An industrial wastewater water quality treatment agent, its preparation method and application

Abstract

The present invention provides an industrial wastewater treatment agent and a preparation method and application thereof, belonging to the technical field of wastewater treatment. The water treatment agent of the present invention comprises the following components by mass: 10 to 30 parts of a mixed extract pre-filming agent of lobster shells and crab shells, 60 to 80 parts of ferrous sulfate heptahydrate and 15 to 20 parts of slaked lime. The water treatment agent is compounded with a mixed extract pre-filming agent of lobster shells and crab shells, which are waste from aquatic product processing plants, ferrous sulfate heptahydrate and slaked lime, which effectively implements the recycling of waste, has a green and environmentally friendly concept, solves the problem of increased TDS in wastewater, ensures that the total amount of soluble solids in the treated water is significantly reduced, and removes organic pollutants COD and heavy metals at the same time, improves biodegradability and ensures the goal of stable operation of the subsequent biochemical treatment process of industrial wastewater.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater treatment, and particularly relates to an industrial wastewater water quality treatment agent, a preparation method thereof, and an application thereof. Background Art

[0002] The wastewater discharged from industrial production not only contains various organic acids, alcohols, aldehydes, ketones, ethers, and epoxides, etc., but also has relatively high biochemical oxygen demand and chemical oxygen demand. At the same time, industrial wastewater also has strong acidity and alkalinity, unstable pH, contains a large amount of dissolved solids and heavy metals, which are extremely harmful to aquatic organisms, structures, and crops. At present, physical and chemical treatment is used for industrial wastewater followed by biochemical treatment. During the treatment process, the change of dissolved solids in industrial wastewater is often ignored and not taken seriously enough. Due to the existence of dissolved solids, the biochemical treatment is unstable, affecting the final effect of the entire industrial wastewater treatment and greatly increasing the treatment cost. For example, Chinese Patent CN105126773A discloses a renewable heavy metal adsorption material made from shrimp and crab shells, a preparation method, a regeneration method, and an application thereof. This patent prepares a new type of shrimp and crab shell adsorption material to adsorb heavy metals in water, but the adsorption effect on dissolved solid substances in water is not good; CN105439216A discloses a printing and dyeing wastewater treatment agent and a preparation method thereof. This treatment agent has a good removal effect on substances such as inorganic salts in wastewater, but this treatment agent only has a good treatment effect on printing and dyeing wastewater, mainly because the content of inorganic salts in printing and dyeing wastewater is relatively high. Therefore, this treatment agent is difficult to be used in other industrial wastewaters, such as industrial wastewater with a high content of heavy metals.

[0003] In summary, it is necessary to develop an industrial wastewater water quality treatment agent that can solve the problem of the increase in TDS during the wastewater treatment process and ensure the stable operation of the subsequent biochemical treatment process. Summary of the Invention

[0004] The purpose of the present invention is to provide an industrial wastewater water quality treatment agent, a preparation method thereof, and an application thereof, which can solve the problem of the increase in TDS during the wastewater treatment process, ensure a reduction in the total amount of dissolved solids in the treated water quality, and ensure the stable operation of the subsequent biochemical treatment process. To achieve the above purpose, the present invention provides an industrial wastewater water quality treatment agent and an application method thereof:

[0005] In the first aspect, the present invention provides an industrial wastewater water quality treatment agent, the components of which include a mixed extract prefilm agent of lobster shells and crab shells, ferrous sulfate heptahydrate, and slaked lime.

[0006] Further, by mass, the water quality treatment agent includes 10 - 30 parts of a mixed extract prefilm agent of lobster shells and crab shells, 60 - 80 parts of ferrous sulfate heptahydrate, and 15 - 20 parts of slaked lime;

[0007] Preferably, by mass parts, the water treatment agent comprises 12-20 parts of a prefilming agent which is a mixed extract of lobster shells and crab shells, 64-72 parts of ferrous sulfate heptahydrate, and 16-18 parts of slaked lime.

[0008] Further, the mass ratio of the mixed extract of lobster shells and crab shells as the prefilming agent, ferrous sulfate heptahydrate, and slaked lime is 0.1-2:3-5.0:1, preferably 0.2-1.2:3.75-4:1.

[0009] More preferably, by mass parts, the water treatment agent comprises 15 parts of a prefilming agent which is a mixed extract of lobster shells and crab shells, 67.5 parts of ferrous sulfate heptahydrate, and 17.5 parts of slaked lime;

[0010] In a second aspect, the present invention also provides a preparation method of a prefilming agent which is a mixed extract of lobster shells and crab shells, comprising the following steps:

[0011] S1. Pretreatment of raw materials

[0012] First, remove the meat and dirt impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them.

[0013] S2. Acid leaching treatment

[0014] Place the pretreated lobster shells and crab shells in a dilute hydrochloric acid solution, soak them at room temperature, and then filter and wash them with water until neutral.

[0015] S3. Digestion treatment

[0016] Place the lobster shells and crab shells after acid leaching treatment in a sodium hydroxide solution and boil them, then filter and wash them with water until neutral, and then dry them.

[0017] S4. Reaction extraction

[0018] Place the lobster shells and crab shells after the digestion treatment in S3 in a sodium hydroxide solution for hydrolysis, then filter and wash them with water until neutral, and then dry them to obtain a mixed extract of lobster shells and crab shells.

