Industrial sewage treatment agent and preparation method thereof

Abstract

The invention discloses an industrial sewage treatment agent and a preparation method thereof, belongs to the technical field of sewage treatment, and is used to solve the problem that the components of the industrial sewage treatment agent in the prior art are impure and cannot have high adsorption and impurity removal efficiency for both nitrogen and phosphorus inorganic pollutants and organic pollutants. The invention is obtained by mixing a water treatment auxiliary agent and a multi-polymerized organic flocculant, the water treatment auxiliary agent comprises carboxymethyl cellulose and sodium alginate, and the multi-polymerized organic flocculant comprises a nano-scale inorganic mixture, a copolymerized polyacrylamide and a spherical macroporous weak acid resin. The invention utilizes the nano-scale inorganic mixture to improve the adsorption and removal rate of nitrogen and phosphorus elements, and utilizes the designed copolymerized polyacrylamide and the spherical macroporous weak acid resin to improve the removal rate of organic matter. On the other hand, the nano-scale inorganic mixture, the copolymerized polyacrylamide and the spherical macroporous weak acid resin are combined into a stable whole through functional groups to further improve their own adsorption efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and specifically relates to an industrial sewage treatment agent and a preparation method thereof. Background Art

[0002] Industrial wastewater mainly refers to intermediate products, by-products, cleaning fluids and extraction solvents generated in the industrial production process. The vast majority of discharged industrial wastewater is organic chemical raw materials or intermediates in various forms. Typical industries such as electronics, coking, steel, printing and dyeing have always been major emitters of organic pollutants. In addition, there are chemicals such as pesticides, fertilizers and herbicides and related additives, as well as heavy metal pollutants. These substances enter the environment through various channels and are eventually discharged into rivers and lakes in the form of wastewater.

[0003] On the one hand, due to the limited self-purification capacity of natural water bodies, if the pollutants discharged into the water bodies exceed the ecological carrying capacity of natural water bodies or cause irreversible pollution to them, on the other hand, these pollutants discharged into the environment have certain biological activity, which will cause toxic reactions or carcinogenic effects in aquatic plants and animals, and even directly cause harm to human health.

[0004] Patent application CN107758877A discloses an industrial wastewater treatment agent and a preparation method thereof. The industrial wastewater treatment agent includes pectinase, orange peel, laccase, sodium hydroxide solution, humic acid, polyferric phosphate, aluminum sulfate, fly ash, nano titanium dioxide, sodium acetate, isopropyl alcohol, activated carbon, manganese nitrate, ferric chloride, calcium bromide, perlite powder and flax slurry, which can improve the removal rate of nitrogen, phosphorus and potassium elements. However, the above-mentioned prior art has low removal efficiency for organic pollutants in industrial wastewater.

[0005] Patent application CN115231648A discloses an industrial sewage treatment agent and a preparation method thereof. The industrial sewage treatment agent includes titanium dioxide, silver nitrate, starch, epoxypropyltrimethylammonium chloride, montmorillonite, aluminum hydroxide, sodium silicate, acrylamide, dimethyldiallyl chloride, sodium tripolyphosphate, azobisisobutylcyanide, ammonium sulfate and polyferric chloride. Acrylamide and modified starch are grafted to form a network macromolecular polymer to improve its own adsorption and flocculation effect. However, the components of the industrial sewage treatment agent disclosed in the above patent application are mixed. The modified acrylamide only improves its own spatial structure and molecular weight by grafting starch. The prepared modified acrylamide has a small molecular weight and a poor flocculation effect.

[0006] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a method for preparing an industrial sewage treatment agent, which is used to solve the technical problem that the components of the industrial sewage treatment agent in the prior art are mixed and cannot simultaneously have a high adsorption and impurity removal efficiency for nitrogen and phosphorus inorganic pollutants and organic pollutants.

[0008] The object of the present invention can be achieved by the following technical scheme: an industrial sewage treatment agent is obtained by mixing 1 part of a water treatment aid and 2-3 parts of a multi-polymerized organic flocculant in parts by weight;

[0009] The water treatment aid comprises 30-40 parts of carboxymethyl cellulose and 40-50 parts of sodium alginate in parts by weight;

[0010] In terms of weight, the multi-component copolymer organic flocculant comprises 10-20 parts of a nano-scale inorganic mixture, 30-40 parts of copolymerized polyacrylamide and 10-20 parts of a spherical macroporous weakly acidic resin.

