CN112777699B - A kind of compound agent for advanced treatment of biochemical tail water and preparation method thereof - Google Patents

Abstract

The invention discloses a compound agent for advanced treatment of biochemical tail water and a preparation method thereof. The compounding agent is made of raw materials containing the following weights: 25% to 35% of charge donor, 7% to 10% of organic flocculant, 0.2% to 2% of charge carrier, 0.5% to 1.5% of stabilizer, and 3% of freezing point conditioner ~5%, the balance is water; it has the advantages of removing organic matter, trace elements, heavy metals and phosphorus and other pollutants in sewage, and at the same time removing H2S odor gas. The preparation method is as follows: firstly prepare the mixed solution I and the mixed solution III respectively, then mix the mixed solution I and the mixed solution III, then add a freezing point conditioner, and adjust the pH to make the pH of the solution 0.5-2, and then the product can be prepared. Compound medicament; the preparation method of the present invention has the advantages of reducing the agglomeration of the charge carrier, so that the charge carrier and the charge donor are stably existing in the same solution, and a stable compound medicament is obtained.

Description

A kind of compound agent for advanced treatment of biochemical tail water and preparation method thereof

technical field

The invention relates to the technical field of sewage treatment, and more particularly, to a compound agent for advanced treatment of biochemical tail water and a preparation method thereof.

Background technique

Sewage treatment technology is to use physical, chemical or biological treatment methods to separate the pollutants contained in the sewage, or convert the pollutants into harmless and stable substances, so as to purify the sewage.

Sewage treatment includes primary treatment, secondary treatment and tertiary treatment. The primary treatment is mainly to remove the suspended solid pollutants in the sewage. The sewage treated in the primary treatment belongs to the pretreatment of the secondary treatment and cannot be discharged. Secondary treatment: mainly remove organic pollutants in colloidal and dissolved state and nutrients (including BOD, COD, nitrogen, phosphorus and other pollutants) that cause eutrophication in sewage, so that the sewage can meet the discharge standard; three Secondary treatment: On the basis of secondary treatment, refractory organic matter, residual nitrogen and phosphorus and other soluble inorganic matter that can lead to eutrophication of water body, and bacterial substances such as Escherichia coli are further removed.

With the introduction of local standards in various provinces, sewage treatment plants are faced with the urgent need to upgrade the standard from the first-level A to the local standard. The solution is to carry out advanced treatment of the biochemical tailwater after the second-level treatment to meet the high-standard effluent requirements. . However, the advanced treatment of biochemical tail water mainly adopts advanced oxidation technology or membrane technology. It is a technology that oxidizes macromolecular refractory organic substances into low-toxic or non-toxic small molecular substances; membrane technology uses the pressure exerted by the outside world and the selective permeability of the membrane to make small molecules such as water The technology that particles can pass through the membrane and the particulate matter or colloidal matter with relatively large molecular weight is blocked by the membrane, so that part of the pollutants in the water can be separated.

The prior art solutions in the above have the following defects: the advanced oxidation technology is aimed at the removal of macromolecular organic substances, and the membrane technology is aimed at the removal of substances with relatively large molecular weights or colloidal substances, whether it is advanced oxidation technology or membrane treatment technology. , the object of sewage treatment is relatively single, and the treatment efficiency is relatively low.

SUMMARY OF THE INVENTION

Aiming at the deficiencies in the prior art, the first object of the present invention is to provide a composite agent for biochemical tail water treatment, which has the ability to remove various pollutants such as organic matter, antibiotics and other trace elements, heavy metal elements and phosphorus in sewage , The advantages of high treatment efficiency and wide application range of compound medicaments.

The second object of the present invention is to provide a method for preparing a compound agent for biochemical tail water treatment, firstly preparing the mixed solution I and the mixed solution III, and then mixing the mixed solution I and the mixed solution III, which has the advantages of making The stabilizer is first adsorbed on the surface of the charge carrier, reducing the agglomeration of the charge carrier, so that the charge carrier and the charge donor stably exist in the same solution, obtaining a stable composite drug, and making the composite drug exert the advantages of maximum effect.

For realizing above-mentioned first purpose, the present invention provides following technical scheme:

A composite medicament for advanced treatment of biochemical tail water, the composite medicament is made from raw materials comprising the following weights:

Charge donor 25%-35%, organic flocculant 7%-10%, charge carrier 0.2%-2%, stabilizer 0.5%-1.5%, freezing point conditioner 3%-5%, the balance is water;

The pH value of the compound medicament is 0.5-2.