[0019] S5. Production and preparation

[0020] Mix the mixed extract of lobster shells and crab shells in S4 with a prefilming aid, modified carboxymethyl cellulose, in a mass ratio of 18-25:1 evenly to obtain the prefilming agent which is a mixed extract of lobster shells and crab shells.

[0021] Further, the drying temperature in the S1 step is 100°C - 110°C, and the drying time is 1 hour;

[0022] Further, the mass concentration of the dilute hydrochloric acid solution in step S2 is 1% - 15%, and the soaking time is 2 hours;

[0023] Further, the mass concentration of the sodium hydroxide solution in step S3 is 10% - 20%, and the boiling time is 2 hours;

[0024] Further, the drying temperature in step S3 is 50°C - 70°C, and the drying time is 2 hours;

[0025] Further, the mass concentration of the sodium hydroxide solution in step S4 is 40% - 50%, the hydrolysis temperature is 100 - 110°C, and the hydrolysis time is 2 hours;

[0026] Further, the drying temperature in step S4 is 100°C - 120°C, and the drying time is 2 hours.

[0027] Further, the pre - film forming aid in step S5 is modified carboxymethyl cellulose, and the preparation method of the modified carboxymethyl cellulose is as follows: Under stirring conditions, carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator are successively dissolved in water, where the mass ratio of carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator is 1:5 - 10:0.02, the pH is adjusted to 6 - 8, and the reaction is carried out at 70°C - 90°C for 3 - 5 h to obtain modified carboxymethyl cellulose.

[0028] The modified carboxymethyl cellulose is a film - forming agent and a stabilizer, which helps to stabilize the formulation components and exert the effects of each component.

[0029] In the third aspect, the present invention also provides a preparation method of an industrial wastewater water quality treatment agent. The preparation method is as follows: The mixed extract pre - film forming agent of lobster shells and crab shells is first added with ferrous sulfate heptahydrate for mixed pre - film forming, then slaked lime is added and mixed evenly by mass parts, and then pulverized into a powdery material for immediate preparation and use.

[0030] In the fourth aspect, the present invention also provides an application of the industrial wastewater water quality treatment agent in the field of wastewater treatment.

[0031] Further, the usage method of the water quality treatment agent during the application process is as follows:

[0032] Adjust the pH of the wastewater, keep it in a stirring state, then add the above - mentioned industrial wastewater water quality treatment agent for reaction, and after aeration, carry out flocculation and precipitation.

[0033] Further, the pH of the wastewater is adjusted to 6.5 - 9.0, and the stirring rate is 80 - 120 revolutions per minute.

[0034] Further, the dosage of the industrial wastewater water quality treatment agent is 0.5 - 5 grams per liter of wastewater, the aeration time is 0.5 - 3 hours, and the flocculation time is 0.1 - 12 hours.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] The water quality treatment agent of the present invention is prepared by compounding a pre - film agent with a mixed extract of waste lobster shells and crab shells from aquatic product processing plants, effectively implementing the recycling of waste, and having the concept of environmental protection. The pre - film agent with a mixed extract of lobster shells and crab shells has excellent adsorption characteristics and flocculation functions. Within a specific mixing ratio range with ferrous sulfate heptahydrate and slaked lime, it solves the problem of increased TDS during wastewater treatment, ensures that the total dissolved solids in the treated water meet the standards, simultaneously removes organic pollutants COD and heavy metals, improves biodegradability, effectively overcomes the problem of insufficient understanding of total dissolved solids in biochemical treatment in existing water treatment technologies, and achieves the goal of stable operation of subsequent biochemical treatment processes. Specific Embodiments

[0037] In the following embodiments of the present invention, the experimental methods without specific conditions noted are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. All common chemical reagents used in the embodiments are commercially available products.

[0038] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0039] The terms "comprising" and "having" and any variations thereof in the present invention are intended to cover non - exclusive inclusion. For example, a process, method, device, product, or equipment that includes a series of steps is not limited to the listed steps or modules, but may optionally further include steps not listed, or may optionally further include other steps inherent to these processes, methods, products, or equipment.

[0040] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of well - known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present invention.

[0041] The following embodiments further describe the present invention, but these embodiments are not intended to limit the protection scope of the present invention.

[0042] Embodiment 1

[0043] The water treatment agent of Example 1 contains, by mass, 12 g of a pre-film forming agent which is a mixed extract of lobster shells and crab shells, 70 g of ferrous sulfate heptahydrate, and 18 g of slaked lime.

[0044] The specific preparation steps of the pre-film forming agent which is a mixed extract of lobster shells and crab shells are as follows:

[0045] S1. Pretreatment of raw materials

[0046] First, remove the meat and dirt impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them at 100 °C for 1 h.

[0047] S2. Acid leaching treatment

[0048] Put 200 g of the pretreated lobster shells and crab shells into 500 mL of 5% dilute hydrochloric acid solution, soak them at room temperature for 2 h, then filter and wash them with water until neutral.

[0049] S3. Digestion treatment

[0050] Put the lobster shells and crab shells after acid leaching treatment into 10% sodium hydroxide solution, boil them for 2 h, then filter and wash them with water until neutral, and then dry them at 55 °C for 2 h.