[0011] The industrial sewage treatment agent prepared by the invention comprises carboxymethyl cellulose, sodium alginate and a synthetic multi-polymer organic flocculant. The multi-polymer organic flocculant is prepared by physical adsorption and chemical reaction of a nano-scale inorganic mixture, copolymerized polyacrylamide and a spherical macroporous weakly acidic resin to finally obtain an organic-inorganic hybrid flocculant.

[0012] Furthermore, the preparation method of the nanoscale inorganic mixture comprises the following steps:

[0013] A1. Crushing the sulfuric acid plant dust, passing through a 100-300 mesh sieve, and placing it in a reactor; adding 30-40%wt of industrial hydrochloric acid and water to the reactor, heating the reactor to 90-95°C, then adding sodium chlorate, and reacting at a constant temperature for 1-2h; after the reaction is complete, evaporating and concentrating the filtrate to obtain a solid; washing the solid with deionized water 3 times to obtain the pretreated sulfuric acid plant dust;

[0014] The effective components of the sulfuric acid plant slag dust include ferric oxide and aluminum oxide. The iron element contained in the sulfuric acid plant slag dust is oxidized to the highest valence using sodium chlorate oxidant to obtain the pretreated sulfuric acid plant slag dust.

[0015] A2, bentonite, hydrotalcite, zeolite and diatomaceous earth are mixed and stirred uniformly to obtain an inorganic mixture; the inorganic mixture is washed with water, the upper slurry is extracted, the upper slurry is filtered into solids by pressure filtration to obtain solids after pressure filtration, the solids after pressure filtration are mixed with pre-treated sulfuric acid plant slag dust to obtain a mixture; the mixture is vacuum dried at 60-70° C. to constant weight, and crushed to pass through a 200-300 mesh sieve to obtain a nano-scale inorganic mixture.

[0016] Furthermore, in step A1, the weight ratio of sulfuric acid plant dust, industrial hydrochloric acid, water and sodium chlorate is 1000:2000-2500:1000:0.5-1; in step A2, the weight ratio of bentonite, hydrotalcite, zeolite and diatomaceous earth is 3-4:5:3:3-5; when the inorganic mixture is washed with water, the weight ratio of the inorganic mixture to water is 1:1.5; the weight ratio of the solid after filter pressing and the pretreated sulfuric acid plant dust is 10:1.

[0017] Furthermore, the preparation method of the co-polyacrylamide comprises the following steps:

[0018] B1. Evenly mix acrylamide and deionized water to obtain an acrylamide solution; evenly mix diallyldimethylammonium chloride, the acrylamide solution, trichloroethylene and ethanol to obtain a mixed solution; transfer the mixed solution to a three-necked flask, adjust the pH value of the mixed solution to 7-8 with 0.1 mol / L hydrochloric acid, and then introduce nitrogen until the inside of the three-necked flask is filled with nitrogen;

[0019] B2, K2S2O8 and Na2SO4 are mixed to obtain a composite initiator; the composite initiator is added into a three-necked flask, and then the acrylamide solution is uniformly added dropwise into the three-necked flask within 30 minutes, and then the three-necked flask is heated to 70-80°C, and the reaction is carried out at a constant temperature for 2-3 hours to obtain a polymerization product; the polymerization product is sequentially washed with anhydrous ethanol and deionized water for three times, and then dried in a vacuum drying oven at 60-70°C to constant weight to obtain copolymerized polyacrylamide.

[0020] K2S2O8 and Na2SO4 are mixed to obtain a composite initiator; under the action of the composite initiator, acrylamide monomer, diallyldimethylammonium chloride and trichloroethylene undergo copolymerization to obtain a polymer main chain containing multiple functional groups such as chloride ions, amino groups, ammonium ions, etc. The ammonium ions and amine groups on the prepared copolymer polyacrylamide are positively charged, the chloride ions are negatively charged, and the two carbons linked to the chloride ions are positively charged, making the prepared copolymer polyacrylamide an amphoteric copolymer organic matter.

[0021] The reaction principle of the copolymerization of acrylamide, diallyldimethylammonium chloride and trichloroethylene is as follows:

[0022]

[0023] Further, in step B1, the ratio of acrylamide to deionized water is 10-20 mL:100 mL; the ratio of diallyldimethyl chloride, acrylamide solution, trichloroethylene and ethanol is

[0024] 15-25g:50-60mL:10-15g:200-300mL; in step B2, the usage ratio of K2S2O8, Na2SO4 and acrylamide solution is 3-5g:1.5-3g:50-60mL.

