CN112457446A - Micro-crosslinked star-shaped flocculant for sludge dewatering and preparation method and application thereof - Google Patents
Micro-crosslinked star-shaped flocculant for sludge dewatering and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/56—Acrylamide; Methacrylamide
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention relates to a micro-crosslinked star-shaped flocculant for sludge dewatering, which comprises the following monomer and auxiliary agent components: monomer (b): acrylamide, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, a functional monomer, a monomer additive and deionized water; auxiliary agent: chelating agent, azo initiator, activator, chain transfer agent, cross-linking agent, oxidant and reductant. Preparing a monomer reaction solution, adjusting the pH value of the solution, cooling, blowing nitrogen to remove oxygen, adding an auxiliary agent for reaction initiation, and reacting and preserving heat to obtain a flocculant colloid; the colloid is crushed, dried and sieved to obtain flocculant powder which is mainly applied to a sludge dewatering treatment process. According to the invention, the polymerization process, the raw materials and the auxiliary agents are selected, the addition amounts of the raw materials and the auxiliary agents are improved, and the functional monomer, the chain transfer agent and the trace cross-linking agent are added, so that the excellent performance of the polymer flocculant in the aspect of sludge dewatering is enhanced.
Description
Technical Field
The invention belongs to the technical field of flocculant preparation, is applied to a sludge dewatering treatment process, and particularly relates to a preparation method and application of a micro-crosslinked star-shaped flocculant for sludge dewatering.
Background
Along with the continuous improvement of urbanization in China, the scale and population of cities are also continuously improved, urban sewage plants are also continuously built, the amount of sludge in sewage is rapidly increased, and the sludge yield in China is estimated to reach about 6000 million tons in 2020. The huge amount of sludge also brings considerable pressure to municipal sewage treatment plants, which is not only related to economic and environmental problems, so how to improve the sludge dewatering performance and improve the sludge dewatering efficiency has become an important issue in the field of sludge treatment.
Among the sludge treatment technologies of the existing acid treatment process, advanced oxidation process, freezing and thawing process, chemical conditioning process and bioleaching process, the flocculation treatment sludge process is more concerned due to the characteristics of simplicity, economy and high efficiency. The flocculation sedimentation technology for treating sludge dehydration has high requirements on the performance of a flocculating agent, so that how to develop a novel and efficient flocculating agent is a key point and a hotspot of research. The sludge contains substances with high negative ion content, and the cationic polyacrylamide can perform electric neutralization and adsorption bridging with colloid particles with negative electricity, so that the colloid particles are promoted to destabilize, aggregate and settle, and the efficient flocculation effect is realized.
In each sludge dewatering technology, the flocculation dewatering agent disclosed in patent CN108083614A is an inorganic-organic composite flocculant, but the dosage of the dewatering agent is 0.2 percent, the dosage is huge, the cost is higher, and the economic benefit is not obvious; the optimal dosage of the sludge dewatering flocculant disclosed in patent CN109824819A is above 70ppm, the preferable dosage needs to be controlled within 30ppm, the construction is not safe, the influence of the amount of the flocculant on flocs is high, the efficiency is not high, and the flocculant is a water-oil emulsion, so that the effective content of a finished product is low, and secondary pollution to the environment can be caused; the star anionic polyacrylamide flocculant disclosed in patent CN106699964B is not added with a small amount of cross-linking agent to form a micro-area network structure, can only be used in 20.5-28.5% of wet-process phosphoric acid sedimentation, and has a small application range. Therefore, it is imperative to develop a flocculant with less dosage, high treatment efficiency, large feeding range, high feeding safety, reduced operability and stable flocculation effect.
Disclosure of Invention
The invention aims to design a micro-crosslinked star-shaped flocculant for sludge dewatering and a preparation method and application thereof. The polymerization process, the raw materials and the auxiliary agents are selected, and the addition amounts of the raw materials and the auxiliary agents are improved, so that functional monomers are added into the raw materials, and a chain transfer agent and a trace amount of a cross-linking agent are introduced into the auxiliary agents, so that the excellent performance of the polymer flocculant in the sludge dewatering aspect is enhanced.
