CN111675296B

CN111675296B - Composite efficient environment-friendly water treatment agent and preparation method and application thereof

Info

Publication number: CN111675296B
Application number: CN202010405981.3A
Authority: CN
Inventors: 郑文东; 陈永辉; 江进富
Original assignee: Panlin Xiamen Biotechnology Co ltd
Current assignee: Panlin Xiamen Biotechnology Co ltd
Priority date: 2020-05-14
Filing date: 2020-05-14
Publication date: 2022-07-12
Anticipated expiration: 2040-05-14
Also published as: CN111675296A

Abstract

The invention provides a composite efficient environment-friendly water treatment medicament and a preparation method and application thereof, wherein the water treatment medicament comprises the following raw materials in parts by weight: 97-99 parts of compound medicament A and 1-3 parts of compound medicament B; the preparation method comprises the steps of firstly preparing the agent A, then preparing the agent B, then uniformly mixing the agent A and the agent B, and obtaining the composite high-efficiency water treatment agent after ultrasonic treatment. The water treatment agent can be applied to high-difficulty wastewater treatment in industry, agriculture, life and the like, the raw materials of the agent are cheap and easy to purchase, the production is convenient, the using modes of the agent are various, the application link of the agent does not depend on complex facilities and equipment for sewage treatment, the investment of sewage treatment equipment can be reduced by more than 60 percent compared with the investment and the agent dosage of the current conventional sewage treatment facility, the agent dosage for sewage treatment can be reduced by 30-50 percent, and the water treatment agent is economic, environment-friendly, simple and efficient.

Description

Composite efficient environment-friendly water treatment agent and preparation method and application thereof

[ technical field ] A method for producing a semiconductor device

The invention relates to the field of water treatment agents and environmental engineering, in particular to a composite efficient environment-friendly water treatment agent and a preparation method and application thereof.

[ background of the invention ]

China is one of countries with water resource shortage and serious pollution, and from the national situation, the water shortage of various industries is serious at present, so that serious economic loss and social environment problems are caused. The water saving, sewage treatment and new water source development have the same important significance. The water treatment agent is developed vigorously to play an important role in saving water and treating sewage.

The water treatment agent is a chemical agent which is necessary to be used in the treatment process of industrial water, domestic water and waste water. Through the use of the chemical agents, the water meets certain quality requirements. The water treatment agent has the main functions of controlling the formation of water scales and sludge, reducing foams, reducing corrosion of materials in contact with water, removing suspended solids and toxic substances in water, deodorizing and decolorizing, softening and stabilizing water quality and the like. Therefore, the water treatment agent comprises a flocculant, a flocculating agent, a scale inhibitor, a corrosion inhibitor, a dispersing agent, a bactericide, a cleaning agent, a pre-filming agent, a defoaming agent, a decoloring agent, a chelating agent, an oxygen scavenger and ion exchange resin.

The unlimited discharge of industrial sewage and domestic wastewater causes serious pollution to water resources, and with the increasing importance of people on water resource environment problems, sewage treatment becomes urgent. The development of water treatment chemical agents is very important for saving water and treating sewage, the development of related industries is driven by the vigorous pollution treatment, and novel environment-friendly water treatment agents become an investment hotspot.

Currently, most of water treatment agents in China have small production scale, small yield, various single products and fast variety updating. However, with the increasing of environmental protection treatment strength in China, the requirements of sewage discharge standards are stricter and stricter, and the disadvantages of single water treatment products with low technical content are more and more obvious. In the field of wastewater treatment, technical service is indispensable, and the space for improving service is mainly realized by product compounding and upgrading, and the compounded product for water treatment in the market has strong specificity and technical closure, and cannot be comprehensively applied in different wastewater treatment industries. In order to achieve the effect of wastewater treatment, the components of a plurality of wastewater treatment compound reagents are not environment-friendly and easily cause secondary pollution. Therefore, the development of novel wastewater treatment agents which are environment-friendly, efficient, simple and convenient to use and wide in application range is an important technical approach and method for solving the technical problems.

[ summary of the invention ]

One of the technical problems to be solved by the invention is to provide a composite efficient environment-friendly water treatment agent, which can rapidly and efficiently treat sewage without secondary environmental pollution and has the advantages of economy, environmental protection, simple and convenient use and wide application range.

The present invention achieves one of the above technical problems:

a composite efficient environment-friendly water treatment medicament comprises the following raw materials in parts by weight: 97-99 parts of compound medicament A and 1-3 parts of compound medicament B;

wherein, the raw materials of the compound medicament A comprise fly ash, activated carbon powder, attapulgite powder, alumina powder, sodium bicarbonate, diatomite, polyaluminium chloride, zeolite powder, polyferric chloride, magnesium oxide and water glass;

the raw materials of the compound medicament B comprise sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer.

Preferably, the water treatment medicament comprises the following raw materials in parts by weight: 97.5 parts of compound medicament A and 1.5 parts of compound medicament B.

Preferably, the compound medicament A comprises the following raw materials in parts by weight: 5-20 parts of fly ash, 10-30 parts of attapulgite, 2-5 parts of activated carbon powder, 1-5 parts of alumina powder, 1-5 parts of sodium bicarbonate, 1-10 parts of diatomite, 20-50 parts of polyaluminum chloride, 1-5 parts of zeolite powder, 1-5 parts of polyferric chloride, 1-5 parts of magnesium oxide and 1-3 parts of water glass;

the compound medicament B comprises the following raw materials in parts by weight: 75-90 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 5-10 parts of sodium alginate; 5-15 parts of magnesium lignosulfonate-acrylamide graft copolymer.

Preferably, the compound medicament A comprises the following raw materials in parts by weight: 15 parts of fly ash, 15 parts of attapulgite, 4 parts of activated carbon powder, 3 parts of alumina powder, 2 parts of sodium bicarbonate, 6 parts of diatomite, 45 parts of polyaluminium chloride, 3 parts of zeolite powder, 3 parts of polyferric chloride, 2 parts of magnesium oxide and 2 parts of water glass; the raw material components are completely crushed to the fineness of 80-200 meshes for use.

Preferably, the compound medicament B comprises the following raw materials in parts by weight: 85 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 7 parts of sodium alginate; 8 parts of magnesium lignosulfonate-acrylamide graft copolymer.

The invention aims to solve the second technical problem and provides a preparation method of a composite efficient environment-friendly water treatment agent, and the produced product can be used for quickly and efficiently treating sewage without secondary environmental pollution and has the advantages of economy, environmental protection, simple and convenient use and wide application range.

The invention realizes the second technical problem in the way that:

a preparation method of a composite efficient environment-friendly water treatment medicament comprises the following steps: respectively preparing a compound medicament A agent and a compound medicament B agent, then uniformly mixing the compound medicament A agent and the compound medicament B agent according to the weight part ratio, and compounding after ultrasonic treatment to obtain the compound high-efficiency environment-friendly water treatment medicament.