[0025] As another aspect of the present invention, a method for preparing an industrial wastewater treatment agent comprises the following steps:

[0026] S1. Mix 2,4-dihydroxybenzaldehyde and ethanol evenly, then add NaCl and phenol, mix evenly, cool in an ice water bath, add formaldehyde, heat up to react, and obtain dark red viscous resin slurry; evenly disperse the resin slurry in turbine oil, then heat up to polymerize, and then heat up to dehydrate, to obtain spherical macroporous weakly acidic resin;

[0027] 2,4-Dihydroxybenzaldehyde and formaldehyde undergo condensation reaction, and NaCl is used as a porogen to prepare the condensation product - spherical macroporous weakly acidic resin.

[0028] S2, weighing spherical macroporous weakly acidic resin, nano-scale inorganic mixture, copolymerized polyacrylamide and deionized water, mixing them evenly, and adding them into a conical flask; placing the conical flask in a constant temperature oscillator, oscillating at 100-120 rpm for 30-60 min at 25° C. to obtain a mixed solid-liquid; placing the mixed solid-liquid in a vacuum drying oven at 60-70° C. to dry to constant weight, to obtain a multi-component copolymerized organic flocculant;

[0029] The polyhydroxyl and polycarboxyl groups contained in the spherical macroporous weakly acidic resin can decompose protons and react with various functional groups such as amino groups, ammonium groups and chloride ions in the copolymer polyacrylamide to combine the two organic adsorbents, while the nanoscale inorganic mixture can fill the pores of the multi-polymer organic flocculant to prepare an organic-inorganic hybrid multi-polymer organic flocculant.

[0030] S3, mixing carboxymethyl cellulose and sodium alginate to obtain a water treatment aid; mixing the water treatment aid and a multi-polymer organic flocculant to obtain an industrial wastewater treatment agent.

[0031] Furthermore, in step S1, the cooling temperature of the ice water bath is 0°C, and the cooling time of the ice water bath is 30-60 minutes; the temperature of the temperature rise reaction is 40-50°C, and the time of the temperature rise reaction is 60 minutes; the temperature of the resin slurry temperature rise polymerization is 55-60°C, and the time of the resin slurry temperature rise polymerization is 1-2 hours; the temperature of the temperature rise dehydration is 110-120°C, and the time of the temperature rise dehydration is 30 minutes.

[0032] Furthermore, in step S1, the usage ratio of 2,4-dihydroxybenzaldehyde, ethanol, NaCl and phenol is 10-20g:100mL:5-10g:60g; and the usage ratio of resin slurry and turbine oil is 30mL:120-150mL.

[0033] Furthermore, in step S2, the dosage ratio of the spherical macroporous weakly acidic resin, the nanoscale inorganic mixture, the copolymerized polyacrylamide and the deionized water is 10-20 g: 10 g: 30-40 g: 100 mL.

[0034] The present invention has the following beneficial effects:

[0035] 1. The nano-scale inorganic mixture prepared by the present invention comprises pre-treated sulfuric acid plant slag dust, bentonite, hydrotalcite, zeolite and diatomaceous earth. The sulfuric acid plant slag dust contains ferric oxide and aluminum oxide, which is equivalent to an aluminum-iron copolymer composite flocculant. In water, it can be electrically neutralized and destabilized, and adsorbed and bridged with water particles to form coarse flocs. By removing the flocs, the water body is purified. The zeolite skeleton has a relatively large porous structure, and the adsorption and removal rate of phosphorus and nitrogen elements in industrial wastewater is relatively high through ion exchange, physical adsorption and other methods. Furthermore, the above-mentioned inorganic mixture is crushed to nanoscale. Due to the large specific surface area and high surface energy of the nano-scale powder, the overall reaction activity and reaction speed are further improved. In addition, the interlayer anions of the nano-inorganic adsorbent powder can be exchanged with Cl in the copolymerized polyacrylamide to prepare an inorganic-organic composite organic flocculant.

[0036] 2. The copolymerized polyacrylamide prepared by the present invention is obtained by copolymerizing diallyldimethylammonium chloride, acrylamide and trichloroethylene. The copolymerization of acrylamide monomers itself can obtain a water-soluble high molecular polymer, which has good flocculation properties for organic COD. The present invention selects diallyldimethylammonium chloride, trichloroethylene and acrylamide monomers with multiple functional groups for co-condensation, further improving the adsorption performance of the copolymerized polyacrylamide for organic pollutants and enriching the number and types of functional groups on the main chain of the organic adsorption material. The spherical macroporous weakly acidic resin prepared by the present invention is essentially a cation exchange resin, which can specifically remove ammonia nitrogen elements, and utilizes the hydroxyl and carboxyl functional groups of the spherical macroporous weakly acidic resin and the multifunctional groups of the copolymerized polyacrylamide for chemical adsorption and reaction to prepare a multi-polymerized organic flocculant with good adsorption properties for nitrogen, phosphorus and organic COD. And the multi-polymerized organic flocculant is mixed with a water treatment additive to prepare an industrial sewage treatment agent. DETAILED DESCRIPTION

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. 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.