By adopting the above-mentioned technical scheme, the composite agent of the present invention is put into the secondary sedimentation tank or the high-density clarification tank, which can realize the rapid separation of mud and water, the removal of trace elements such as organic substances and antibiotics, and the removal of pollutants such as heavy metal elements, thereby realizing sewage purification. With the return of sludge, some chemicals enter the biochemical system and participate in biological denitrification and phosphorus removal as electron donors, replacing organic carbon sources to strengthen denitrification and phosphorus removal. In addition, under low temperature conditions, the agent can activate microbial enzymatic reactions. Compared with the advanced oxidation technology or membrane technology in the existing technology, it can remove various pollutants such as organic matter, antibiotics and other trace elements, heavy metal elements and phosphorus in sewage, and can also remove H2S odor gas. . The compound medicament can remove many kinds of pollutants and has high treatment efficiency, thus expanding the scope of use.

In the composite agent, the stabilizer is adsorbed on the surface of the charge carrier, which can prevent the charge carrier from agglomerating in water, so as to enhance the stability of the charge carrier in water, thereby helping the charge carrier to remove heavy metals and micropollutants in sewage; the charge donor is sewage The microorganisms in it provide electrons to strengthen the effect of microbial denitrification and phosphorus removal. After the charge donor loses electrons, it can play the role of chemical phosphorus removal, and under the action of the charge carrier and stabilizer, the flocculation speed is accelerated and the flocculation effect is strengthened; adding the freezing point The conditioner can reduce the freezing point of the compound medicine to -20℃±2℃, and expand the application conditions and use range of the compound medicine; the pH of the compound medicine is 0.5～2, and the compound medicine is acidic, which can maintain the characteristics of each component of the compound medicine, and It can remove alkaline pollutants in sewage.

Further, the charge donor is FeCl ₂ or FeSO ₄ .

By adopting the above technical solution, in the present invention, the charge donor is a ferrous salt, preferably FeCl ₂ or FeSO ₄ , and FeCl 2 or FeSO 4 provides electrons for the microorganisms in the sewage, which strengthens the effect of microbial denitrification and phosphorus removal; After the body loses electrons, it can react with PO42- in sewage to generate insoluble Fe2(PO4)3, and then Fe2(PO4)3 can be removed from sewage through solid-liquid separation, so as to achieve the effect of chemical phosphorus removal; charge donor selection FeCl2 or FeSO4 can form organic-inorganic composite flocculants with organic flocculants after the charge donor loses electrons, which can make up for the defects of using inorganic polymer flocculants or organic flocculants alone and strengthen the flocculation effect.

Further, the organic flocculant is selected from one or more of polyacrylamide, polydimethyldiallylammonium chloride, dimethyldiallylammonium chloride and polyquaternary ammonium salts.

By adopting the above technical solutions, organic flocculants refer to natural or artificially synthesized organic molecular substances that can produce flocculation. Polyacrylamide, polydimethyldiallyl ammonium chloride, dimethyl diallyl ammonium chloride and polyquaternary ammonium salt are all cationic flocculants, which have good water solubility and can be dissolved in water in any proportion And insoluble in organic solvents, the cationic flocculant can electrically neutralize the negatively charged organic colloids in the sewage through the positively charged groups contained in it, or through the excellent bridging and coagulation function of the polymer, to promote the colloidal particles to aggregate into large pieces. Flocs, separated from their suspensions; one or more of polyacrylamide, polydimethyldiallylammonium chloride, dimethyldiallylammonium chloride and polyquaternary ammonium salts The flocculant has a strong flocculation and sedimentation effect on various suspended particles in the aqueous medium, and the flocculation effect is obvious and the dosage is small.

The polyacrylamide flocculant has active cationic groups on its molecular chain. Through electric neutralization and adsorption bridging, the suspended particles and negatively charged water-soluble substances in the water are destabilized and flocculated, forming larger flocs to settle. Or float, to achieve the purpose of removing pollutants in sewage or reducing the moisture content of sludge. Polydimethyldiallyl ammonium chloride, as a strong cationic polyelectrolyte, is safe, non-toxic, easily soluble in water, strong in cohesion and good in hydrolytic stability. Dimethyl diallyl ammonium chloride and its copolymer, as a water-soluble cationic polymer, have the advantages of high positive charge density, good water solubility, easy molecular weight control, high efficiency, non-toxicity and low cost. Polyquaternium salt has good solubility in water, has broad-spectrum and high-efficiency sterilization and algae killing ability, can effectively control the reproduction of bacteria and algae in water and the growth of slime, and has good slime stripping effect and certain dispersion, It has a certain degreasing, deodorizing ability and corrosion inhibition effect at the same time. In the present invention, polyacrylamide, polydimethyl diallyl ammonium chloride, dimethyl diallyl ammonium chloride and polyquaternary ammonium salt can be used alone or in combination, all of which can play a better role flocculation to remove pollutants from sewage.

Further, the charge carrier is selected from one or more of nano-zero-valent iron, nano-scale metal oxide FeO, Fe ₂ O ₃ and Fe ₃ O ₄ .