Preferably, the preparation steps of the compound medicament A are as follows:

(1) firstly, feeding the fly ash, the alumina powder and the magnesium oxide into a solid stirring reaction kettle simultaneously, wherein the stirring speed per minute is 80-100 revolutions, and reacting for 10-20 minutes at 80-120 ℃;

(2) after the reaction step (1) is carried out, sequentially adding activated carbon powder, attapulgite powder and diatomite, maintaining the stirring speed at 100 plus 200 revolutions per minute, controlling the temperature at 100 plus 110 ℃, and gradually cooling to 60 ℃ after the reaction time is 45-60 minutes;

(3) after the reaction step (2), sequentially adding the polyaluminium chloride, the zeolite powder and the polyferric chloride, maintaining the temperature at 55-60 ℃, and maintaining the stirring speed at 90-100 revolutions per minute for reaction for 50-70 minutes;

(4) after the reaction step (3), finally adding water glass and sodium bicarbonate, maintaining the temperature at 45-50 ℃, and maintaining the stirring speed at 100-; after the reaction is finished, the temperature is reduced to normal temperature, and the compound medicament A is obtained for standby.

Preferably, the preparation steps of the compound medicament B are as follows:

(1) preparation of sulfomethacrylamide-dimethyldiallylammonium chloride copolymer: firstly, injecting 60-80L of pure water into a reaction kettle, adding 25-30KG of dimethyl diallyl ammonium chloride, stirring and dissolving uniformly at 55-65 ℃, supplementing the pure water to a constant volume of 100L, and preparing a dimethyl diallyl ammonium chloride solution with the content of 25-30%;

adding 22-25KG of acrylamide with the purity of 98% into 25-30% dimethyl diallyl ammonium chloride solution, and stirring for reaction at 60-70 ℃ for 50-60 minutes. Then adding 0.1-0.3% of disodium ethylene diamine tetraacetate and 0.1-0.6% of initiator to react for 5 minutes, wherein: the initiator is potassium persulfate/urea with a molar concentration ratio of 5.25-5.5:1.0-1.31 or sodium persulfate/sodium bisulfite with a molar concentration ratio of 7.0-7.33: 1.9-2.26; then introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid; adding 25-30% of a-sodium hydroxymethanesulfonate solution and a proper amount of catalyst into a viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product;

(2) preparation of magnesium lignosulfonate-acrylamide graft copolymer: in a reaction kettle according to the ratio of 2-3: 1-1.5, adding distilled water and magnesium lignosulfonate, controlling the temperature at 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide, stirring for reaction at 20-35 ℃, wherein the reaction time is 48-52 hours, and obtaining the magnesium lignosulfonate-acrylamide graft copolymer; wherein the concentration of acrylamide is 1.4mol/L, the mass ratio of magnesium lignosulfonate to acrylamide is 1-2:5-9, and the solid-liquid ratio is 1-2: 50-100, the concentration of initiator potassium persulfate/sodium sulfite is 0.5X10^-2mol/L-1.0×10^-2mol/L. Wherein, the solid-to-liquid ratio refers to the ratio of the total mass of the magnesium lignosulfonate and the acrylamide to the mass of the distilled water.

(3) Uniformly mixing sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer in parts by weight; injecting distilled water into the emulsification reaction kettle, and mixing the prepared mixture and the distilled water according to the mass ratio of 1-2: 5-10 deg.C, dissolving in emulsifying reactor at 30-45 deg.C for 12-18 hr, adding 0.5 × 10^-2mol/L-1.0×10^-2The initiator potassium persulfate/sodium sulfite is mol/L; continuously reacting for 28-30 hours, cooling to room temperature to form latex block polymer, and granulating, drying and crushing to obtain the compound medicament B.

Preferably, the mixing step of the compound medicament A and the compound medicament B is as follows:

(1) mixing the medicaments: uniformly mixing the compound medicament A and the compound medicament B according to the weight part ratio to obtain 100 parts of a mixture of the A and the B;

(2) ultrasonic treatment: feeding the mixture into an ultrasonic reaction kettle, controlling the ultrasonic frequency to be 28000Hz-32000Hz, controlling the stirring speed to be 400-600 revolutions per minute, continuously dropwise adding 2-5L of 10% ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes; controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours; after the reaction is finished, a mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes, thus obtaining the composite efficient environment-friendly water treatment agent.

Preferably, the water treatment agent can be used for treating various industrial, agricultural and domestic wastewater, and is applied to treatment of river, lake, landscape pool, black and odorous ditch and marine pollution.

The invention has the following advantages:

the water treatment agent can be widely used for treating various industrial, agricultural and domestic wastewater, and is also applied to the treatment of pollution of rivers, lakes, landscape ponds, black and odorous ditches, oceans and the like. Suspended matters, COD, BOD, ammonia nitrogen, phosphorus elements, heavy metals, chromaticity and the like in the sewage are removed quickly and efficiently. The raw materials of the medicament are cheap and easy to purchase, the production is convenient, the price is low, the efficiency is high, and no secondary environmental pollution exists. The medicament is simple to use, small in dosage, various in using method and mode, and the medicament using link does not depend on complex facilities and equipment for sewage treatment. Compared with the investment and the medicament dosage of the current conventional sewage treatment facility, the investment of the sewage treatment facility can be reduced by more than 60 percent, the medicament dosage of the sewage treatment can be reduced by 30 to 50 percent, and the method is economic, environment-friendly, simple and efficient.

[ detailed description ] embodiments

The present invention is further illustrated in detail by the following examples, which are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.

The starting materials used in the following examples are commercially available or can be prepared by methods generally customary in the art.

Example 1

1. The compound efficient environment-friendly water treatment medicament comprises 97.5 parts of a compound medicament A and 1.5 parts of a compound medicament B according to the weight parts of raw materials.

The compound medicament A comprises the following raw materials in parts by weight: 15 parts of fly ash, 15 parts of attapulgite, 4 parts of activated carbon powder, 3 parts of alumina powder, 2 parts of sodium bicarbonate, 6 parts of diatomite, 45 parts of polyaluminium chloride, 3 parts of zeolite powder, 3 parts of polyferric chloride, 2 parts of magnesium oxide and 2 parts of water glass. The above raw materials are all crushed to fineness of 80-200 meshes for use.

The compound medicament B comprises the following raw materials in parts by weight: 85 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer, 7 parts of sodium alginate and 8 parts of magnesium lignosulfonate-acrylamide graft copolymer.