[0051] S4. Reaction extraction

[0052] Put the lobster shells and crab shells after digestion treatment in S3 into 40% sodium hydroxide solution, hydrolyze them at 100 °C for 2 h, then filter and wash them with water until neutral, and then dry them at 105 °C for 2 h to obtain 25.6 g of a mixed extract of lobster shells and crab shells.

[0053] S5. Production and preparation

[0054] Add 1.35 g of a pre-film aid, modified carboxymethyl cellulose, to the mixed extract of lobster shells and crab shells in S4, mix them evenly, and then obtain 26.95 g of a pre-film forming agent which is a mixed extract of lobster shells and crab shells.

[0055] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in a mass ratio of 1:5:0.02 in sequence, adjust the pH to 6, and react at 80 °C for 3 h to obtain modified carboxymethyl cellulose.

[0056] The preparation method of the water treatment agent of Example 1 is as follows: First add 12 g of the pre-film forming agent which is a mixed extract of lobster shells and crab shells to 70 g of ferrous sulfate heptahydrate, mix them evenly for pre-filming, then add 18 g of slaked lime and mix them evenly, and crush them into powdery materials for immediate use.

[0057] The method for applying the above-prepared water treatment agent to the engineering site is as follows:

[0058] Raw water quality of industrial wastewater: pH is 5.5, COD is 3425 mg / L, and TDS (total dissolved solids) is 16800 mg / L.

[0059] Steps for applying the water quality treatment agent are as follows:

[0060] (1) Adjust the pH of the industrial wastewater to 7.5, and the stirring rate is 100 revolutions per minute;

[0061] (2) Then add the water quality treatment agent, and the dosage is 2 grams of the water quality treatment agent per liter of wastewater. Aerate for 1 hour and then perform flocculation precipitation, and the flocculation time is 2 hours;

[0062] (3) Then filter, and detect the supernatant of the industrial wastewater. The results are: pH is 8.0, COD is 1201 mg / L, the COD removal rate is 64.9%, and TDS (total dissolved solids) is 9800 mg / L, meeting the requirement of subsequent biochemical TDS < 10000 mg / L (process design requirement).

[0063] Example 2

[0064] The water quality treatment agent, by mass, contains the following components: 14 g of a pre-film agent which is a mixed extract of lobster shells and crab shells, 68 g of ferrous sulfate heptahydrate, and 18 g of slaked lime.

[0065] The specific preparation steps of the pre-film agent which is a mixed extract of lobster shells and crab shells are as follows:

[0066] S1. Pretreatment of raw materials

[0067] First, remove the meat and dirt impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them at 105 °C for 1 h;

[0068] S2. Acid leaching treatment

[0069] Put 200 g of the pretreated lobster shells and crab shells into 500 mL of 8% dilute hydrochloric acid solution, soak at room temperature for 2 h, and then filter and wash with water until neutral;

[0070] S3. Digestion treatment

[0071] Put the lobster shells and crab shells after acid leaching treatment into 15% sodium hydroxide solution and boil for 2 h, then filter and wash with water until neutral, and then dry at 50 °C for 2 h;

[0072] S4. Reaction extraction

[0073] Put the lobster shells and crab shells after digestion treatment in step S3 into 45% sodium hydroxide solution, hydrolyze at 110 °C for 2 h, then filter and wash with water until neutral, and then dry at 115 °C for 2 h to obtain 24.8 g of a mixed extract of lobster shells and crab shells.

[0074] S5. Production and Preparation

[0075] Add 1.3 g of pre-film aid modified carboxymethyl cellulose to the mixed extract of S4 lobster shells and crab shells, and mix evenly to obtain 26.1 g of the pre-film agent for the mixed extract of lobster shells and crab shells.

[0076] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in a mass ratio of 1:5:0.02 in sequence, adjust the pH to 6.8, and react at 80 °C for 3 h to obtain modified carboxymethyl cellulose.

[0077] The preparation method of the water treatment agent in this Example 2 is as follows: First, add 14 g of the pre-film agent for the mixed extract of lobster shells and crab shells to 68 g of ferrous sulfate heptahydrate, mix evenly for pre-filming, then add 18 g of slaked lime and mix evenly, and crush to form a powdery material for immediate use.

[0078] The method for applying the above-prepared water treatment agent to the engineering site is as follows:

[0079] Raw water quality of industrial wastewater: pH is 5.5, COD is 3425 mg / L, and TDS (total dissolved solids) is 16800 mg / L.

[0080] The application steps of the water treatment agent are as follows:

[0081] (1) Adjust the pH of the industrial wastewater to 8.0, and the stirring rate is 80 revolutions per minute;

[0082] (2) Then add the water treatment agent, and the dosage is 1 g of the water treatment agent per liter of wastewater, and aerate for 1 hour and then flocculate and precipitate, and the flocculation time is 5 hours;

[0083] (3) Then filter, and detect the supernatant of the industrial wastewater. The results are pH is 8.2, COD is 1186 mg / L, the COD removal rate is 65.4%, and TDS (total dissolved solids) is 9500 mg / L, meeting the requirement of subsequent biochemical TDS < 10000 mg / L (process design requirement).