By adopting the above technical solutions, the nano-zero valent iron has reducibility, which can provide electrons for microorganisms in sewage to enhance the effect of denitrification and phosphorus removal; after the nano-zero valent iron loses electrons, it becomes free Fe2+, which can react quickly with H2S, A black precipitate of FeS is formed, and due to this instantaneous reaction, the odor is hardly noticeable anywhere in the sewage treatment plant during sewage treatment. Nano-scale metal oxides FeO, Fe2O3 and Fe3O4 do not react with water, and have nanoparticle special effects, with large surface area and surface energy, which can effectively adsorb metal ions (Cu2+, Hg2+, etc.) in sewage, and their adsorption capacity. The process is a spontaneous process; at the same time, the special functional group of the organic acid of the stabilizer has a strong complex effect. After it is modified and regulated on the nano-iron particles, the removal of heavy metals has a double superposition effect, which greatly improves the removal of heavy metals. Rate. Nano-zero-valent iron and nano-metal oxides FeO, Fe2O3 and Fe3O4 can be used alone as charge carriers, or two or three kinds of them can be used together, and they can all play a better role.

Further, the stabilizer is selected from one or more of 3-mercaptopropyltriethoxysilane, humic acid, citric acid and dimercaptosuccinic acid.

By adopting the above technical scheme, the stabilizer is one or more of 3-mercaptopropyltriethoxysilane, humic acid, citric acid and dimercaptosuccinic acid, 3-mercaptopropyltriethoxysilane Functional groups of silane--mercaptopropyl, silane, unsaturated functional groups of humic acid--quinone, carbonyl and carboxyl and various functional groups on aromatic rings--carboxyl, phenol, hydroxyl, methoxy and Quinone groups, etc., functional groups of citric acid (3-hydroxy-1,3,5-pentatrilic acid) - hydroxyl, carboxyl and functional groups of dimercaptosuccinic acid, such as sulfhydryl, can have strong complexation with heavy metal ions , after combining it with the nano-iron particles, the total specific surface area of the nanoparticles is increased, which can greatly enhance the removal effect of heavy metals and micro-pollutants.

Further, the freezing point conditioner is selected from at least one of glycerol and ethylene glycol.

By adopting the above technical solution, generally, the freezing point of the aqueous solution is around 0°C. In the compound agent, adding at least one of the freezing point conditioners glycerol and ethylene glycol can reduce the freezing point of the compound agent to -20°C ± 2°C , at a lower temperature (-20°C ± 2°C), the composite medicament of the present invention can still be used to treat sewage, so that the use range of the composite medicament can be expanded.

In order to achieve the above-mentioned second purpose, the present invention provides the following technical scheme: a preparation method of a composite agent for advanced treatment of biochemical tail water, the preparation method comprising the following steps:

S1. The charge carrier is added in batches to the mixed solution composed of stabilizer and water that accounts for 10% to 20% of the weight of the composite drug under ultrasonic stirring according to the set ratio, so that the charge carrier is completely dissolved and dispersed in the mixed solution. and then continue ultrasonic treatment for 30min-60min, and finally let stand for 20h-28h to prepare mixed solution I;

S2, adding the organic flocculant to the remaining water, stirring while adding, and stirring evenly to obtain a mixed solution II;

S3. Under anaerobic conditions, add the charge donor into the mixed solution II, stir while adding, and stir evenly to obtain the mixed solution III;

S4, mixing the mixed solution I and the mixed solution III, and stirring at a stirring speed of 100 r/min to 1000 r/min for 30 min to 60 min to obtain a mixed solution IV;

S5. Add a freezing point conditioner to the mixed solution IV, and adjust the pH so that the pH of the solution is 0.5-2, so that the compound medicine can be prepared.

By adopting the above technical scheme, firstly, the charge carrier, the stabilizer and the water accounting for 10% to 20% of the compound agent are mixed, and the mixed solution I is obtained by ultrasonic treatment; then the organic flocculant is added to the remaining water to obtain the solution II. The donor is added to the mixed solution II to the mixed solution III; then the mixed solution I is mixed with the mixed solution III to obtain the mixed solution IV, and finally the freezing point conditioner is added to the mixed solution IV and the pH value of the solution is adjusted. Preparation of compound medicines. In the preparation process, the process parameters such as the feeding sequence, time, temperature, stirring speed and rotation speed are strictly controlled, and the compound medicine can be prepared more accurately, so that the compound medicine can exert the maximum effect.

The mixed solution I and the mixed solution III are prepared respectively, and then the purpose of mixing the two is to coat the stabilizer on the surface of the charge carrier. If the charge carrier is directly mixed with the charge donor without stably dispersing the charge carrier in the solution containing the stabilizer first, the stabilizer (organic acid) cannot be wrapped on the surface of the charge carrier, and the charge carrier will agglomerate in the solution. Poor, the effect of heavy metal removal is greatly reduced. First prepare mixed solution I and mixed solution III respectively, and then mix the two to obtain mixed solution IV. The advantages of this preparation: the charge carrier and the charge donor can stably exist in the same solution to obtain a stable composite drug; The stability of the agent is good, so in the process of use, the compound agent can be put in together, and it does not need to be put in separately like the existing flocculant compounded with polyaluminum and polyvinylamide, and there is no need to add heavy metal chelating agent, odor removal agent Odors, etc., do not involve multiple sets of dosing devices, and the cost of compound medicaments is low, and it is liquid, which can be directly added through a metering pump, saving time and effort during delivery.