2. The preparation method of the water treatment agent comprises the following steps:

step one, preparing a compound medicament A:

(3) after the reaction step (2), sequentially adding the polyaluminium chloride, the zeolite powder and the polyferric chloride, maintaining the temperature at 55-60 ℃, and maintaining the stirring speed at 90-100 revolutions per minute for reaction for 50 minutes;

(4) and (4) after the reaction step (3), finally adding water glass and sodium bicarbonate, maintaining the temperature at 45-50 ℃, and maintaining the stirring speed at 100-180 revolutions per minute, and reacting for 20-30 minutes. After the reaction is finished, the temperature is reduced to normal temperature, and the compound medicament A is obtained for standby.

Step two, preparation of compound medicament B:

(1) preparation of sulfomethacrylamide-dimethyldiallylammonium chloride copolymer: firstly, injecting 60-80L of pure water into a reaction kettle, adding 25KG of dimethyl diallyl ammonium chloride, stirring and dissolving uniformly at the temperature of 55-65 ℃, and supplementingPure water is added to the solution to a constant volume of 100L, and the solution of dimethyl diallyl ammonium chloride with the content of 25% is prepared. Adding acrylamide (CH) with the purity of 98% into a 25% dimethyl diallyl ammonium chloride solution₂＝CHCONH₂C₃H₅NO)23.6KG, and reacting for 50-60 minutes at 60-70 ℃ with stirring. Then adding 0.1 to 0.3 percent of ethylene diamine tetraacetic acid (EDTA-2Na) and 0.5 percent of initiator to react for 5 minutes. Wherein: the initiator is preferably potassium persulfate/urea in a molar ratio of 5.25:1.31 or sodium persulfate/sodium bisulfite in a molar ratio of 7.33: 2.26.

Adding an initiator for 5 minutes, introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid. Adding 30% of a-sodium hydroxymethanesulfonate solution and a proper amount of catalyst into the viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product.

(2) Preparation of magnesium lignosulfonate-acrylamide graft copolymer: in the autoclave, the reaction mixture was stirred as follows: 1, adding distilled water and magnesium lignosulfonate, controlling the temperature to be 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide in a ratio, stirring for reaction at 20-35 ℃, and reacting for 48-52 hours to obtain the magnesium lignosulfonate-acrylamide graft copolymer. Wherein the concentration of acrylamide is 1.4mol/L, the mass ratio of the lignosulfonic acid to the acrylamide is 1:5, and the solid-to-liquid ratio is 1: 50, initiator Potassium persulfate/sodium sulfite (K)₂S₂O₈/NaS₂O₃) Is 0.5X10^-2mol/L. Wherein, the solid-to-liquid ratio refers to the ratio of the total mass of the magnesium lignosulfonate and the acrylamide to the mass of the distilled water.

(3) Taking 85 parts of a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer according to the proportion; 7 parts of sodium alginate; 8 parts of magnesium lignosulfonate-acrylamide graft copolymer are uniformly mixed to prepare a mixture. Injecting distilled water into the emulsification reaction kettle, and mixing the prepared mixture and the distilled water according to the mass ratio of 1:5 at a concentration of 30-Dissolving in an emulsion reactor at 45 deg.C for 12-18 hr, adding initiator potassium persulfate/sodium sulfite (K)₂S₂O₈/NaS₂O₃) In a concentration of 0.8X10^-2And (3) continuing to react for 28-30 hours, cooling to room temperature to form latex block polymers, and granulating, drying and crushing to obtain the compound medicament B. And (5) standby.

Step three, mixing the compound medicament A and the compound medicament B, and specifically comprising the following steps:

(1) mixing the medicaments: and (3) uniformly mixing the compound medicament A obtained in the step (I) and the compound medicament B obtained in the step (II) according to the weight part ratio to obtain 100 parts of a mixture of the agent A and the agent B.

(2) Ultrasonic treatment: and (3) feeding the mixture of the agent A and the agent B into an ultrasonic reaction kettle, controlling the ultrasonic frequency to be 28000Hz-32000Hz, controlling the stirring speed to be 400-600 revolutions per minute, continuously dropwise adding 2.5L of 10% ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes. Controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours. After the reaction is finished, mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes to prepare the composite efficient environment-friendly water treatment agent.

Example 2

1. The compound efficient environment-friendly water treatment medicament comprises 97 parts of a compound medicament A and 3 parts of a compound medicament B according to the weight parts of raw materials.

The compound medicament A comprises the following raw materials in parts by weight: 11 parts of fly ash, 10 parts of attapulgite, 5 parts of activated carbon powder, 5 parts of alumina powder, 5 parts of sodium bicarbonate, 10 parts of diatomite, 50 parts of polyaluminium chloride, 1 part of zeolite powder, 1 part of polyferric chloride, 1 part of magnesium oxide and 1 part of water glass. The raw materials are completely crushed to the fineness of 80-200 meshes for use.

The compound medicament B comprises the following raw materials in parts by weight: 75 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 10 parts of sodium alginate; 15 parts of magnesium lignosulfonate-acrylamide graft copolymer.

step one, preparing a compound medicament A:

(1) firstly, simultaneously feeding the fly ash, the alumina powder and the magnesium oxide into a solid stirring reaction kettle, wherein the stirring speed per minute is 80-100 revolutions, and reacting for 10-20 minutes at 80-120 ℃;

(3) after the reaction step (2), sequentially adding the polyaluminium chloride, the zeolite powder and the polyferric chloride, maintaining the temperature at 55-60 ℃, and maintaining the stirring speed at 90-100 revolutions per minute for reaction for 70 minutes;

(4) and (3) the reaction step is carried out, and finally, water glass and sodium bicarbonate are added, the temperature is maintained to be 45-50 ℃, the stirring speed is maintained to be 100-180 r/min, and the reaction is carried out for 20-30 min. After the reaction is finished, the temperature is reduced to normal temperature, and the compound medicament A is obtained for standby.

Step two, preparation of compound medicament B:

(1) preparation of sulfomethacrylamide-dimethyldiallylammonium chloride copolymer: firstly, injecting 60-80L of pure water into a reaction kettle, adding 30KG of dimethyl diallyl ammonium chloride, stirring and dissolving uniformly at 55-65 ℃, supplementing pure water to a constant volume of 100L, and preparing a 30% dimethyl diallyl ammonium chloride solution;

then adding 25KG of acrylamide with the purity of 98% into the 30% dimethyl diallyl ammonium chloride solution, and stirring and reacting for 50-60 minutes at the temperature of 60-70 ℃. And then 0.3% of disodium ethylene diamine tetraacetate and 0.6% of initiator are added to react for 5 minutes, wherein: the initiator is potassium persulfate/urea with a molar ratio of 5.5:1.31 or sodium persulfate/sodium bisulfite with a molar ratio of 7.33: 2.26; then introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid; adding 30% of a-sodium hydroxymethanesulfonate solution and a proper amount of catalyst into a viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product;

(2) preparation of magnesium lignosulfonate-acrylamide graft copolymer: in the autoclave, the reaction was carried out as follows 3: 1.5, adding distilled water and magnesium lignosulfonate according to the mass ratio, controlling the temperature to be 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide, stirring for reaction at 20-35 ℃, and reacting for 48-52 hours to obtain a magnesium lignosulfonate-acrylamide graft copolymer; wherein the acrylamide concentration is 1.4mol/L, and the mass ratio of the lignosulfonic acid to the acrylamide is 2: 9, the solid-to-liquid ratio is 2: 100, concentration of initiator potassium persulfate/sodium sulfite is 1.0X 10^-2mol/L; wherein, the solid-to-liquid ratio refers to the ratio of the total mass of the magnesium lignosulfonate and the acrylamide to the mass of the distilled water.