[0038] Example 1

[0039] This embodiment provides a method for preparing a nanoscale inorganic mixture, comprising the following steps:

[0040] 1. 1000g of sulfuric acid plant dust is crushed by a crusher, passed through a 300-mesh sieve, and placed in a reactor; 2000g of 40%wt industrial hydrochloric acid is pumped from a storage tank into an acid high-level tank by an acid-resistant pump, and then quantitatively flows into the reactor from the acid high-level tank, and then 1000g of water is added, and heated to 90°C by steam, and then 0.5g of sodium chlorate is added, and the reaction is carried out at a constant temperature for 1h. After the reaction is complete, the filtrate flows into a product tank through a plate and frame filter, and evaporates and concentrates to obtain a solid; the solid is washed 3 times with deionized water to obtain the pretreated sulfuric acid plant dust.

[0041] 2. Add bentonite, hydrotalcite, zeolite and diatomaceous earth into a mixing and blending machine in a weight ratio of 3:5:3:3, set the electric heating temperature of the mixing and blending machine to 70°C, start the driving device and stir for 30 minutes to obtain an inorganic mixture. Wash the inorganic mixture with water, and the weight ratio of the inorganic mixture to water is 1:1.5; then extract the upper slurry, and filter the upper slurry into solids to obtain solids after filter pressing; mix the solids after filter pressing with the pre-treated sulfuric acid plant slag dust in a weight ratio of 10:1 to obtain a mixture; vacuum dry the mixture at 60°C to constant weight, crush it with a jet mill, and pass it through a 200-mesh sieve to obtain a nano-scale inorganic mixture.

[0042] Example 2

[0043] This embodiment provides a method for preparing a nanoscale inorganic mixture, comprising the following steps:

[0044] 1. 1000 parts of sulfuric acid plant dust are crushed to 200 meshes by a crusher and put into a reactor; 2200g of 35%wt industrial hydrochloric acid is pumped from a storage tank into an acid high-level tank by an acid-resistant pump, and then quantitatively flows into the reactor from the acid high-level tank, and then 1000g of water is added, and heated to 92°C by steam, and then 0.8g of sodium chlorate is added, and the reaction is carried out for 1.5h. After the reaction is complete, the filtrate flows into a product tank through a plate and frame filter, and evaporates and concentrates to obtain a solid; the solid is washed 3 times with deionized water to obtain the pretreated sulfuric acid plant dust.

[0045] 2. Add bentonite, hydrotalcite, zeolite and diatomaceous earth into a mixing and blending machine in a weight ratio of 3.5:5:3:4, set the electric heating temperature of the mixing and blending machine to 72°C, start the driving device and stir for 50 minutes to obtain an inorganic mixture. Wash the inorganic mixture with water in a weight ratio of 1:1.5 to extract the upper layer of slurry; filter the upper layer of slurry into solids, mix the solids after filtration and the pre-treated sulfuric acid plant slag dust in a weight ratio of 10:1 to obtain a mixture; vacuum dry the mixture at 65°C to constant weight, crush it with a jet mill, and pass it through a 250-mesh sieve to obtain a nano-scale inorganic mixture.

[0046] Example 3

[0047] This embodiment provides a method for preparing a nanoscale inorganic mixture, comprising the following steps:

[0048] 1. 1000g of sulfuric acid plant dust is crushed to 100 mesh by a crusher and put into a reactor; 2500g of 40%wt industrial hydrochloric acid is pumped from a storage tank into an acid high-level tank by an acid-resistant pump, and then quantitatively flows into the reactor from the acid high-level tank, and then 1000g of water is added and heated to 95°C by steam, and then 1g of sodium chlorate is added and reacted for 2h. After the reaction is complete, the filtrate flows into a product tank through a plate and frame filter, and evaporates and concentrates to obtain a solid; the solid is washed 3 times with deionized water to obtain the pretreated sulfuric acid plant dust.

[0049] 2. Add bentonite, hydrotalcite, zeolite and diatomaceous earth into a mixing and blending machine in a weight ratio of 4:5:3:5, set the electric heating temperature of the mixing and blending machine to 75°C, start the driving device and stir for 60 minutes to obtain an inorganic mixture. Wash the inorganic mixture with water in a weight ratio of 1:1.5 to extract the upper layer of slurry; filter the upper layer of slurry into solids, mix the solids after filtration and the pre-treated sulfuric acid plant slag dust in a weight ratio of 10:1 to obtain a mixture; vacuum dry the mixture to constant weight, crush it with a jet mill, and pass it through a 300-mesh sieve to obtain a nano-scale inorganic mixture.