Mixed solution I has both nanoparticle effects and strong complexation effects of special functional groups of organic acids, and has a double superposition effect on the removal of heavy metals; at the same time, under the action of electrodes in mixed solution I, the flocculation effect is quickly produced by the action of electrodes, and the suspension is released. The quiescent state of the solid, continuously expands the agglomeration of the suspended solids and sinks rapidly, further promotes the flocculation of the mixed solution III, and achieves rapid settling.

Further, in the S1, when the charge carriers are added in batches, 0.2%-0.5% of the weight of the composite drug is added each time, and the time interval between adjacent batches is 28min-32min; the S1 Among them, the frequency of the ultrasound is 50-150 Hz.

By adopting the above technical solution, in the present invention, in step S1, ultrasonic treatment is performed using an ultrasonic reactor. Compared with general stirring, ultrasonic treatment is more conducive to uniform dispersion of charge carriers of nano-scale metal oxides in the solution. Stirring at an ultrasonic frequency of 50-150 Hz is beneficial to the uniform dispersion of the charge carriers of the nano-scale metal oxides in the solution, which saves the stirring time to a certain extent and improves the efficiency of preparing the compound medicine. Adding charge carriers in batches is conducive to the uniform dispersion of the charge carriers into the solution, reducing the agglomeration of the charge carriers in sewage, and facilitating the uniform adsorption of the stabilizer on the surface of the charge carriers, enhancing its stability in water, thus facilitating the removal of sewage heavy metal ions in it. When the charge carrier is added in batches, the charge carrier which accounts for 0.2% to 0.5% of the weight of the composite drug is added each time. If the total amount of the charge is less than 0.5%, it can be added at one time.

Further, in the S2, the stirring temperature is 45-65°C, and the stirring speed is 300 r/min-3000 r/min; in the S3, the stirring speed is 100-1000 r/min.

By adopting the above technical scheme, in step S2, a medium-temperature stirring reaction kettle (temperature 45-65° C.) is used for stirring, and the reaction temperature of the mixed solution II is controlled to facilitate the stabilization of the organic flocculant. Add the organic flocculant to the remaining water, and strictly control the stirring speed of the solution II and the stirring speed of the mixed solution III, which is conducive to the uniform stirring of the solution, which is conducive to the stable mixing of inorganic-organic composite agents, and is conducive to inorganic-organic. The compound agent can stably play the function of sewage treatment and purification during sewage treatment.

Generally, the dissolving speed of the organic flocculant is relatively slow. Therefore, in step S2, when the organic flocculant is added to the remaining water, continuous stirring and intermittent addition are adopted while adding the organic flocculant. 2% to 3% of the flocculant by weight of the compound agent. In step S2, when the charge donor is added to the mixed solution II, it can be added at one time and then continuously stirred, or it can be added intermittently under continuous stirring, that is, every 8min to 12min, 5% of the weight of the composite drug will be added. % to 10% of the charge donor was added to solution II.

Further, in the S5, a pH conditioner is used to adjust the pH of the solution, and the pH conditioner is hydrochloric acid with a concentration of 10%-30% or sulfuric acid with a concentration of 10%-20%.

By adopting the above technical solution, in the present invention, when the charge carrier is FeCl ₂ , hydrochloric acid with a concentration of 10% to 30% is preferred as the pH conditioner; when the charge carrier is FeSO ₄ , the preferred concentration is 10% to 20% of hydrochloric acid. Sulfuric acid acts as a pH conditioner.

To sum up, the present invention has the following beneficial effects:

First, the components of the compound agent cooperate with each other, which can remove organic matter, trace elements such as antibiotics, heavy metal elements and phosphorus and other pollutants in sewage, and can also remove odorous gases such as H ₂ S. The compound agent can be used in a wide range. , high removal efficiency;

Second, after the charge donor loses electrons, it forms an organic-inorganic composite flocculant with the organic flocculant, which can make up for the defects of using inorganic polymer flocculant or organic flocculant alone, and strengthen the flocculation effect;

Third, the mixed solution I has both nanoparticle special effects and strong complexation effects with special functional groups of organic acids, so it has a double superposition effect on the removal of heavy metals, and the removal efficiency of heavy metals is good;

Fourth, the mixed solution I is mixed with the mixed solution III. The mixed solution I can be used as an organic charge carrier, and the static state of the suspended matter can be relieved by the action of the electrode, so that the flocculation effect can be produced quickly. , to achieve rapid settlement, which can further accelerate the flocculation effect;

Fifth, in the preparation process, firstly prepare mixed solution I and mixed solution III, and finally mix mixed solution I and mixed solution III, which can make the stabilizer adsorb on the surface of the charge carrier first, reduce the agglomeration of the charge carrier, and make the charge The carrier and the charge donor stably exist in the same solution to obtain a stable compound drug;

Sixth, the compound medicine is relatively stable, it can be put into use at one time, it will not involve multiple sets of dosing devices, the cost is low, and it is liquid, which can be directly added through the metering pump, saving time and effort when putting the compound medicine.