(3) Uniformly mixing sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer in parts by weight; injecting distilled water into the emulsification reaction kettle, and mixing the prepared mixture and the distilled water according to the mass ratio of 2: 10, dissolving in an emulsion reactor at 30-45 deg.C for 12-18 hr, adding initiator potassium persulfate/sodium sulfite with concentration of 1.0 × 10^-2mol/L; continuously reacting for 28-30 hours, cooling to room temperature to form latex block polymer, and granulating, drying and crushing to obtain the compound medicament B.

(2) Ultrasonic treatment: and (3) feeding the mixture of the agent A and the agent B into an ultrasonic reaction kettle, wherein the ultrasonic frequency is 28000Hz-32000Hz, the stirring speed is controlled at 400-600 revolutions per minute, continuously dropwise adding 2L of 10% ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes. Controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours. After the reaction is finished, a mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes to prepare the composite high-efficiency environment-friendly water treatment agent.

Example 3

1. The compound efficient environment-friendly water treatment medicament comprises 99 parts of a compound medicament A and 1 part of a compound medicament B according to the weight parts of raw materials.

The compound medicament A comprises the following raw materials in parts by weight: 20 parts of fly ash, 30 parts of attapulgite, 1 part of activated carbon powder, 1 part of alumina powder, 1 part of sodium bicarbonate, 1 part of diatomite, 28 parts of polyaluminum chloride, 5 parts of zeolite powder, 5 parts of polyferric chloride, 5 parts of magnesium oxide and 3 parts of water glass. The raw materials of the components are completely crushed to the fineness of 80-200 meshes for use.

The compound medicament B comprises the following raw materials in parts by weight: 90 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 5 parts of sodium alginate; 5 parts of magnesium lignosulfonate-acrylamide graft copolymer.

step one, preparing a compound medicament A:

(3) after the reaction step (2), sequentially adding the polyaluminium chloride, the zeolite powder and the polyferric chloride, maintaining the temperature at 55-60 ℃, and maintaining the stirring speed at 90-100 revolutions per minute for reaction for 60 minutes;

Step two, preparation of compound medicament B:

(1) preparation of sulfomethacrylamide-dimethyldiallylammonium chloride copolymer: firstly, injecting 60-80L of pure water into a reaction kettle, adding 27.5KG of dimethyl diallyl ammonium chloride, stirring and dissolving uniformly at the temperature of 55-65 ℃, supplementing pure water to a constant volume of 100L, and preparing a dimethyl diallyl ammonium chloride solution with the content of 27.5%;

adding 22KG of acrylamide with the purity of 98% into a dimethyldiallylammonium chloride solution with the content of 27.5%, and stirring for reaction for 50-60 minutes at the temperature of 60-70 ℃. Then adding 0.1% of disodium ethylene diamine tetraacetate and 0.1% of initiator to react for 5 minutes, wherein: the initiator is potassium persulfate/urea with a molar concentration ratio of 5.25:1.0 or sodium persulfate/sodium bisulfite with a molar concentration ratio of 7.0: 1.9; introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid; adding 25% of a-sodium hydroxymethanesulfonate solution and a proper amount of catalyst into a viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product;

(2) preparation of magnesium lignosulfonate-acrylamide graft copolymer: in the autoclave, the reaction was carried out as follows: 1, adding distilled water and magnesium lignosulfonate according to the mass ratio, controlling the temperature to be 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide, stirring for reaction at the temperature of 20-35 ℃, wherein the reaction time is 48-52 hours, and thus obtaining the magnesium lignosulfonate-acrylamide graft copolymer; wherein the concentration of acrylamide is 1.4mol/L, the mass ratio of the lignosulfonic acid to the acrylamide is 1:5, and the solid-to-liquid ratio is 1: 50, concentration of initiator potassium persulfate/sodium sulfite is 0.5X10^-2mol/L; wherein, the solid-to-liquid ratio refers to the ratio of the total mass of the magnesium lignosulfonate and the acrylamide to the mass of the distilled water.

(3) Uniformly mixing sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer according to the weight part ratio; injecting distilled water into an emulsification reaction kettle to obtain a mixtureAnd distilled water mass ratio of 1:5, dissolving in an emulsion reactor at 30-45 deg.C for 12-18 hr, adding initiator potassium persulfate/sodium sulfite with concentration of 0.5 × 10^-2mol/L; and continuously reacting for 28-30 hours, cooling to room temperature to form latex block polymers, and granulating, drying and crushing to obtain the compound medicament B.

(2) Ultrasonic treatment: and (3) feeding the mixture of the agent A and the agent B into an ultrasonic reaction kettle, wherein the ultrasonic frequency is 28000Hz-32000Hz, the stirring speed is controlled at 400-600 revolutions per minute, continuously dropwise adding 5L of 10% ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes. Controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours. After the reaction is finished, mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes to prepare the composite efficient environment-friendly water treatment agent.

Example 4

1. The compound efficient environment-friendly water treatment medicament comprises 98 parts of a compound medicament A and 2 parts of a compound medicament B according to the raw materials in parts by weight.

The compound medicament A comprises the following raw materials in parts by weight: 18 parts of fly ash, 28 parts of attapulgite, 4 parts of activated carbon powder, 4 parts of alumina powder, 4 parts of sodium bicarbonate, 8 parts of diatomite, 20 parts of polyaluminium chloride, 4 parts of zeolite powder, 4 parts of polyferric chloride, 4 parts of magnesium oxide and 2 parts of water glass. The raw materials of the components are completely crushed to the fineness of 80-200 meshes for use.