[0050] Example 4

[0051] This embodiment provides a method for preparing a co-polyacrylamide, comprising the following steps:

[0052] 1. Mix 10 mL of acrylamide and 100 mL of deionized water to obtain an acrylamide solution. Mix 15 g of diallyldimethylammonium chloride, 50 mL of acrylamide solution, 10 g of trichloroethylene and 200 mL of ethanol to obtain a mixed solution, and then transfer the mixed solution to a three-necked flask. The ports of the three-necked flask are respectively connected to a dropping funnel, an air guide tube, and a thermometer, and a stirrer is provided inside; adjust the pH value of the mixed solution to 7 with 0.1 mol / L hydrochloric acid, and then introduce nitrogen until the inside of the three-necked flask is filled with nitrogen.

[0053] 2. Mix 3g of K2S2O8 and 1.5g of Na2SO4 to obtain a composite initiator. Add the composite initiator into a three-necked flask, then uniformly add 50mL of acrylamide solution to the three-necked flask through a dropping funnel within 30min, then heat the three-necked flask to 70°C, and react at constant temperature for 2h to obtain a polymerization product; the polymerization product is sequentially washed with anhydrous ethanol and deionized water for three times, and then dried in a vacuum drying oven at 60°C to constant weight to obtain copolymerized polyacrylamide.

[0054] Example 5

[0055] This embodiment provides a method for preparing a co-polyacrylamide, comprising the following steps:

[0056] 1. Mix 15 mL of acrylamide and 100 mL of deionized water to obtain an acrylamide solution. Mix 20 g of diallyldimethylammonium chloride, 55 mL of acrylamide solution, 12 g of trichloroethylene and 260 mL of ethanol to obtain a mixed solution, and then transfer the mixed solution to a three-necked flask. The ports of the three-necked flask are respectively connected to a dropping funnel, an air guide tube, and a thermometer, and a stirrer is provided inside; adjust the pH value of the mixed solution to 7.7 with 0.1 mol / L hydrochloric acid, and then introduce nitrogen until the inside of the three-necked flask is filled with nitrogen.

[0057] 2.4 g of K2S2O8 and 2.5 g of Na2SO4 were mixed to obtain a composite initiator. The composite initiator was added to a three-necked flask, and then 55 mL of acrylamide solution was uniformly added to the three-necked flask through a dropping funnel within 30 minutes, and then the three-necked flask was heated to 76°C and reacted at a constant temperature for 2.6 hours to obtain a polymerization product; the polymerization product was sequentially washed with anhydrous ethanol and deionized water for three times, and then dried in a vacuum drying oven at 66°C to constant weight to obtain copolymerized polyacrylamide.

[0058] Example 6

[0059] This embodiment provides a method for preparing a co-polyacrylamide, comprising the following steps:

[0060] 1. Mix 20 mL of acrylamide and 100 mL of deionized water to obtain an acrylamide solution. Mix 25 g of diallyldimethylammonium chloride, 60 mL of acrylamide solution, 15 g of trichloroethylene and 300 mL of ethanol to obtain a mixed solution, and then transfer the mixed solution to a three-necked flask. The ports of the three-necked flask are respectively connected to a dropping funnel, an air guide tube, and a thermometer, and a stirrer is provided inside; adjust the pH value of the mixed solution to 8 with 0.1 mol / L hydrochloric acid, and then introduce nitrogen until the inside of the three-necked flask is filled with nitrogen.

[0061] 2. Mix 5g of K2S2O8 and 3g of Na2SO4 to obtain a composite initiator. Add the composite initiator to a three-necked flask, then uniformly add 60mL of acrylamide solution to the three-necked flask through a dropping funnel within 30 minutes, then heat the three-necked flask to 80°C, and react at a constant temperature for 3 hours to obtain a polymerization product. The polymerization product is sequentially washed with anhydrous ethanol and deionized water three times, and then dried in a vacuum drying oven at 70°C to constant weight to obtain copolymerized polyacrylamide.