Detailed ways

The present invention will be described in further detail below in conjunction with the embodiments.

Example

Example 1

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

S1, 0.5kg 3-mercaptopropyl triethoxysilane and 10kg water are joined in the ultrasonic reactor, open the ultrasonic reactor, the frequency of the ultrasonic reactor is set to 100Hz, then add 2kg Fe ₃ O under ultrasonic stirring ₄ (add in 4 batches, add 0.5kg in each batch, and the time interval between adjacent batches is 30min), to complete dissolution and dispersion into the solution, then ultrasonically treat for 45min, close the ultrasonic reactor, stand for 24h, and obtain a mixed solution I;

S2, add 8.5kg of polyacrylamide and 49kg of water into a medium-temperature reaction kettle with a temperature of 55°C, add and stir at a stirring speed of 1500 r/min, and stir evenly to obtain mixed solution II;

S3. Under anaerobic conditions and a stirring speed of 500 r/min, add 25 kg of FeCl ₂ into mixed solution II, stir while adding, and stir evenly to obtain mixed solution III;

S4. Mix the mixed solution I and the mixed solution III, and stir for 45 minutes in an environment with a stirring speed of 500 r/min to obtain a mixed solution IV;

S5. Add 5kg of glycerol to the mixed solution IV, stir evenly, and adjust the pH to 1 with hydrochloric acid with a concentration of 10%, so as to prepare the compound medicine.

Example 2

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

S1, 1kg 3-mercaptopropyl triethoxysilane and 20kg water are added in the ultrasonic reactor, open the ultrasonic reactor, the frequency of the ultrasonic reactor is set to 100Hz, then add 0.2kg Fe ₃ O under ultrasonic stirring _4. To completely dissolve and disperse into the solution, then ultrasonically treat for 45min, close the ultrasonic reactor, and let stand for 24h to prepare mixed solution I;

S2, adding 7kg polyacrylamide and 47.8kg water into a medium temperature reaction kettle with a temperature of 55°C, adding and stirring at a stirring speed of 1500 r/min, and stirring evenly to obtain mixed solution II;

S3. Under anaerobic conditions and a stirring speed of 500 r/min, add 30kg FeCl ₂ into mixed solution II, stir while adding, and stir evenly to obtain mixed solution III;

S4. Mix the mixed solution I and the mixed solution III, and stir for 45 minutes in an environment with a stirring speed of 500 r/min to obtain a mixed solution IV;

S5. Add 4 kg of glycerol to the mixed solution IV, stir evenly, and adjust the pH to 1 with hydrochloric acid with a concentration of 10% to obtain a compound medicine.

Example 3

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

S1, 1.5kg 3-mercaptopropyl triethoxysilane and 15kg water are added in the ultrasonic reactor, open the ultrasonic reactor, the frequency of the ultrasonic reactor is set to 100Hz, then add 1kg Fe ₃ O under ultrasonic stirring ₄ (Add in 2 batches, add 0.5kg in each batch, and the time interval between adjacent batches is 30min), to complete dissolution and dispersion into the solution, then ultrasonically treat for 45min, close the ultrasonic reactor, and let stand for 24h to obtain a mixed solution I;

S2, add 10kg of polyacrylamide and 34.5kg of water into a medium-temperature reaction kettle with a temperature of 55°C, add and stir at a stirring speed of 1500 r/min, and stir evenly to obtain mixed solution II;

S3. Under anaerobic conditions and a stirring speed of 500 r/min, add 35kg FeCl ₂ into mixed solution II, stir while adding, and stir evenly to obtain mixed solution III;

S4. Mix the mixed solution I and the mixed solution III, and stir for 45 minutes in an environment with a stirring speed of 500 r/min to obtain a mixed solution IV;

S5. Add 3 kg of glycerol to the mixed solution IV, stir evenly, and adjust the pH to 1 with hydrochloric acid with a concentration of 10% to prepare a compound medicine.

Example 4

The difference between embodiment 4 and embodiment 3 is: in embodiment 4, the charge donor added is 30kg FeSO ₄ , the addition of remaining water in step S2 is 39.5kg, and all the other are consistent with embodiment 3.

Example 5

The difference between embodiment 5 and embodiment 3 is: in embodiment 5, in step S4, pH is adjusted to 1 with the sulfuric acid that concentration is 10%, and the addition of remaining water in step S2 is 39.5kg, and all the other are the same as in embodiment. 3 Be consistent.