The compound medicament B comprises the following raw materials in parts by weight: the compound medicament B consists of the following raw materials in parts by weight: 82 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 8 parts of sodium alginate; 10 parts of magnesium lignosulfonate-acrylamide graft copolymer.

step one, preparing a compound medicament A:

(2) after the reaction step (1) is carried out, sequentially adding the activated carbon powder, the attapulgite powder and the diatomite, maintaining the stirring speed at 100 plus 200 revolutions per minute, controlling the temperature at 100 plus 110 ℃, and gradually cooling to 60 ℃ after the reaction time is 45-60 minutes;

(3) after the reaction step (2), sequentially adding the polyaluminium chloride, the zeolite powder and the polyferric chloride, maintaining the temperature at 55-60 ℃, and maintaining the stirring speed at 90-100 revolutions per minute for 65 minutes;

Step two, preparation of compound medicament B:

(1) preparation of sulfomethacrylamide-dimethyldiallylammonium chloride copolymer: firstly, injecting 60-80L of pure water into a reaction kettle, adding 28KG of dimethyl diallyl ammonium chloride, stirring and dissolving uniformly at the temperature of 55-65 ℃, supplementing the pure water to a constant volume of 100L, and preparing a dimethyl diallyl ammonium chloride solution with the content of 28%;

adding 24KG of acrylamide with the purity of 98% into a solution of the dimethyl diallyl ammonium chloride with the content of 28%, and stirring and reacting for 50-60 minutes at the temperature of 60-70 ℃. Then adding 0.2% of disodium ethylene diamine tetraacetate and 0.4% of initiator to react for 5 minutes, wherein: the initiator is potassium persulfate/urea with a molar concentration ratio of 5.3:1.2 or sodium persulfate/sodium bisulfite with a molar concentration ratio of 7.2: 2.0; then introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid; adding 28% of a-sodium hydroxymethanesulfonate solution and a proper amount of catalyst into a viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product;

(2) preparation of magnesium lignosulfonate-acrylamide graft copolymer: in the autoclave, the reaction was carried out as follows: 1, adding distilled water and magnesium lignosulfonate according to the mass ratio, controlling the temperature to be 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide, stirring for reaction at the temperature of 20-35 ℃, wherein the reaction time is 48-52 hours, and thus obtaining the magnesium lignosulfonate-acrylamide graft copolymer; wherein the concentration of acrylamide is 1.4mol/L, and the mass ratio of the lignosulfonic acid to the acrylamide is 1.5: 7.5. The solid-liquid ratio is 1.5: 85, the concentration of the initiator potassium persulfate/sodium sulfite is 0.7X 10^-2mol/L. Wherein, the solid-to-liquid ratio refers to the ratio of the total mass of the magnesium lignosulfonate and the acrylamide to the mass of the distilled water.

(3) Uniformly mixing sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer according to the weight part ratio; injecting distilled water into the emulsification reaction kettle, and mixing the prepared mixture and the distilled water according to the mass ratio of 2.5: 8.5, dissolving in an emulsion reactor at 30-45 deg.C for 12-18 hr, adding initiator potassium persulfate/sodium sulfite with concentration of 0.8 × 10^-2mol/L; and continuously reacting for 28-30 hours, cooling to room temperature to form latex block polymers, and granulating, drying and crushing to obtain the compound medicament B.

(1) mixing medicaments: and (3) uniformly mixing the compound medicament A obtained in the step (I) and the compound medicament B obtained in the step (II) according to the weight part ratio to obtain 100 parts of a mixture of the agent A and the agent B.

(2) Ultrasonic treatment: and (3) feeding the mixture of the agent A and the agent B into an ultrasonic reaction kettle, wherein the ultrasonic frequency is 28000Hz-32000Hz, the stirring speed is controlled at 400-600 revolutions per minute, continuously dropwise adding 4L of 10% ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes. Controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours. After the reaction is finished, mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes to prepare the composite efficient environment-friendly water treatment agent.

Example 5 application of the composite water high-efficiency environment-friendly water treatment agent prepared in example 1 of the present invention in biochemical pharmaceutical wastewater

1. Basic conditions of pollution discharge enterprises in application test field

The low molecular weight heparin sodium production capacity of a certain biochemical pharmaceutical company in Jiangsu is expanded, the whole drainage quantity and the drainage type of a project are changed, the discharge of the substances of benzethonium chloride, heparin sodium, ethanol, methanol, dichloromethane and tris (hydroxymethyl) aminomethane is increased in the low molecular weight heparin sodium production capacity expansion project, and a sewage treatment station cannot treat the substances.

2. Quality characteristics of waste water

(1) The original wastewater treatment process system of a certain biochemical pharmaceutical company in Jiangsu adopts: pharmaceutical wastewater → salt water collecting tank → homogenizing tank sulfuric acid regulation → aerobic tank → secondary sedimentation → flexible filtration → effluent water. Wherein, the secondary precipitation adopts the conventional medicament coagulation in the market, and the subsequent drainage can not reach the new environmental protection emission standard.

(2) The process for treating the medicament by adopting the invention comprises the following steps: collecting → homogenizing → using the composite water high-efficiency environment-friendly water treatment medicament provided by the invention for pretreatment → enzyme catalysis and anaerobism → using the composite water high-efficiency environment-friendly water treatment medicament provided by the invention for secondary sedimentation tank advanced treatment → standard discharge.

According to the analysis of the on-site investigation situation, the main problems and difficulties are as follows:

(1) the salt content in the wastewater is high, wherein the salt content of the strong brine can reach 12 ten thousand mg/L at most, the high salt content causes that a sewage treatment system cannot normally operate, particularly microorganisms in a biochemical system are difficult to culture, so that the microorganisms are poisoned and cannot survive, the operation of the biochemical system is seriously influenced, the pollutant degradation effect cannot be exerted, and the COD value in the effluent water is influenced. Therefore, the sewage station mainly utilizes clean water (including equipment cleaning water, pump circulating water and domestic sewage) to dilute saline water and then enters the aerobic tank for treatment.

(2) The change of the quality and the quantity of the wastewater is large, and the impact load resistance of a treatment system is poor.

(3) The biochemical pool of the original wastewater treatment system has small volume, so that the pollutant degradation effect is poor.

(4) When meeting sodium metabisulfite waste water, the existing sewage treatment station is difficult to treat.

(5) The existing system can not treat newly added mixed wastewater containing benzethonium chloride, heparin sodium, ethanol, methanol, dichloromethane, tris (hydroxymethyl) aminomethane and the like.

(6) The existing sewage station occupies a small area, and the space of a newly-built facility is very limited on the basis, so that difficulty is brought to the technical improvement and expansion design.

3. Design objective by adopting medicament and technology of the invention

Emission standard: CODCr (mg/L) < 30; ammonia nitrogen (mg/L) < 15; pH: 6-9.

Secondly, the treatment capacity of the production wastewater is met, and the process can treat the current production wastewater with the same water quality and the respective expansion capacity of at least 1.5 times to the total treatment capacity of 500 tons (containing clear water).