[0084] Example 3

[0085] The water treatment agent, by mass, contains the following components: 15 g of the pre-film agent for the mixed extract of lobster shells and crab shells, 67.5 g of ferrous sulfate heptahydrate, and 17.5 g of slaked lime.

[0086] The specific preparation steps of the pre-film agent for the mixed extract of lobster shells and crab shells are as follows:

[0087] S1. Pretreatment of Raw Materials

[0088] First, remove the meat, dirt and impurities from the collected lobster shells and crab shells, wash them clean with water, and then dry them at 110°C for 1 h.

[0089] S2. Acid leaching treatment

[0090] Put 200 g of the pretreated lobster shells and crab shells into 500 mL of 5% dilute hydrochloric acid solution, soak them at room temperature for 2 h, and then filter and wash them with water until neutral.

[0091] S3. Digestion treatment

[0092] Put the lobster shells and crab shells after acid leaching treatment into 10% sodium hydroxide solution, boil them for 2 h, then filter and wash them with water until neutral, and then dry them at 55°C for 2 h.

[0093] S4. Reaction extraction

[0094] Put the lobster shells and crab shells after the digestion treatment in S3 into 45% sodium hydroxide solution, hydrolyze them at 110°C for 2 h, then filter and wash them with water until neutral, and then dry them at 120°C for 2 h to obtain 24.2 g of the mixed extract of lobster shells and crab shells.

[0095] S5. Production and preparation

[0096] Add 1.27 g of pre-film aid modified carboxymethyl cellulose to the mixed extract of lobster shells and crab shells in S4, and mix them evenly to obtain 25.47 g of the pre-film agent of the mixed extract of lobster shells and crab shells.

[0097] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in a mass ratio of 1:5:0.02 in sequence, adjust the pH to 7.4, and react at 80°C for 3 h to obtain modified carboxymethyl cellulose.

[0098] The preparation method of the water quality treatment agent in this Example 3 is as follows: Add 15 g of the pre-film agent of the mixed extract of lobster shells and crab shells, first add 67.5 g of ferrous sulfate heptahydrate, mix them evenly for pre-filming, then add 17.5 g of slaked lime, mix them evenly, and crush them into powdery materials for immediate use.

[0099] The method for applying the prepared water quality treatment agent to the engineering site is as follows:

[0100] The raw water quality of industrial wastewater: pH is 5.5, COD is 3425 mg / L, and TDS (total dissolved solids) is 16800 mg / L.

[0101] The application steps of the water quality treatment agent are as follows:

[0102] (1) Adjust the pH of the industrial wastewater to 8.5, and the stirring rate is 120 revolutions per minute;

[0103] (2) Then add a water quality treatment agent, with a dosage of 3 grams of the water quality treatment agent per liter of wastewater, and aerate for 1 hour and then flocculate and precipitate, with a flocculation time of 0.5 hour;

[0104] (3) Then filter, and detect the supernatant of the industrial wastewater. The results are that the pH is 8.6, the COD is 1066 mg / L, the COD removal rate is 68.8%, and the TDS (total dissolved solids) is 9200 mg / L, meeting the requirement of the subsequent biochemical TDS < 10000 mg / L (process design requirement).

[0105] Example 4

[0106] The water quality treatment agent, by mass, contains the following components: 16 g of a pre - film agent which is a mixed extract of lobster shells and crab shells, 67 g of ferrous sulfate heptahydrate, and 17 g of slaked lime.

[0107] The specific preparation steps of the pre - film agent which is a mixed extract of lobster shells and crab shells are as follows:

[0108] S1. Pretreatment of raw materials

[0109] First, remove the meat and dirt impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them at 110 °C for 1 h;

[0110] S2. Acid leaching treatment

[0111] Put 200 g of the pretreated lobster shells and crab shells into 500 mL of 5% dilute hydrochloric acid solution, soak at room temperature for 2 h, and then filter and wash with water until neutral;

[0112] S3. Digestion treatment

[0113] Put the lobster shells and crab shells after acid leaching treatment into 20% sodium hydroxide solution, boil for 2 h, then filter and wash with water until neutral, and then dry at 65 °C for 2 h;

[0114] S4. Reaction extraction

[0115] Put the lobster shells and crab shells after the digestion treatment in S3 into 50% sodium hydroxide solution, hydrolyze at 100 °C for 2 h, then filter and wash with water until neutral, and then dry at 115 °C for 2 h to obtain 23.6 g of a mixed extract of lobster shells and crab shells.

[0116] S5. Production and preparation

[0117] Add 1.24 g of a pre - film auxiliary agent, modified carboxymethyl cellulose, to the mixed extract of lobster shells and crab shells in S4, and mix evenly to obtain 24.84 g of a pre - film agent which is a mixed extract of lobster shells and crab shells.

[0118] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator are dissolved in water in a mass ratio of 1:8:0.02 in sequence, the pH is adjusted to 8, and the reaction is carried out at 80 °C for 3 h to obtain modified carboxymethyl cellulose.

[0119] The preparation method of the water treatment agent in Example 4 of this embodiment is as follows: 16 g of the mixed extract prefilm agent of lobster shells and crab shells is first added with 67 g of ferrous sulfate heptahydrate, mixed evenly for prefilming, then 17 g of slaked lime is added and mixed evenly, and then pulverized into a powdery material for immediate preparation and use.