[0062] Example 7

[0063] This embodiment provides a method for preparing an industrial sewage treatment agent, comprising the following steps:

[0064] 1. Add 10g of 2,4-dihydroxybenzaldehyde and 100mL of ethanol to a beaker, mix well, then add 5g of NaCl and 60g of phenol, mix well, cool in an ice water bath at 0℃ for 30min, then add 30g of formaldehyde, heat to 40℃ and react for 60min to obtain dark red viscous resin slurry. Disperse 30mL of resin slurry evenly in 120mL of turbine oil, then heat to 55℃ for polymerization for 1h, and then heat to 110℃ for dehydration to obtain spherical macroporous weakly acidic resin.

[0065] 2. Weigh 10 parts of the nanoscale inorganic mixture prepared in Example 1, 30 parts of the co-polyacrylamide prepared in Example 4, 10 parts of the spherical macroporous weakly acidic resin and 100 parts of deionized water, mix them evenly, add them into a conical flask, and then place the conical flask in a digital constant temperature oscillator, oscillate at 100 rpm for 30 min at 25°C to obtain a mixed solid-liquid; place the mixed solid-liquid in a vacuum oven at 60°C and dry to constant weight to obtain a multi-polymer organic flocculant.

[0066] 3. According to parts by weight, 30 parts of carboxymethyl cellulose and 400 parts of sodium alginate are mixed to prepare a water treatment aid; according to parts by weight, 1 part of the water treatment aid and 3 parts of the multi-polymer organic flocculant are mixed to obtain an industrial wastewater treatment agent.

[0067] Example 8

[0068] This embodiment provides a method for preparing an industrial sewage treatment agent, comprising the following steps:

[0069] 1. Add 15g of 2,4-dihydroxybenzaldehyde and 100mL of ethanol into a beaker, mix well, then add 7g of NaCl and 60g of phenol, mix well, and then cool in an ice water bath at 0°C for 40min, then add 38g of formaldehyde, heat to 46°C and react for 60min to obtain a dark red viscous resin slurry; evenly disperse 30mL of the resin slurry in 140mL of turbine oil, then heat to 58°C for polymerization for 1.5h, and then heat to 115°C for dehydration to obtain a spherical macroporous weakly acidic resin.

[0070] 2. Weigh 18 parts of the nanoscale inorganic mixture prepared in Example 2, 35 parts of the co-polyacrylamide prepared in Example 5, 17 parts of the spherical macroporous weakly acidic resin and 100 parts of deionized water, mix them evenly, add them into a conical flask, and then place the conical flask in a digital constant temperature oscillator, oscillate at 110 rpm for 50 minutes at 25°C to obtain a mixed solid-liquid mixture. Dry the mixed solid-liquid mixture in a vacuum oven at 66°C to constant weight to obtain a multi-component copolymer organic flocculant.

[0071] 3. According to parts by weight, 35 parts of carboxymethyl cellulose and 44 parts of sodium alginate are mixed to prepare a water treatment aid; according to parts by weight, 1 part of the water treatment aid and 2 parts of the multi-polymer organic flocculant are mixed to obtain an industrial wastewater treatment agent.

[0072] Example 9

[0073] This embodiment provides a method for preparing an industrial sewage treatment agent, comprising the following steps:

[0074] 1. Add 20g of 2,4-dihydroxybenzaldehyde and 100mL of ethanol to a beaker, mix well, then add 10g of NaCl and 60g of phenol, mix well, then cool in an ice water bath at 0℃ for 60min, then add 40g of formaldehyde, heat to 50℃ and react for 60min to obtain dark red viscous resin slurry. Disperse 30mL of resin slurry evenly in 150mL of turbine oil, then heat to 60℃ for polymerization for 2h, then heat to 120℃ for dehydration to obtain spherical macroporous weakly acidic resin.

[0075] 2. Weigh 20 parts of the nanoscale inorganic mixture prepared in Example 3, 40 parts of the co-polyacrylamide prepared in Example 6, 20 parts of the spherical macroporous weakly acidic resin and 100 parts of deionized water, mix them evenly, add them into a conical flask, and then place the conical flask in a digital constant temperature oscillator, oscillate at 120 rpm for 60 minutes at 25°C to obtain a mixed solid-liquid mixture. Dry the mixed solid-liquid mixture in a vacuum oven at 70°C to constant weight to obtain a multi-component copolymer organic flocculant.

[0076] 3. According to parts by weight, 40 parts of carboxymethyl cellulose and 50 parts of sodium alginate are mixed to prepare a water treatment aid; according to parts by weight, 1 part of the water treatment aid and 3 parts of the multi-polymer organic flocculant are mixed to obtain an industrial wastewater treatment agent.

[0077] Comparative Example 1

[0078] The difference between this comparative example and Example 9 is that in step 2, the nanoscale inorganic mixture prepared in Example 3 is not added.