4. Phase of operation

a. The average COD of the inlet raw water is 5000-6500 mg/L, and after the pretreatment by adding the medicament provided by the invention, the COD is 500-800 mg/L. The average salt content of the raw water of the inlet water is more than 10000mg/L, and the salt content is less than 600mg/L after the pretreatment by adding the medicament provided by the invention. The subsequent advanced treatment is carried out at the pH value of 6.5-9.0 and the temperature of 15-35 ℃, and the subsequent treatment is preferably carried out by adopting enzyme catalytic contact oxidation → the medicament provided by the invention is used for advanced treatment in a secondary sedimentation tank → the medicament is discharged after reaching the standard.

b. Operating at full load for 14d, and treating water amount 300m on average³/d。

(1) The medicament is used for treating various biochemical pharmaceutical wastewater, different types of wastewater are pretreated firstly, and finally, comprehensive centralized treatment is carried out.

The following are the indexes of the reagent of the invention for pretreatment of different kinds of wastewater, such as reagent usage amount, effluent COD detection and COD removal rate, as shown in the following table 1:

TABLE 1

(2) After the biochemical pharmaceutical wastewater is treated comprehensively according to the process by adding the medicament of the invention, the average detailed index detection results of the water outlet are shown in the following table 2:

TABLE 2

Contaminants	Average water outlet index	Determination of the Condition	Index standard condition
				CODcrmg/L	25.51	Outlet sampling and actual measurement	Reach the standard
BOD5mg/L	10.22	Outlet sampling and actual measurement	Reach the standard
				SSmg/L	3.37	Outlet sampling and actual measurement	Reach the standard
NH3-Nmg/L	0.12	Outlet sampling and actual measurement	Reach the standard
				pH range	7.85	Outlet sampling and actual measurement	Reach the standard
TPmg/L	0.15	Outlet sampling and actual measurement	Reach the standard
				Colour(s)	Colorless and colorless	Appearance observation	Reach the standard
Smell of rice	Has no peculiar smell	Sense of smell	Reach the standard
				Salt content mg/L	93.5	Outlet sampling and actual measurement	Reach the standard

Example 6 application of the composite water-efficient environment-friendly water treatment agent prepared in example 2 of the present invention in treating coating wastewater

1. Basic conditions of application test pollution discharge enterprises

The waste water produced by a certain coating project enterprise in Guangdong province is mainly the workshop production waste water. The domestic sewage is directly discharged into a municipal sewage treatment plant. The work is carried out for 8 hours in one shift every day and for 251 days every year. The amount of wastewater produced was 60000 t/a. Wherein the comprehensive wastewater runs for 24 hours, and the second and third shifts are on duty. The production wastewater comprises pre-degreasing, degreasing wastewater, surface conditioning, phosphorization, electrophoresis, spray painting and other waste liquids and cleaning wastewater.

(1) The pre-degreasing and degreasing waste liquid is subjected to pre-degreasing and degreasing treatment before phosphorizing the component, wherein the generation amount of the pre-degreasing and degreasing waste liquid is as follows: 0.97t/d, namely 360t/a, the quality condition of the degreasing waste liquid: CODcr is 5000mg/L, SS1000mg/L, and petroleum concentration is 1000 mg/L.

(2) Surface conditioning and phosphating waste liquid: surface conditioning and phosphating are carried out before the component is sprayed with paint, wherein surface conditioning waste liquid 260t/a and phosphating waste liquid 608t/a are obtained. The CODcr in the waste water is 100mg/L, the oil concentration is 10mg/L, and the phosphate concentration is 400 mg/L.

(3) Electrophoretic waste liquid: the electrophoretic waste liquid is recycled, and the annual waste liquid yield is 10 t/a. CODcr is 20000mg/L, SS is 1000mg/L, and Pb concentration is 750 mg/L.

(4) Paint spraying wastewater: the water for spraying paint is recycled and discharged intermittently once a month. The annual wastewater production is 450 t/a. CODcr is 3000mg/L, SS 1500 mg/L.

(5) Cleaning wastewater: the components need to be cleaned after degreasing, phosphorization, electrophoresis and other processes, and the production amount of cleaning wastewater is calculated as 20t/d, namely 7300 t/a. The water quality condition of the cleaning wastewater: CODcr is 200mg/L, SS is 300mg/L, oil concentration is 15mg/L, phosphate concentration is 10mg/L, and Zn concentration is 20 mg/L.

2. The discharge conditions of the factory sewage and wastewater are shown in the following table 3:

TABLE 3

3. Water treatment medicine and dosage

(1) Alkali: is prepared from refined lime (containing 65-75% of Ca (OH))₂]Dissolving in water to obtain lime milk (Ca (OH)₂And a concentration of 40% (w/v).

(2) Acid: industrial 20-30% sulfuric acid is selected.

(3) Main water treatment agents: the invention relates to a compound water treatment medicament.

(4) The dosage is as follows: and determining according to water sample test data during field debugging.

4. The reagent beaker test is adopted to treat the comparative result data of the coating wastewater

(1) The purpose is as follows: the medicament is directly dosed according to a proportion, the optimal on-site dosing amount of the medicament is found out through laboratory simulation, and the industrial treatment test of the coating for a certain enterprise in Guangdong is determined.

(2) The principle is as follows: when the pollutants in water are mainly in a colloid state (or an emulsified state), the medicament agent is added to destabilize and agglomerate the pollutants, and precipitate sludge and water to separate. The optimal dosage of the medicament is the minimum dosage of the flocculant reaching the set water quality target, and has important technical and economic significance for sewage flocculant treatment.

(3) The invention relates to a medicament dosage simulation experiment method and comparison data: the medicament of the invention is used by 3 different medicament dosages, and the PH value is adjusted by using on-site 10% lime water and dilute sulfuric acid.

1) The test method of the drug dosage of the invention comprises the following steps: adding 1000ml of coating wastewater into a beaker with the capacity of 2000ml, weighing 0.1g of the composite medicament, uniformly stirring for about 5min, separating sludge from water after the sludge is settled, and measuring related numerical values, wherein the numerical values are shown in the following table 4:

TABLE 4

Index of water quality	Average raw water intake on site	Average drainage index after treatment	The removal rate is as follows: by%
				CODCr mg/L	15956.3	2215.2	86.1
Phosphorus mg/L	66.25	4.95	92.5
				SS mg/L	1480.6	5.63	99.6
Petroleum mg/L	103	9.35	90.9
				Heavy metals in mg/L in Pb	750	25.09	96.65

2) The test method for the drug administration amount of the invention 2: adding 1000ml of coating wastewater into a beaker with the capacity of 2000ml, weighing 0.15g of the composite medicament, uniformly stirring for about 10min, separating mud from water after the sludge is settled, and measuring related numerical values as shown in the following table 5:

TABLE 5

Index of water quality	Average raw water intake on site	Average drainage index after treatment	The removal rate is as follows: by%
				CODCr mg/L	15956.3	1845.3	88.4
Phosphorus mg/L	66.25	3.05	95.4
				SS mg/L	1480.6	4.01	99.73
Petroleum in mg/L	103	5.35	94.8
				Heavy metals in mg/L as Pb	750	15.22	97.97

3) The test method for the dosage of the medicament of the invention comprises the following steps: adding 1000ml of coating wastewater into a beaker with the capacity of 2000ml, weighing 0.2g of the composite medicament, uniformly stirring for about 15min, separating mud from water after the sludge is settled, and measuring related numerical values as shown in the following table 6:

TABLE 6

Index of water quality	Average raw water intake on site	Average drainage index after treatment	The removal rate is as follows: by%
				CODCr mg/L	5956.3	1104.2	93.07
Phosphorus mg/L	66.25	1.06	98.4
				SS mg/L	1480.6	2.25	99.85
Petroleum in mg/L	103	1.33	98.7
				Heavy metals in mg/L in Pb	750	7.16	99.09

5. The coating wastewater is treated in sections on site by adopting the primer, and the result is judged according to the paint industry water pollutant discharge standard.