[0120] The method for applying the prepared water treatment agent to the engineering site is as follows:

[0121] The raw water quality of industrial wastewater: pH is 5.0, COD is 1560 mg / L, and TDS (total dissolved solids) is 26600 mg / L.

[0122] The application steps of the water treatment agent are as follows:

[0123] (1) Adjust the pH of the industrial wastewater to 7.0, and the stirring rate is 120 revolutions per minute;

[0124] (2) Then add the water treatment agent, and the dosage is 3 grams of the water treatment agent per liter of wastewater, and aerate for 1 hour and then flocculate and precipitate, and the flocculation time is 0.5 hour;

[0125] (3) Then filter, detect the supernatant of the industrial wastewater, and the results are pH is 7.2, COD is 750 mg / L, the COD removal rate is 51.9%, and TDS (total dissolved solids) is 18200 mg / L, meeting the requirement of the subsequent biochemical TDS < 20000 mg / L (process design requirement).

[0126] Example 5

[0127] The water treatment agent contains the following components by mass: 18 g of the mixed extract prefilm agent of lobster shells and crab shells, 65.5 g of ferrous sulfate heptahydrate, and 16.5 g of slaked lime.

[0128] The specific preparation steps of the mixed extract prefilm agent of the lobster shells and crab shells are as follows:

[0129] S1. Pretreatment of raw materials

[0130] First, remove the meat, dirt and impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them at 105 °C for 1 h;

[0131] S2. Acid leaching treatment

[0132] Place 200 g of pretreated lobster and crab shells in 500 mL of 12% dilute hydrochloric acid solution, soak at room temperature for 2 h, then filter and wash with water until neutral;

[0133] S3. Digestion treatment

[0134] Place the acid-leached lobster and crab shells in 15% sodium hydroxide solution and boil for 2 h, then filter and wash with water until neutral, and then dry at 50 °C for 2 h;

[0135] S4. Reaction extraction

[0136] Place the lobster and crab shells after S3 digestion treatment in 45% sodium hydroxide solution, hydrolyze at 105 °C for 2 h, then filter and wash with water until neutral, and then dry at 110 °C for 2 h to obtain 26.4 g of a mixed extract of lobster and crab shells.

[0137] S5. Production and preparation

[0138] Add 1.39 g of pre-film aid modified carboxymethyl cellulose to the mixed extract of lobster and crab shells in S4, and mix evenly to obtain 27.79 g of a pre-film agent of the mixed extract of lobster and crab shells.

[0139] The preparation method of the water treatment agent in Example 5 of this embodiment is as follows: First, add 18 g of the pre-film agent of the mixed extract of lobster and crab shells, then add 65.5 g of ferrous sulfate heptahydrate, mix evenly for pre-filming, then add 16.5 g of slaked lime, mix evenly, and crush to form a powdery material for immediate use.

[0140] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in a mass ratio of 1:8:0.02 in sequence, adjust the pH to 7.4, and react at 80 °C for 3 h to obtain modified carboxymethyl cellulose.

[0141] The method for applying the prepared water treatment agent to the engineering site is as follows:

[0142] The raw water quality of industrial wastewater: pH is 5.0, COD is 1560 mg / L, and TDS (total dissolved solids) is 26600 mg / L.

[0143] The application steps of the water treatment agent are as follows:

[0144] (1) Adjust the pH of industrial wastewater to 6.5, and the stirring rate is 120 revolutions per minute;

[0145] (2) Then add the water treatment agent, and the dosage is 1.5 grams of the water treatment agent per liter of wastewater, and aerate for 1 hour and then flocculate and precipitate, and the flocculation time is 1 hour;

[0146] (3) Then filter and detect the supernatant of the industrial wastewater. The results show that the pH is 6.8, the COD is 770 mg / L, the COD removal rate is 50.6%, and the TDS (total dissolved solids) is 16,200 mg / L, meeting the requirement of the subsequent biochemical TDS < 20,000 mg / L (process design requirement).

[0147] Example 6

[0148] The water quality treatment agent, by mass, contains the following components: 20 g of the mixed extract prefilm agent of lobster shells and crab shells, 64 g of ferrous sulfate heptahydrate, and 16 g of slaked lime.

[0149] The specific preparation steps of the mixed extract prefilm agent of lobster shells and crab shells are as follows:

[0150] S1. Pretreatment of raw materials

[0151] First, remove the meat, dirt, and impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them at 100 °C for 1 h.

[0152] S2. Acid leaching treatment

[0153] Place 200 g of the pretreated lobster shells and crab shells in 500 mL of 2% dilute hydrochloric acid solution, soak them at room temperature for 2 h, and then filter and wash them with water until neutral.

[0154] S3. Digestion treatment

[0155] Place the acid-leached lobster shells and crab shells in 10% sodium hydroxide solution and boil for 2 h, then filter and wash them with water until neutral, and then dry them at 55 °C for 2 h.