The technical scheme adopted by the invention is as follows: the micro-crosslinked star-shaped flocculant for sludge dewatering is characterized in that: comprises the following monomer and auxiliary components:
the mass fraction of the monomers is as follows: acrylamide accounts for 5-25% of the total mass; 4-48% of acryloyloxyethyl trimethyl ammonium chloride in the total mass; methacryloyloxyethyltrimethyl ammonium chloride (75 wt% aqueous solution) accounts for 0-4% of the total mass; the functional monomer accounts for 0.035-0.35% of the total mass; the monomer additive accounts for 2.5-5% of the total mass; deionized water accounts for 30-88% of the total mass;
the mass fraction of the auxiliary agent is as follows: the concentration of the chelating agent is 50-200ppm of the total mass; the concentration of the azo initiator is 500-1500ppm of the total mass; the concentration of the active agent is 10-100ppm of the total mass; the concentration of the chain transfer agent is 200-600ppm of the total mass; the concentration of the cross-linking agent is 0-50ppm of the total mass; the concentration of the oxidant is 1-10ppm of the total mass; the concentration of the reducing agent is 0.5-8.0ppm of the total mass.
The functional monomer is one or more of trimethylolpropane triacrylate (TMPTA), trimethylolpropane tri-N-propenyl ether, pentaerythritol triacrylate (PETA), pentaerythritol, trimethylolethane or trimethylolpropane and N- [ tri (hydroxymethyl) methyl ] acrylamide.
The monomer additive is one or more of ammonium sulfate, citric acid, succinic acid, sebacic acid, adipic acid, pimelic acid or azelaic acid.
The chelating agent is one or two of diethylene triamine pentaacetic acid pentasodium (Versenex80) and diethylene triamine penta methylene phosphonic acid sodium (DTPMP. Nax).
The active agent is one or two of zinc sulfate or copper sulfate.
The chain transfer agent is one or more of sodium Hypophosphite (HYPO), Sodium Bisulfite (SBS), S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetoxy) trithiocarbonate (DDAT) or sodium formate (HCOONa).
The azo initiator is azo, such as one or more of Azobisisobutyronitrile (AZDN), azobisisobutylimidazoline hydrochloride (VA044) or azobisisobutylamidine hydrochloride (AIBI).
The cross-linking agent is one or more of N, N-Methylene Bisacrylamide (MBA), N-dimethylacryloylethylene diamine, N' - [ oxybis (methylene) ] bisacrylamide, pentaerythritol triallyl ether (APE) or triallyl isocyanurate (TAIC).
The oxidant is one or two of tert-butyl hydroperoxide (TBHP) and Sodium Persulfate (SPS).
The reducing agent is one or two of sodium Metabisulfite (MBS) and ferrous ammonium sulfate (MS).
A preparation method of a micro-crosslinked star-shaped flocculant for sludge dewatering is characterized by comprising the following steps: firstly, preparing a reaction solution; uniformly mixing acrylamide, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, a functional monomer, a monomer additive and supplementary deionized water, and then adjusting the pH of the whole solution to 3-4 by using sulfuric acid and a sodium hydroxide solution; putting the mixture into a refrigerator, cooling to-5 ℃, injecting the mixture into a reaction device, blowing nitrogen to remove oxygen, respectively adding an azo initiator, a chelating agent, an active agent, a chain transfer agent, a crosslinking agent, an oxidant and a reducing agent, taking out the nitrogen blower after reaction initiation, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain a flocculant colloid; then the colloid is crushed, dried at the high temperature of 60-80 ℃, and then crushed and sieved to obtain flocculant powder with the particle size of less than 0.5 mm.
An application of a micro-crosslinked star-shaped flocculant for sludge dehydration is to apply the micro-crosslinked star-shaped flocculant to a sludge dehydration treatment process.
The invention is applied to the sludge dewatering treatment aspect and aims at improving the flocculation effect performance of the high polymer cationic flocculant. The improvement of the preparation process of the polymeric flocculant is reflected in the selection of synthesis temperature, synthesis time and synthesis environment; designing the polymer property and structure, namely selecting synthetic monomers; and the aspects of selecting the reaction auxiliary agent of the polymeric flocculant and the like are improved, so that the flocculant for sludge dewatering is applied to develop the purposes of small using amount, high treatment efficiency, larger feeding range, higher feeding safety, reduced operation difficulty and stable flocculation effect.