(2) Acid: industrial 20% -30% sulfuric acid is selected.

(4) The dosage is as follows: and determining according to laboratory test result data during field debugging.

(5) The total amount of the coating wastewater subjected to field sectional treatment is 319M³。

(6) Adding the medicament and matched process flow

Water inlet, pH value adjustment in an adjusting tank, coagulation treatment (mud-water separation) in a first-stage feeding in a coagulation tank, biochemical tank treatment, sedimentation treatment (mud-water separation) in a second-stage feeding in the coagulation tank, and standard discharge. Wherein the dosage of the medicament is 250g/M after the coagulation treatment of the coagulation tank is added in one section³The dosage of the medicament added in the secondary coagulation tank is 100g/M³. The average dosage of the two times is 175g/M³. The results of the treatments are shown in table 7 below:

TABLE 7

Index of water quality	Average raw water intake on site	Average drainage index after treatment	Compliance condition
				CODCr mg/L	15956.3	85.9	Reach the standard
Phosphorus mg/L	66.25	0.4	Reach the standard
				SS mg/L	1480.6	2.9	Reach the standard
Petroleum in mg/L	103	2.2	Reach the standard
				Heavy metals in mg/L as Pb	750	0.05	Reach the standard

Example 7 application of the composite water efficient environment-friendly water treatment agent prepared in the invention in example 3 and example 4 in treating domestic wastewater

1. Basic condition of domestic wastewater of application test project

In a domestic wastewater treatment station in a certain village of Changsha city, Hunan province, the daily average amount of domestic wastewater to be treated is about 1000 tons.

2. The water quality index of the sewage from the domestic sewage treatment station is shown in the following table 8:

TABLE 8

3. Discharge standard of sewage treatment

According to the relevant regulations of the State environmental protection administration and the division standards of water area functional areas, the class B primary standard of the discharge Standard of pollutants for municipal wastewater treatment plant (GB18918-2002) is executed. The wastewater after treatment should meet the following criteria as shown in table 9:

TABLE 9 Sewage discharge control Standard

4. Domestic wastewater treatment process and treatment agent selection

(1) Design of process scheme

According to the above analysis of the quality of wastewater, BOD is required₅The removal rate of CODcr, SS and animal and vegetable oil is high. The sewage treatment process designed by the scheme selects a mature treatment process which has strong adaptability, flexible adjustment, low energy consumption, low investment, small occupied area and convenient operation and management and is considered aiming at the sewage quantity and the sewage quality of the village, local economic conditions, management level and the like.

1)BOD₅Ratio of/CODcr

General BOD₅/CODcr>0.45 of good biodegradability, BOD₅/CODcr<0.3 Biochemical resistance, BOD₅/CODcr<0.25 is not biochemical.

Influent water quality, BOD, of village sewage treatment plant₅＝300mg/L，CODcr＝500mg/L，BOD₅The biodegradability of the/CODcr-300/500-0.6 is a good type of town sewage, but the animal and vegetable oil content is high, so the treatment in the front section and the middle section is suitable for the treatment by adopting a primary coagulation treatment and a secondary biological treatment process.

2)BOD₅The ratio of/TN (i.e., C/N)

The C/N ratio is an important index for judging whether effective denitrification can be realized. Theoretically, the denitrification can be carried out with C/N ≥ 2.86, but it is generally considered that the effective denitrification can be carried out with C/N ≥ 3.50. And analyzing and determining the quality of the inlet water, wherein C/N is 300/25-12, and the requirement of biological denitrification is met.

3)BOD₅Ratio of/TP

The index is a main index for identifying whether biological phosphorus removal can be carried out. BOD₅The ratio of TP is an important index for measuring whether the dephosphorization effect can be achieved, generally, the value is more than 20, and the larger the ratio is, the more obvious the biological dephosphorization effect is.

The influent water quality of the village, BOD₅And the TP (300/4) is 75, and meets the condition of adopting the biological phosphorus removal process. But is not suitable for adopting the biological nitrogen and phosphorus removal process.

In conclusion, the inlet water quality of the village sewage treatment station is suitable for adopting a process method of primary coagulation sedimentation, secondary biochemistry and third-stage coagulation sedimentation treatment.

(2) Water treatment agent selection

The compound water treatment agent is put into the domestic wastewater of the village.

5. The invention sets the drug administration mode and the drug dosage

The medicament prepared in the embodiment 3 of the invention is added into the first-level coagulation tank, and the medicament prepared in the embodiment 4 of the invention is added into the third-level coagulation sedimentation tank. After the laboratory test of on-site beaker dosing, the dose of the medicament prepared in the embodiment 3 of the invention is 10mg/L added into the first-level coagulation tank; 2mg/L of the medicament prepared in the embodiment 4 of the invention is added in the three-stage coagulation sedimentation. The total dosage of the wastewater treatment in the whole section is 12g/m³. The administration mode is not dilutedReleasing and directly adding.

6. The detection data after the treatment of the first-stage coagulation tank added with the medicament prepared in the embodiment 3 of the invention is shown in the following table 10 (field dosage: 10 mg/L):

watch 10

7. After biochemical effluent is discharged, the detection data of the medicament prepared in the embodiment 4 of the invention added into the three-stage coagulation pond after treatment is shown in the following table 11 (the field dosage is 2 mg/L):

TABLE 11

8. 1000 tons of domestic wastewater is treated daily, and the economic cost of using the medicament of the invention is as follows:

(1) the water treatment agent prepared by the invention is calculated according to the market sale price of 5000 yuan per ton, namely 5 yuan/KG. 1000 tons of domestic wastewater are treated daily, and the consumed medicament amount is as follows: 1000 ton × 12 g/ton 12000 g-12 KG.

(2) 1000 tons of domestic wastewater is treated daily, and the total cost of the medicine put in every day is as follows: 12KG × 5-membered/KG ═ 60-membered.

