation of a porous cross-linked network structure of amphoteric monomers and cross-linking monomers on the zeolite surface. This structure has high adsorption performance and adsorption capacity, thereby improving the removal efficiency of pollutants in wastewater. Furthermore, it imparts a large number of active functional groups, which can be uniformly dispersed in the wastewater, avoiding the aggregation and precipitation of the composite adsorbent.

[0183] In Comparative Example 3, a composite adsorbent prepared by replacing acrylic acid with an amphoteric monomer was used for the treatment of high-chlorine phenol-cyanide wastewater. The wastewater collected after biochemical treatment had a higher content of organic pollutants, which proves that acrylic acid, as a crosslinking monomer, is beneficial to forming a porous crosslinking network structure on the zeolite surface, thereby improving the removal efficiency of pollutants in wastewater. Furthermore, the carboxyl groups carried by the crosslinking monomer acrylic acid endow the composite adsorbent with more adsorption sites, thereby improving the removal efficiency of cationic pollutants in wastewater.

[0184] In Comparative Example 4, the modified rice husk powder was replaced with a microbial agent prepared from rice husk powder for the treatment of high-chlorine phenol-cyanide wastewater. The collected wastewater after biochemical treatment had a higher content of organic pollutants, proving that the formation of a network structure with silicon-oxygen-aluminum bonds in the pores of rice husk powder serves as a supporting skeleton structure for rice husk powder. This structure can improve the impact strength of rice husk powder and prevent it from being crushed due to hydraulic shearing during the biochemical treatment of wastewater, thus losing its ability to support microbial strains and affecting the biochemical treatment of wastewater.

[0185] In Comparative Example 5, the microbial agent prepared by replacing tannic acid with deionized water was used for the treatment of high-chlorine phenol-cyanide wastewater. The wastewater collected after biochemical treatment had a higher content of organic pollutants, which proved that applying tannic acid to the surface of rice husk powder loaded with microorganisms can increase the force on the composite microorganisms, prevent the composite microorganisms from falling off and affecting the biological action of the composite microorganisms on the wastewater, and facilitate the coating of polyethyleneimine on the surface of rice husk powder loaded with microorganisms, thereby improving the dispersibility of rice husk powder in wastewater.

[0186] In Comparative Example 6, a microbial agent prepared by replacing polyethyleneimine with tannic acid was used for the treatment of perchloric phenol-cyanide wastewater. The wastewater collected after biochemical treatment had a high content of organic pollutants, proving that the molecular structure of polyethyleneimine contains a large number of primary, secondary, and tertiary amine functional groups, which carry positive charges. This results in a good adsorption effect on the remaining volatile phenols, cyanides, and chloride ions in the perchloric phenol-cyanide wastewater after adsorption, improving the removal efficiency. Furthermore, it works synergistically with microbial strains to effectively improve the wastewater treatment efficiency.

[0187] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0188] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for treating wastewater containing high concentrations of chlorophenol and cyanide, characterized by, The method comprises the following steps: S1, adjusting the pH of the high-chlorine phenol cyanide wastewater to 6-8 by using an alkaline substance, and standing to form a precipitate, skimming, filtering, and collecting the pretreated high-chlorine phenol cyanide wastewater; S2, adding a composite adsorbent to the pretreated high-chlorine phenol cyanide wastewater, and performing adsorption treatment for 1-2 hours, filtering, and collecting the wastewater and the precipitate after adsorption; S3, mixing the wastewater after adsorption with a microbial agent, performing biochemical treatment, standing to precipitate, filtering, collecting the wastewater after biochemical treatment, and performing detection and discharge; The composite adsorbent is obtained by reacting methacrylic acid-N,N-diethyl amine ethyl ester and 1,3-propane sulfolane to form an amphoteric monomer, then modifying the surface of zeolite with KH570, and then mixing and reacting the amphoteric monomer and a crosslinking monomer. The composite adsorbent is specifically prepared by the following steps: A1, adding 1,3-propane sulfolane and methacrylic acid-N,N-diethyl amine ethyl ester to acetonitrile, stirring uniformly, stirring and refluxing at 80-85°C for 15-17 hours, adding methyl acetate to precipitate white solids after removing acetonitrile by distillation to form a viscous liquid, filtering and drying to obtain an amphoteric monomer; A2, adding KH570 to ethanol and deionized water, stirring uniformly, adding zeolite, stirring and reacting, cooling to room temperature, filtering, washing, and drying to obtain a functionalized zeolite; A3, adding a crosslinking monomer and an amphoteric monomer to deionized water, stirring uniformly, adding potassium persulfate and the functionalized zeolite, stirring and reacting, filtering, washing, and drying to obtain a composite adsorbent; The microbial agent is obtained by treating rice husk powder with a sodium hydroxide solution and aluminum sulfate, then loading a composite bacterial solution, and then mixing and reacting with tannic acid and polyethylene imine. The microbial agent is specifically prepared by the following steps: B1, placing the rice husk powder in a sodium hydroxide solution, stirring and reacting, adding aluminum sulfate, stirring uniformly, adjusting the pH by adding hydrochloric acid, stirring and reacting, aging, filtering, washing, and drying to obtain modified rice husk powder; B2, mixing the modified rice husk powder and the composite bacterial solution, stirring and adsorbing, and drying overnight at room temperature to obtain rice husk powder loaded with the composite bacterial species; B3, mixing the rice husk powder loaded with the composite bacterial species, tannic acid, and deionized water, stirring uniformly, adding polyethylene imine, stirring and reacting, filtering, and drying overnight at room temperature to obtain a microbial agent.

2. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step A1, the mass ratio of 1,3-propane sulfolane, methacrylic acid-N,N-diethyl amine ethyl ester, and acetonitrile is (2-2.4):(3-3.4):(10-15).

3. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step A2, the mass ratio of KH570, ethanol, deionized water, and zeolite is (0.6-1):(25-30):(8-15):(1-2).

4. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step A3, the mass ratio of the crosslinking monomer, the amphoteric monomer, deionized water, potassium persulfate, and the functionalized zeolite is (1-1.2):(3-3.2):(45-55):(0.5-0.7):(2-2.2).

5. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step B1, the mass ratio of the rice husk powder, the sodium hydroxide solution, and aluminum sulfate is (3-5):(60-70):(0.3-0.7).

6. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step B2, the mass ratio of the modified rice husk powder and the complex bacteria solution is (2-5):

1.

7. The method for treating high chlorophenol cyanide wastewater according to claim 1, characterized in that, In step B3, the mass ratio of the rice husk powder loaded with the complex bacteria, tannic acid, deionized water and polyethyleneimine is (2-3):(0.6-1):(20-25):(1-1.2).

Images