[0156] S4. Reaction extraction

[0157] Place the lobster shells and crab shells after the digestion treatment in S3 in 40% sodium hydroxide solution, hydrolyze at 110 °C for 2 h, then filter and wash them with water until neutral, and then dry them at 100 °C for 2 h to obtain 28.2 g of the mixed extract of lobster shells and crab shells.

[0158] S5. Production and preparation

[0159] Add 1.48 g of the prefilm aid modified carboxymethyl cellulose to the mixed extract of lobster shells and crab shells in S4, and mix evenly to obtain 29.68 g of the mixed extract prefilm agent of lobster shells and crab shells.

[0160] The preparation method of the above-mentioned modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in a mass ratio of 1:10:0.02 in sequence, adjust the pH to 6.5, and react at 80 °C for 3 h to obtain the modified carboxymethyl cellulose.

[0161] The preparation method of the water quality treatment agent in Example 6 is as follows: First, add 20 g of the pre-film agent, which is a mixed extract of lobster shells and crab shells, to 64 g of ferrous sulfate heptahydrate, mix evenly for pre-filming, then add 16 g of slaked lime, mix evenly, and crush to form a powdery material for immediate use.

[0162] The method of applying the above-prepared water quality treatment agent to the engineering site is as follows:

[0163] The raw water quality of industrial wastewater: pH is 5.0, COD is 1560 mg / L, and TDS (total dissolved solids) is 26600 mg / L.

[0164] The application steps of the water quality treatment agent are as follows:

[0165] (1) Adjust the pH of the industrial wastewater to 7.2, and the stirring rate is 90 revolutions per minute;

[0166] (2) Then add the water quality treatment agent, with a dosage of 2.5 grams of the water quality treatment agent per liter of wastewater, aerate for 1 hour, and then flocculate and precipitate, with a flocculation time of 4 hours;

[0167] (3) Then filter, and detect the supernatant of the industrial wastewater. The results are: pH is 7.7, COD is 720 mg / L, the COD removal rate is 53.8%, and TDS (total dissolved solids) is 14500 mg / L, meeting the requirement of subsequent biochemical TDS < 20000 mg / L (process design requirement).

[0168] From the data results of Examples 1 to 6, it can be seen that the TDS of the industrial wastewater treated by the water quality treatment agent prepared in the present invention has all decreased, and at the same time, part of the organic pollutants COD and heavy metals have been removed, which can ensure the process requirements for the total dissolved solids in subsequent biochemical treatment.

[0169] The influence of the preparation method of the pre-film agent of the mixed extract of lobster shells and crab shells in Comparative Examples 1 to 8 on the effect of the water quality treatment agent

[0170] The difference between Comparative Example 1 and Example 3 lies in the different components of the pre-film agent of the mixed extract of lobster shells and crab shells. After the lobster shells and crab shells pretreated in step S1 are prepared into a mixed powder of lobster shells and crab shells at 800 °C by the preparation method of Example 1 of CN114890492A, the water quality treatment agent is then prepared according to the preparation method of the water quality treatment agent in Example 3.

[0171] The difference between Comparative Example 2 and Example 3 lies in the different components of the pre-film agent of the mixed extract of lobster shells and crab shells. The lobster shells and crab shells are prepared into a mixed adsorption material of lobster shells and crab shells by the method of Example 1 of CN105126773A, and then the water quality treatment agent is prepared according to the preparation method of the water quality treatment agent in Example 3.

[0172] The difference between Comparative Example 3 and Example 3 is that the mass concentration of the hydrochloric acid solution in step S2 is 20%, and the others are the same as in Example 3. The mixed extract prefilm agent of lobster shell and crab shell prepared is used to prepare a water treatment agent according to the preparation method of the water treatment agent in Example 3.

[0173] The difference between Comparative Example 4 and Example 3 is that the mass concentration of the sodium hydroxide solution in step S3 is 25%, and the others are the same as in Example 3. The mixed extract prefilm agent of lobster shell and crab shell prepared is used to prepare a water treatment agent according to the preparation method of the water treatment agent in Example 3.

[0174] The difference between Comparative Example 5 and Example 3 is that the mass concentration of the sodium hydroxide solution in step S4 is 30%, and the others are the same as in Example 3. The mixed extract prefilm agent of lobster shell and crab shell prepared is used to prepare a water treatment agent according to the preparation method of the water treatment agent in Example 3.

[0175] The difference between Comparative Example 6 and Example 3 is that the specific preparation steps of the mixed extract prefilm agent of lobster shell and crab shell are as follows:

[0176] The preparation steps of S1 and S2 are the same as those in Example 3.

[0177] S3. The lobster shell and crab shell after acid leaching treatment are placed in a 30% sodium hydroxide solution and boiled for 2 h, then filtered, washed with water until neutral, and then dried at 120 °C for 2 h to obtain a mixed extract of lobster shell and crab shell.

[0178] S4. The mixed extract of lobster shell and crab shell prepared in S3 and the prefilm aid modified carboxymethyl cellulose are mixed evenly at a mass ratio of 19:1 to obtain the mixed extract prefilm agent of lobster shell and crab shell.

[0179] The water treatment agent is prepared by using the mixed extract prefilm agent of lobster shell and crab shell prepared according to the preparation method of the water treatment agent in Example 3.