(3) The cost of the univalent agent for treating 1 ton of domestic wastewater is as follows: the cost of the medicament is 6 cents (no field technical labor cost is contained), and the cost of the medicament is 0.06 yuan/ton when 60 yuan/1000 ton is changed into 0.06 yuan/ton, namely 1 ton of domestic wastewater is treated.

Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.

Claims

1. The composite high-efficiency environment-friendly water treatment agent is characterized in that: the water treatment medicament comprises the following raw materials in parts by weight: 97-99 parts of compound medicament A and 1-3 parts of compound medicament B;

raw materials of the compound medicament B comprise sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer;

the preparation steps of the compound medicament A are as follows:

(4) after the reaction step (3), finally adding water glass and sodium bicarbonate, maintaining the temperature at 45-50 ℃, and maintaining the stirring speed at 100-180 revolutions per minute for reaction for 20-30 minutes; after the reaction is finished, the temperature is reduced to normal temperature to obtain a compound medicament A for later use;

the preparation steps of the compound medicament B are as follows:

adding 22-25KG of acrylamide with the purity of 98% into a 25-30% dimethyl diallyl ammonium chloride solution, stirring and reacting for 50-60 minutes at the temperature of 60-70 ℃, and then adding 0.1-0.3% of disodium ethylene diamine tetraacetate and 0.1-0.6% of initiator to react for 5 minutes, wherein: the initiator is potassium persulfate/urea with a molar concentration ratio of 5.25-5.5:1.0-1.31 or sodium persulfate/sodium bisulfite with a molar concentration ratio of 7.0-7.33: 1.9-2.26; then introducing nitrogen to expel oxygen for 30-45 minutes, and reacting for 1-2 hours at the temperature of 5-30 ℃ to form viscous liquid; adding 25-30% of a-sodium hydroxymethyl sulfonate solution and a proper amount of catalyst into a viscous liquid system, reacting for 4-6 hours at 70-95 ℃, cooling to 25-35 ℃ to form a rubber block polymer, and granulating, drying and crushing to obtain a sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer finished product;

(2) preparation of magnesium lignosulfonate-acrylamide graft copolymer: in a reaction kettle according to the ratio of 2-3: 1-1.5, adding distilled water and magnesium lignosulfonate, controlling the temperature to be 48-55 ℃, stirring for reaction for 10-15 minutes, activating lignin, adding an initiator and acrylamide, stirring for reaction at 20-35 ℃, and reacting for 48-52 hours to obtain a magnesium lignosulfonate-acrylamide graft copolymer; wherein the concentration of acrylamide is 1.4mol/L, the mass ratio of magnesium lignosulfonate to acrylamide is 1-2:5-9, and the solid-liquid ratio is 1-2: 50-100, the concentration of initiator potassium persulfate/sodium sulfite is 0.5X10^-2 mol/L-1.0×10^-2 mol/L；

(3) Uniformly mixing sulfomethacrylamide-dimethyl diallyl ammonium chloride copolymer, sodium alginate and magnesium lignosulfonate-acrylamide graft copolymer according to the weight part ratio; injecting distilled water into the emulsification reaction kettle, and mixing the prepared mixture and the distilled water according to the mass ratio of 1-2: 5-10 deg.C, dissolving in emulsifying reactor at 30-45 deg.C for 12-18 hr, adding 0.5 × 10^-2 mol/L-1.0×10^-2And (3) continuously reacting potassium persulfate or sodium sulfite serving as an initiator in mol/L for 28-30 hours, cooling to room temperature to form latex block polymers, and granulating, drying and crushing to obtain the compound medicament B.

2. The compound efficient environment-friendly water treatment agent as claimed in claim 1, wherein: the water treatment medicament comprises the following raw materials in parts by weight: 97.5 parts of compound medicament A and 1.5 parts of compound medicament B.

3. The compound efficient environment-friendly water treatment agent as claimed in claim 1, wherein: the compound medicament A comprises the following raw materials in parts by weight: 5-20 parts of fly ash, 10-30 parts of attapulgite, 2-5 parts of activated carbon powder, 1-5 parts of alumina powder, 1-5 parts of sodium bicarbonate, 1-10 parts of diatomite, 20-50 parts of polyaluminium chloride, 1-5 parts of zeolite powder, 1-5 parts of polyferric chloride, 1-5 parts of magnesium oxide and 1-3 parts of water glass;

4. The compound high-efficiency environment-friendly water treatment medicament as claimed in claim 3, wherein: the compound medicament A comprises the following raw materials in parts by weight: 15 parts of fly ash, 15 parts of attapulgite, 4 parts of activated carbon powder, 3 parts of alumina powder, 2 parts of sodium bicarbonate, 6 parts of diatomite, 45 parts of polyaluminum chloride, 3 parts of zeolite powder, 3 parts of polyferric chloride, 2 parts of magnesium oxide and 2 parts of water glass; the raw material components are completely crushed to the fineness of 80-200 meshes for use.

5. The compound high-efficiency environment-friendly water treatment medicament as claimed in claim 3, wherein: the compound medicament B comprises the following raw materials in parts by weight: 85 parts of sulfomethylacrylamide-dimethyldiallylammonium chloride copolymer; 7 parts of sodium alginate; 8 parts of magnesium lignosulfonate-acrylamide graft copolymer.

6. The preparation method of the compound high-efficiency environment-friendly water treatment medicament as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps: respectively preparing a compound medicament A agent and a compound medicament B agent, then uniformly mixing the compound medicament A agent and the compound medicament B agent according to the weight part ratio, and compounding after ultrasonic treatment to obtain the compound high-efficiency environment-friendly water treatment medicament.

7. The preparation method of the compound efficient environment-friendly water treatment medicament as claimed in claim 6, wherein the preparation method comprises the following steps:

the mixing steps of the compound medicament A and the compound medicament B are as follows:

(2) ultrasonic treatment: sending the mixture into an ultrasonic reaction kettle, controlling the ultrasonic frequency to be 28000Hz-32000Hz, controlling the stirring speed to be 600 revolutions per minute, continuously dropwise adding 2-5L of 10 percent ferrate solution into the ultrasonic reaction kettle, and finishing dropwise adding within 15 minutes; controlling the reaction temperature to be 45-55 ℃, and continuously mixing and reacting for 1-1.5 hours; after the reaction is finished, a mixed reactant of the agent A and the agent B is obtained, dried at 60 ℃, and crushed to 60-150 meshes, thus obtaining the composite efficient environment-friendly water treatment agent.

8. The use of the compound high-efficiency environment-friendly water treatment medicament as claimed in any one of claims 1 to 5, wherein: the water treatment agent can be used for treating various industrial, agricultural and domestic wastewater, and is also applied to treatment of river, lake, landscape pool, black and odorous ditch and marine pollution.