[0079] Comparative Example 2

[0080] In step 1 of Example 6, trichloroethylene was not added to prepare the copolymerized polyacrylamide. In step 2 of Example 9, the copolymerized polyacrylamide was prepared without adding trichloroethylene.

[0081] Comparative Example 3

[0082] The difference between this comparative example and Example 9 is that in step 2, the co-polyacrylamide prepared in Example 6 is not added.

[0083] Performance test 1: adsorption performance of phosphorus-containing wastewater

[0084] Prepare 6 250mL conical flasks, add 100mL and 20mg / mL phosphorus-containing wastewater; add 25g of the industrial wastewater treatment agent prepared in Example 1-3 and Comparative Example 1-3 respectively, fix the adsorption temperature at 30°C, and fix the adsorption time for 10h, then use a 0.45μm filter to take out the water sample of the adsorbed phosphorus-containing wastewater, determine the phosphorus concentration in the adsorbed phosphorus-containing wastewater, and calculate the phosphorus adsorption rate.

[0085] Phosphorus adsorption rate = C 吸附前含磷废水 -C 吸附后含磷废水 / C 吸附前含磷废水

[0086] Performance test 2: adsorption performance of nitrogen-containing wastewater

[0087] Prepare 6 250mL conical flasks, add 100mL and 20mg / mL nitrogen-containing wastewater; add 25g of industrial wastewater treatment agent prepared in Example 1-3 and Comparative Example 1-3 respectively, fix the adsorption temperature at 30°C and the adsorption time at 10h, then use a 0.45μm filter to take out the water sample of nitrogen-containing wastewater after adsorption, and measure the nitrogen concentration in the nitrogen-containing wastewater after adsorption. Calculate the nitrogen adsorption rate.

[0088] Nitrogen adsorption rate = C 吸附前含氮废水 -C 吸附后含氮废水 / C 吸附前含氮废水

[0089] Performance test 3: COD adsorption performance

[0090] Prepare 6 250mL conical flasks, add 100mL of wastewater with a COD content of 5mg / mL; add 25g of the industrial wastewater treatment agent prepared in Example 1-3 and Comparative Example 1-3 respectively, fix the adsorption temperature at 30°C, fix the adsorption time at 10h, use the rapid open tube method to determine the COD concentration in the wastewater after adsorption, and calculate the COD adsorption rate.

[0091] COD adsorption rate = C 吸附前废水 -C 吸附后废水 / C 吸附前废水

[0092] The test results are shown in Table 1:

[0093] Table 1 - Test data of each test sample

[0094]

[0095] According to the results in Table 1, the industrial wastewater treatment agents prepared in Examples 1-3 have high adsorption rates for phosphorus, nitrogen and COD; in Comparative Example 1, no nano-scale inorganic mixture was added, and the adsorption rate of nitrogen and phosphorus in the prepared industrial wastewater treatment agent was significantly reduced; in Comparative Example 2, trichloroethylene was not added to the prepared co-polyacrylamide; in Comparative Example 3, no co-polyacrylamide was added to the prepared industrial wastewater treatment agent, which reduced the adsorption and flocculation performance of the industrial wastewater treatment agents prepared in Comparative Examples 2 and 3 for organic matter COD.