[0180] The difference between Comparative Example 7 and Example 3 is that the addition amount of the prefilm aid modified carboxymethyl cellulose in step S5 is 1.61 g, and after mixing evenly, 25.81 g of the mixed extract prefilm agent of lobster shell and crab shell is obtained. The water treatment agent is prepared by using the mixed extract prefilm agent of lobster shell and crab shell prepared according to the preparation method of the water treatment agent in Example 3.

[0181] The difference between Comparative Example 8 and Example 3 is that the addition amount of the pre-film aid-modified carboxymethyl cellulose in step S5 is 0.81 g. After mixing evenly, 25.01 g of the pre-film agent of the mixed extract of lobster shell and crab shell is obtained. The water treatment agent is prepared by the preparation method of the water treatment agent in Example 3 for the pre-film agent of the mixed extract of lobster shell and crab shell thus prepared.

[0182] After the water treatment agents prepared in Comparative Examples 1 to 8 were used to treat the same industrial wastewater as in Example 3, the supernatant of the industrial wastewater was detected, and the results are as follows:

[0183] Comparative Example 1: pH is 5.8, COD is 1080 mg / L, COD removal rate is 68.5%, TDS is 12400 mg / L. The COD removal rates are comparable, but TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0184] Comparative Example 2: pH is 5.8, COD is 1055 mg / L, COD removal rate is 69.2%, TDS (total dissolved solids) is 14500 mg / L. The COD removal rates are comparable, but TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0185] Comparative Example 3: pH is 8.2, COD is 2160 mg / L, COD removal rate is 36.9%, TDS (total dissolved solids) is 12000 mg / L. The COD removal rate is low, and TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0186] Comparative Example 4: pH is 8.8, COD is 1950 mg / L, COD removal rate is 43.1%, TDS (total dissolved solids) is 14300 mg / L. The COD removal rate is low, and TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0187] Comparative Example 5: pH is 8.3, COD is 1880 mg / L, COD removal rate is 45.1%, TDS (total dissolved solids) is 13500 mg / L. The COD removal rate is low, and TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0188] Comparative Example 6: pH is 8.5, COD is 1500 mg / L, COD removal rate is 56.2%, TDS (total dissolved solids) is 11800 mg / L. The COD removal rate is low, and TDS > 10000 mg / L, not meeting the subsequent process requirement of TDS < 10000 mg / L.

[0189] Comparative Example 7: pH is 8.3, COD is 1045 mg / L, COD removal rate is 69.5%, TDS (total dissolved solids) is 14600 mg / L. The COD removal rates are comparable, but TDS > 10000 mg / L, not meeting the process requirement of TDS < 10000 mg / L for subsequent steps.

[0190] Comparative Example 8: pH is 8.4, COD is 1910 mg / L, COD removal rate is 44.2%, TDS (total dissolved solids) is 12700 mg / L. The COD removal rate is relatively low, and TDS > 10000 mg / L, not meeting the process requirement of TDS < 10000 mg / L for subsequent steps.

[0191] It can be seen from the results of Comparative Examples 1 - 8 that the preparation method of the pre - film agent of the mixed extract of lobster shells and crab shells has a great influence on the effect of the water treatment agent, mainly due to the influence of the extraction process on the effective adsorption components and their contents in lobster shells and crab shells.

[0192] Influence of the components of the water treatment agent in Comparative Examples 9 - 14 on its effect in treating industrial wastewater

[0193] The components of the water treatment agents prepared in Comparative Examples 9 - 14 are shown in Table 1 specifically, and the others are the same as in Example 3;

[0194] Table 1:

[0195]

[0196] Six water treatment agents prepared according to the compositions in Table 1 have the following results:

[0197] Comparative Example 9: pH is 8.6, COD is 1250 mg / L, COD removal rate is 63.5%, TDS (total dissolved solids) is 12200 mg / L. The COD removal rate is slightly low, and TDS > 10000 mg / L, not meeting the process requirement of TDS < 10000 mg / L for subsequent steps.

[0198] Comparative Example 10: pH is 9.5, COD is 2050 mg / L, COD removal rate is 40.1%, TDS (total dissolved solids) is 24600 mg / L. The COD removal rate is relatively low, and TDS > 10000 mg / L, not meeting the process requirement of TDS < 10000 mg / L for subsequent steps.

[0199] Comparative Example 11: pH is 7.6, COD is 2210 mg / L, COD removal rate is 35.5%, TDS (total dissolved solids) is 28500 mg / L. The COD removal rate is relatively low, and TDS increases, not meeting the process requirement of TDS < 10000 mg / L for subsequent steps.

[0200] Comparative Example 12: pH is 7.9, COD is 1110 mg / L, COD removal rate is 67.6%, TDS (total dissolved solids) is 25600 mg / L, the COD removal rate is comparable, but the TDS increases, not meeting the process requirement of subsequent TDS < 10000 mg / L.

[0201] Comparative Example 13: pH is 8.0, COD is 4200 mg / L, COD removal rate / , TDS (total dissolved solids) is 32000 mg / L, the COD increases, the TDS increases, not meeting the process requirement of subsequent TDS < 10000 mg / L.

[0202] Comparative Example 14: pH is 8.6, COD is 1100 mg / L, COD removal rate is 67.9%, TDS (total dissolved solids) is 12500 mg / L, the COD removal rate is comparable, but TDS > 10000 mg / L, not meeting the process requirement of subsequent TDS < 10000 mg / L.