Example 6

The difference between embodiment 6 and embodiment 3 is: in embodiment 6, stabilizer is 0.5kg humic acid and 0.5kg humic acid, and the addition of remaining water in step S2 is 35kg, and all the other are consistent with embodiment 3 .

Example 7

The difference between embodiment 7 and embodiment 3 is: in embodiment 7, the charge carrier is 0.5kg FeO, 0.5kg Fe ₂ O ₃ and 0.5kg Fe ₃ O ₄ (add in 3 batches, add 0.5kg in every batch, adjacent The time interval between batches is 30min), the addition of remaining water in step S2 is 34kg, and the rest are all consistent with Example 3.

Example 8

The difference between embodiment 8 and embodiment 3 is: in embodiment 8, charge carrier is 1kg FeO and 0.5kg Fe ₂ O ₃ (add in 2 batches, every batch adds 0.5kg, time interval 30min between adjacent batches) , the addition of remaining water in step S2 is 34kg, and the rest are all consistent with Example 3.

Example 9

The difference between embodiment 9 and embodiment 3 is: in embodiment 9, organic flocculant is 4kg polydimethyldiallyl ammonium chloride and 4kg polyquaternium salt, and the addition of remaining water is 36.5kg in step S2 , and the rest are consistent with Example 3.

Example 10

The difference between embodiment 10 and embodiment 3 is: in embodiment 10, organic flocculant is 5kg polyacrylamide, 3kg dimethyl diallyl ammonium chloride and 2kg polyquaternium salt, and all the other are kept with embodiment 3. Consistent.

Example 11

The difference between embodiment 11 and embodiment 3 is: in embodiment 11, the freezing point conditioner is 2kg ethylene glycol, and the addition of remaining water in step S2 is 35.5kg, and all the other are consistent with embodiment 3.

Example 12

The difference between embodiment 12 and embodiment 3 is: in embodiment 12, in step S1, add 1kg Fe ₃ O ₄ is not divided into batches, add at one time, and the rest are all consistent with embodiment 3.

Example 13

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

S1, 1.5kg 3-mercaptopropyl triethoxysilane and 15kg water are added in the ultrasonic reactor, open the ultrasonic reactor, the frequency of the ultrasonic reactor is set to 50Hz, then add 1kg Fe ₃ O under ultrasonic stirring ₄ (Add in 2 batches, add 0.5kg in each batch, and the time interval between adjacent batches is 30min), to completely dissolve and disperse into the solution, then ultrasonically treat for 60min, close the ultrasonic reactor, and let stand for 20h to obtain a mixed solution I;

S2, add 10kg of polyacrylamide and 34.5kg of water into a medium temperature reaction kettle with a temperature of 65°C, add and stir at a stirring speed of 300r/min, and stir evenly to obtain mixed solution II;

S3. Under anaerobic conditions and a stirring speed of 100 r/min, add 35kg FeCl ₂ into mixed solution II, stir while adding, and stir evenly to obtain mixed solution III;

S4. Mix the mixed solution I and the mixed solution III, and stir for 60 min in the environment with a stirring speed of 1000 r/min to obtain the mixed solution IV;

S5. Add 3 kg of glycerol to the mixed solution IV, stir evenly, and adjust the pH to 0.5 with hydrochloric acid with a concentration of 30% to obtain a compound medicine.

Example 14

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

S1, 1.5kg 3-mercaptopropyl triethoxysilane and 15kg water are added in the ultrasonic reactor, open the ultrasonic reactor, the frequency of the ultrasonic reactor is set to 150Hz, then add 1kg Fe ₃ O under ultrasonic stirring ₄ (Add in 2 batches, add 0.5kg in each batch, and the time interval between adjacent batches is 30min), to completely dissolve and disperse into the solution, then ultrasonically treat for 30min, close the ultrasonic reactor, and let stand for 28h to obtain a mixed solution I;

S2, add 10kg of polyacrylamide and 34.5kg of water into a medium-temperature reaction kettle with a temperature of 45°C, add and stir at a stirring speed of 3000 r/min, and stir evenly to obtain mixed solution II;

S3. Under anaerobic conditions and a stirring speed of 1000 r/min, add 35kg FeCl ₂ into mixed solution II, stir while adding, and stir evenly to obtain mixed solution III;

S4. Mix the mixed solution I and the mixed solution III, and stir for 30 min in the environment with a stirring speed of 100 r/min to obtain the mixed solution IV;

S5. Add 3 kg of glycerol to the mixed solution IV, stir evenly, and adjust the pH to 2 with hydrochloric acid with a concentration of 20% to obtain a compound medicine.

Example 15

The difference between embodiment 15 and embodiment 3 is: in embodiment 15, in step S1, the frequency of the ultrasonic reactor is set to 20Hz, and the rest are all consistent with embodiment 3.

Example 16

The difference between embodiment 16 and embodiment 3 is: in embodiment 16, in step S2, the temperature of the medium temperature reaction kettle is set to 20 ℃, and the rest are all consistent with embodiment 3.