[0096] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0097] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0098] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An industrial wastewater treatment agent, characterized in that: The method is prepared by mixing 1 part of a water treatment aid and 2-3 parts of a multi-polymerized organic flocculant according to weight. The water treatment aid comprises 30-40 parts of carboxymethyl cellulose and 40-50 parts of sodium alginate in parts by weight; In terms of weight, the multi-component copolymer organic flocculant includes 10-20 parts of a nano-scale inorganic mixture, 30-40 parts of a copolymerized polyacrylamide and 10-20 parts of a spherical macroporous weakly acidic resin; The preparation method of the co-polyacrylamide comprises the following steps: B1. Evenly mix acrylamide and deionized water to obtain an acrylamide solution; evenly mix diallyldimethylammonium chloride, the acrylamide solution, trichloroethylene and ethanol to obtain a mixed solution; transfer the mixed solution to a three-necked flask, adjust the pH value of the mixed solution to 7-8 with 0.1 mol / L hydrochloric acid, and then introduce nitrogen until the inside of the three-necked flask is filled with nitrogen; B2, K2S2O8 and Na2SO4 are mixed to obtain a composite initiator; the composite initiator is added into a three-necked flask, and then the acrylamide solution is uniformly added to the three-necked flask within 30 minutes, and then the three-necked flask is heated to 70-80°C, and the reaction is carried out at a constant temperature for 2-3 hours to obtain a polymerization product; the polymerization product is sequentially washed with anhydrous ethanol and deionized water for three times, and then dried in a vacuum drying oven at 60-70°C to constant weight to obtain copolymerized polyacrylamide; The preparation method of the nanoscale inorganic mixture comprises the following steps: A1. Crushing the sulfuric acid plant slag dust, passing through a 100-300 mesh sieve, and putting it into a reactor; adding 30-40%wt of industrial hydrochloric acid and water into the reactor, heating the reactor to 90-95°C, then adding sodium chlorate, and reacting at a constant temperature for 1-2h; after the reaction is complete, evaporating and concentrating the filtrate to obtain a solid; washing the solid with deionized water to obtain the pretreated sulfuric acid plant slag dust; A2, bentonite, hydrotalcite, zeolite and diatomaceous earth are mixed and stirred uniformly to obtain an inorganic mixture; the inorganic mixture is washed with water, the upper slurry is extracted, the upper slurry is filtered into solids by pressure filtration to obtain a solid after pressure filtration, the solid after pressure filtration is mixed with the pre-treated sulfuric acid plant slag dust to obtain a mixture; the mixture is vacuum dried at 60-70° C. to constant weight, and crushed through a 200-300 mesh sieve to obtain a nano-scale inorganic mixture; The preparation method of the industrial sewage treatment agent comprises the following steps: S1. Mix 2,4-dihydroxybenzaldehyde and ethanol evenly, then add NaCl and phenol, mix evenly, cool in an ice water bath, add formaldehyde, heat up to react, and obtain dark red viscous resin slurry; evenly disperse the resin slurry in turbine oil, then heat up to polymerize, and then heat up to dehydrate, to obtain spherical macroporous weakly acidic resin; S2, weighing spherical macroporous weakly acidic resin, nano-scale inorganic mixture, copolymerized polyacrylamide and deionized water, mixing them evenly, and adding them into a conical flask; placing the conical flask in a constant temperature oscillator, oscillating at 100-120 rpm for 30-60 min at 25° C. to obtain a mixed solid-liquid; placing the mixed solid-liquid in a vacuum drying oven at 60-70° C. to dry to constant weight, to obtain a multi-component copolymerized organic flocculant; S3, mixing carboxymethyl cellulose and sodium alginate to obtain a water treatment aid; mixing the water treatment aid and a multi-polymer organic flocculant to obtain an industrial wastewater treatment agent.

2. An industrial wastewater treatment agent according to claim 1, characterized in that: In step A1, the weight ratio of sulfuric acid plant dust, industrial hydrochloric acid, water and sodium chlorate is 1000:2000-2500:1000:0.5-1; in step A2, the weight ratio of bentonite, hydrotalcite, zeolite and diatomaceous earth is 3-4:5:3:3-5; when the inorganic mixture is washed with water, the weight ratio of the inorganic mixture to water is 1:1.5; the weight ratio of the solid after filter pressing and the pretreated sulfuric acid plant dust is 10:

1.

3. An industrial wastewater treatment agent according to claim 1, characterized in that: In step B1, the usage ratio of acrylamide and deionized water is 10-20mL:100mL; the usage ratio of diallyldimethyl chloride, acrylamide solution, trichloroethylene and ethanol is 15-25g:50-60mL:10-15g:200-300mL; in step B2, the usage ratio of K2S2O8, Na2SO4 and acrylamide solution is 3-5g:1.5-3g:50-60mL.

4. An industrial wastewater treatment agent according to claim 1, characterized in that: In step S1, the cooling temperature of the ice water bath is 0°C, and the cooling time of the ice water bath is 30-60 minutes; the temperature of the temperature rise reaction is 40-50°C, and the time of the temperature rise reaction is 60 minutes; the temperature of the resin slurry temperature rise polymerization is 55-60°C, and the time of the resin slurry temperature rise polymerization is 1-2 hours; the temperature of the temperature rise dehydration is 110-120°C, and the time of the temperature rise dehydration is 30 minutes.

5. An industrial wastewater treatment agent according to claim 1, characterized in that: In step S1, the usage ratio of 2,4-dihydroxybenzaldehyde, ethanol, NaCl and phenol is 10-20g:100mL:5-10g:60g; the usage ratio of resin slurry and turbine oil is 30mL:120-150mL.

6. An industrial wastewater treatment agent according to claim 1, characterized in that: In step S2, the dosage ratio of the spherical macroporous weakly acidic resin, the nanoscale inorganic mixture, the copolymerized polyacrylamide and the deionized water is 10-20 g: 10 g: 30-40 g: 100 mL.

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