[0203] From the results of Comparative Examples 9 to 14, it can be seen that the composition and ratio of the pre - film agent of the mixed extract of lobster shell and crab shell, ferrous sulfate heptahydrate and slaked lime have a great influence on the effect of the water treatment agent. Among them, the content and ratio of ferrous sulfate heptahydrate and slaked lime significantly affect the treatment of the total dissolved solids in industrial wastewater by the water treatment agent.

[0204] Influence of the usage method of the water treatment agent in Comparative Examples 15 - 16 on the effect of treating industrial wastewater

[0205] The difference between Comparative Example 15 and Example 3 is that the water treatment agent is applied to the engineering site, the pH of the industrial wastewater is adjusted to 6.0, and the supernatant of the industrial wastewater is detected. The results are that the pH is 6.0, COD is 1172 mg / L, COD removal rate is 65.8%, TDS (total dissolved solids) is 10800 mg / L, and TDS > 10000 mg / L.

[0206] The difference between Comparative Example 16 and Example 3 is that the water treatment agent is applied to the engineering site, the pH of the industrial wastewater is adjusted to 9.5, and the supernatant of the industrial wastewater is detected. The results are that the pH is 9.5, COD is 1085 mg / L, COD removal rate is 68.3%, TDS (total dissolved solids) is 10400 mg / L, and TDS > 10000 mg / L.

[0207] It should be noted that the specific features, structures, materials, or characteristics described in this specification can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. Without contradiction, those skilled in the art can combine and combine the different embodiments and features described in this specification.

[0208] The above-described embodiments merely represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A method for preparing a water quality treatment agent for industrial wastewater, characterized in that, By mass parts, the water quality treatment agent contains 10 - 30 parts of a pre - film agent which is a mixed extract of lobster shells and crab shells, 60 - 80 parts of ferrous sulfate heptahydrate, and 15 - 20 parts of slaked lime; the pre - film agent which is a mixed extract of lobster shells and crab shells is first added to ferrous sulfate heptahydrate and mixed evenly for pre - filming, then slaked lime is added and mixed evenly, and then pulverized to form a powdery material; The preparation method of the pre - film agent which is a mixed extract of lobster shells and crab shells comprises the following steps: S1. Pretreatment of raw materials: First, remove the meat and dirt impurities in the collected lobster shells and crab shells, wash them clean with water, and then dry them; S2. Acid leaching treatment: Place the pretreated lobster shells and crab shells in a dilute hydrochloric acid solution with a mass concentration of 1% - 15%, soak at room temperature for 2 h, then filter and wash with water until neutral; S3. Digestion treatment: Place the lobster shells and crab shells after acid leaching treatment in a sodium hydroxide solution with a mass concentration of 10% - 20% and boil for 2 h, then filter and wash with water until neutral, and then dry; S4. Reaction extraction: Place the lobster shells and crab shells after digestion treatment in step S3 in a sodium hydroxide solution with a mass concentration of 40% - 50% and carry out hydrolysis at 100 - 110 °C for 2 h, then filter and wash with water until neutral, and then dry to obtain a mixed extract of lobster shells and crab shells; S5. Production and preparation: Mix the mixed extract of lobster shells and crab shells obtained in step S4 with modified carboxymethyl cellulose evenly according to a mass ratio of 18 - 25:1 to obtain a pre - film agent which is a mixed extract of lobster shells and crab shells; The preparation method of the modified carboxymethyl cellulose is as follows: Under stirring conditions, dissolve carboxymethyl cellulose CMC, acrylamide monomer, and potassium persulfate initiator in water in sequence, adjust the pH to 6 - 8, and react at 70 °C - 90 °C for 3 - 5 h to obtain modified carboxymethyl cellulose.

2. The method for preparing an industrial wastewater water treatment agent according to claim 1, characterized in that, By mass parts, the water quality treatment agent contains 12 - 20 parts of a pre - film agent which is a mixed extract of lobster shells and crab shells, 64 - 72 parts of ferrous sulfate heptahydrate, and 16 - 18 parts of slaked lime.

3. The method for preparing a water treatment agent for industrial wastewater quality according to claim 1, characterized in that, The mass ratio of the pre - film agent which is a mixed extract of lobster shells and crab shells, ferrous sulfate heptahydrate, and slaked lime is 0.1 - 2:3.0 - 5.0:

1.

4. An industrial wastewater water quality treatment agent, characterized in that, Prepared by the method according to any one of claims 1 - 3.

5. Application of the industrial wastewater water quality treatment agent according to claim 4 in the field of wastewater treatment.

6. The application according to claim 5, characterized in that, The usage method of the water quality treatment agent is: Adjust the pH of the wastewater, keep it in a stirring state, then add the industrial wastewater water quality treatment agent for reaction, and carry out flocculation precipitation after aeration.

7. The application according to claim 6, characterized in that, The dosage of the industrial wastewater water quality treatment agent is 0.5 - 5 grams per liter of wastewater.

8. The application according to claim 6, wherein The aeration time is 0.5 - 3 hours, and the flocculation time is 0.1 - 12 hours.

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