Example 17

The difference between embodiment 17 and embodiment 3 is: in embodiment 17, in step S2, stirring speed is under 100r/min, and the rest are all consistent with embodiment 3.

Example 18

The difference between embodiment 18 and embodiment 3 is: in embodiment 18, in step S3, stirring speed is under 1500r/min, and the rest are all consistent with embodiment 3.

Example 19

The difference between embodiment 19 and embodiment 3 is: in embodiment 19, the stirring speed in steps S1, S2 and S3 is all set to 150r/min, and the rest are all consistent with embodiment 3.

Comparative ratio

Comparative Example 1

The difference between Comparative Example 1 and Example 3 is that no charge carrier is added in Comparative Example 1, and the others are consistent with Example 3.

Comparative Example 2

The difference between Comparative Example 2 and Example 3 is that no charge donor is added in Comparative Example 2, and others are consistent with Example 3.

Comparative Example 3

The difference between Comparative Example 3 and Example 3 is that a common stirring method is used in Step S1 in Comparative Example 3, and the others are consistent with Example 3.

Comparative Example 4

A preparation method of a composite agent for advanced treatment of biochemical tail water comprises the following steps:

Under anaerobic conditions, 1.5kg 3-mercaptopropyl triethoxysilane, 10kg polyacrylamide, 59.5kg water and 35kg FeCl _were added into the ultrasonic reactor, the ultrasonic reactor was opened, and the frequency of the ultrasonic reactor was Set to 100Hz, set the temperature to 55°C, then add 1kg Fe ₃ O ₄ under ultrasonic agitation (add in 2 batches, add 0.5kg in each batch, and the time interval between adjacent batches is 30min), to completely dissolve and disperse into a solution 3 kg of glycerol was added to the mixed solution, stirred evenly, and the pH was adjusted to 1 with 10% hydrochloric acid to prepare a mixed solution. Get compound medicine.

performance test

According to "Comprehensive Sewage Discharge Standard" GB 8978-1996, "Water Quality Standard for Sewage Discharged into Urban Sewers" GB/T31962-2005, "Urban Sewage Treatment Plant Pollutant Discharge Standard" GB 18918, "Determination of Total Phosphorus" GB/T 11893 , "Determination of Copper, Zinc, Lead, Cadmium" GB/T 7475, "Determination of Total Mercury" GB/T 7468, HPLC-MS-MS and GC-MS Determination of Micro-pollutants and other testing standards or methods to detect sewage in sewage various pollutants.

Take equal amount of composite drug samples from the composite drugs prepared in Examples 1 to 19 and Comparative Examples 1 to 4, respectively, and then divide the same batch of sewage after secondary treatment into corresponding equal parts to obtain sewage samples. Under the same conditions The composite chemical samples were reacted with the sewage samples for the same period of time, respectively, and the contents of pollutants in the sewage samples before and after using the composite chemical samples were respectively detected: sludge settling performance index - SV5 (sludge settling ratio within 5 minutes); sludge dewatering Performance indicators - solid content; micropollutants: carbamazepine, diazepam, diclofenac and ciprofloxacin; heavy metals Cd, Hg and Pb; total phosphorus (TP), etc. The specific data are as follows in Table 1 and Table 2 .

Table 1 The record table of the content of each pollutant in the sewage before and after using the compound agent

As can be seen from Table 1, observing and calculating the data of Examples 1 to 19 shows that the reduction rate of the sludge settling performance index (SV5) is 40% to 53%, and the increase of the sludge dewatering performance index (solid content) High rate of 6% to 23.13%; heavy metal removal rate: Cd removal rate of 65% to 99%, Hg removal rate of 75% to 99%, Pb removal rate of 65% to 99%; total phosphorus (TP) reduction rate: 93-98%, it can be seen that the compound agent prepared according to the formula and preparation process of the compound agent in the present invention can realize rapid separation of mud and water, reduce solid content, reduce the total phosphorus content in sewage, remove heavy metal Cd, Hg and Pb pollution, it can be seen that the compound agent can remove many kinds of pollutants and has high treatment efficiency, thus broadening the scope of use, and can be applied to more types of sewage treatment.

Table 2 The content of each micropollutant in the sewage before and after using the compound agent

From the calculation of the data in Table 2, it can be seen that in Examples 1 to 19, the removal rate of each micro-pollutant: the removal rate of carbamazepine is 17.14% to 44.64%; the removal rate of diazepam is 56% to 65%; the removal rate of diclofenac is 20% ～60%; the removal rate of ciprofloxacin is 23.33%～46.7%; it can be seen that the compound agent prepared according to the formula and preparation process of the compound agent in the present invention can effectively remove various micro-pollutants in sewage, such as Carbamazepine, diazepam, diclofenac and ciprofloxacin, etc., and the removal efficiency is high.

Comparing Examples 12, 15 to 19, and Comparative Examples 3 to 4 in Table 1 or Table 2 with other examples, it can be seen that in the present invention, the charge carriers are added in batches, the frequency in step S1, and the stirring speed of each step. Therefore, when preparing the compound agent, preparing the compound agent according to the specific process of the present invention can improve the sewage treatment effect of the compound agent.

Comparing the data in Examples 1 to 11 and Comparative Examples 1 to 3 in Table 1 or Table 2, it can be seen that in the composite drug of the present invention, each component cooperates with each other and interacts to play a role. The effect of chemical treatment of sewage will be greatly reduced.

This specific embodiment is only an explanation of the present invention, and it does not limit the present invention. Those skilled in the art can make modifications without creative contribution to the present embodiment as required after reading this specification, but as long as the rights of the present invention are used All claims are protected by patent law.

Claims (7)

1. The compound medicament for advanced treatment of biochemical tail water is characterized by being prepared from the following raw materials in parts by weight:

25-35% of charge donor, 7-10% of organic flocculant, 0.2-2% of charge carrier, 0.5-1.5% of stabilizer, 3-5% of freezing point conditioner and the balance of water;

the pH value of the composite medicament is 0.5-2;

the charge donor is FeCl₂Or FeSO₄；

The charge carrier is selected from nano zero-valent iron, nano metal oxide FeO and Fe₂O₃And Fe₃O₄One or more of;

the organic flocculant is selected from one or more of polyacrylamide, polydimethyldiallylammonium chloride, dimethyldiallylammonium chloride and polyquaternary ammonium salt;

the stabilizer is selected from one or more of 3-mercaptopropyltriethoxysilane, humic acid, citric acid and dimercaptosuccinic acid;

the compound medicament is prepared by the following preparation method:

s1, adding the charge carriers into a mixed solution consisting of a stabilizer and water accounting for 10-20% of the weight of the composite medicament in batches under ultrasonic stirring according to a set proportion to completely dissolve and disperse the charge carriers in the mixed solution, continuing ultrasonic treatment for 30-60 min, and finally standing for 20-28 h to prepare a mixed solution I;

s2, adding the organic flocculant into the rest water, stirring while adding, and uniformly stirring to obtain a mixed solution II, wherein in S2, the stirring temperature is 45-65 ℃, and the stirring speed is 300-3000 r/min;

s3, adding a charge donor into the mixed solution II under an anaerobic condition, stirring while adding, and stirring uniformly to obtain a mixed solution III;

s4, mixing the mixed solution I and the mixed solution III, and stirring for 30-60 min under the environment that the stirring speed is 100-1000 r/min to obtain a mixed solution IV;

s5, adding a freezing point conditioner into the mixed solution IV, and adjusting the pH value of the solution to 0.5-2 to obtain the composite medicament.

2. The complex reagent for advanced biochemical tailwater treatment according to claim 1, wherein the freezing point conditioner is at least one selected from glycerol and ethylene glycol.

3. The preparation method of the composite medicament for the advanced treatment of biochemical tail water according to any one of claims 1-2, characterized by comprising the following steps:

s1, adding the charge carriers into a mixed solution consisting of a stabilizer and water accounting for 10-20% of the weight of the composite medicament in batches under ultrasonic stirring according to a set proportion to completely dissolve and disperse the charge carriers in the mixed solution, continuing ultrasonic treatment for 30-60 min, and finally standing for 20-28 h to prepare a mixed solution I;

s2, adding the organic flocculant into the rest water, stirring while adding, and uniformly stirring to obtain a mixed solution II, wherein in S2, the stirring temperature is 45-65 ℃, and the stirring speed is 300-3000 r/min;

s3, adding a charge donor into the mixed solution II under an anaerobic condition, stirring while adding, and stirring uniformly to obtain a mixed solution III;

s4, mixing the mixed solution I and the mixed solution III, and stirring for 30-60 min under the environment that the stirring speed is 100-1000 r/min to obtain a mixed solution IV;

s5, adding a freezing point conditioner into the mixed solution IV, and adjusting the pH value of the solution to 0.5-2 to obtain the composite medicament.

4. The method according to claim 3, wherein the charge carriers are added in the S1 in batches, each time the charge carriers account for 0.2-0.5% of the weight of the composite chemical are added, and the time interval between adjacent batches is 28-32 min.

5. The method for preparing the composite reagent for deep treatment of biochemical tail water according to claim 4, wherein in S1, the frequency of the ultrasonic wave is 50-150 Hz.

6. The method for preparing the composite reagent for advanced biochemical tail water treatment according to claim 3, wherein in S3, the stirring speed is 100-1000 r/min.

7. The method for preparing the composite reagent for advanced biochemical tail water treatment according to claim 3, wherein in S5, pH of the solution is adjusted by using pH conditioner, and the pH conditioner is hydrochloric acid with concentration of 10-30% or sulfuric acid with concentration of 10-20%.