The preparation method has the advantages of improving the preparation process of the polymeric flocculant, namely the selection of synthesis temperature, synthesis time and synthesis environment. The invention adopts low-temperature polymerization and uses a heat-preservation reaction device, thereby effectively reducing the temperature loss of the polymeric flocculant in the polymerization process. At low temperature, the polymerization stability of the polymer is improved, and the quenching of free radicals of the polymer in the chain growth process is reduced, so that the molecular weight of the polymeric flocculant is effectively improved; at low temperature, the reaction rate is not too fast, and the production safety and the product quality can be effectively improved. In terms of synthesis time, the product of the invention has longer reaction synthesis time, which is beneficial to improving the molecular weight, thereby improving the quality of the flocculant.
In the selection of the polymerized monomer, the added functional monomer is multifunctional organic molecule, and the functional group includes carbon-carbon double bond, hydroxyl, etc. Because the functional monomers are added, the functional monomers are initiated by free radicals in a polymerization chain initiation stage so as to generate a plurality of free radical active points, and the functional monomers with the plurality of free radical active points are added with the main flocculant monomer to form monomer free radicals; after the monomer free radical is formed, the monomer continues to be subjected to addition polymerization with other main flocculant monomers, so that the multi-arm chain growth is realized, and a micro star structure is formed. The micro-star-shaped flocculant has a star-shaped structure, has lower viscosity and better solubility than linear polyacrylamide under the same molecular weight, and can obtain the flocculation effect which the common linear high-molecular flocculant does not have because the flocculant with the star-shaped structure adopts a more extended conformation in an aqueous solution. The flocculant macromolecule multi-chain with the star-shaped structure is dissolved in water to form a star-shaped structure to form a three-net three-dimensional structure, so that the stretching variable area of the flocculant macromolecule in the water can be increased, the trapping and adsorption effects on colloid are increased, and the charge neutralization of anionic microorganisms is facilitated; secondly, the bridging between colloid and micro suspended solid in the sludge and sewage and the polymer of the flocculating agent can be accelerated. Therefore, the star-shaped flocculant has stronger flocculation effect than a linear flocculant under the same molecular weight.
In the aspects of selection of a reaction auxiliary agent of the polymeric flocculant and the like, a certain amount of chain transfer agent is added, because the high molecular weight cannot be generated in the polymer with a three-dimensional structure, the water solubility of the polymer of the flocculant can be weakened, and the flocculation effect is low. In addition, the addition of cross-linking agents such as an auxiliary agent N, N' -Methylene Bisacrylamide (MBA) and the like can slightly change the structure of a water-soluble polymer chain segment and form micro cross-linking on a polymer chain forming a star structure, so that the flocculant after polymerization has a better water absorption effect and is more soluble in water; moreover, due to the addition of a small amount of crosslinking agents such as crosslinking agent N, N' -Methylene Bisacrylamide (MBA) and the like, the star structure of the star-shaped flocculant is changed into a complex trace net-shaped crosslinking configuration, so that the star structure is changed into a dense net-shaped structure, compared with the prior art, the sludge flocculating effect can be improved, the sludge flocculating effect is more effectively captured, the sludge flocculating agent has very excellent flocculating effect on finer colloids, and the formed flocs are larger; thirdly, the flocs after flocculation are subjected to plate-and-frame filter pressing, so that the flocs have higher shear resistance, are not easy to run mud, and remarkably improve the dewatering effect on the mud. After weak crosslinking, the star-shaped flocculant forms a relatively compact reticular supramolecular structure, hydrolysis is not easy to occur, so that the salt resistance of the star-shaped flocculant is increased, and flocs formed after treatment by the weak crosslinking supramolecular flocculant are relatively compact. Under the same electric neutralization action, the weakly cross-linked flocculant has more adsorption points, so that the dynamic stability of colloidal particles is damaged, and the adsorption effect is better.
According to the invention, the polymerization process, the raw materials and the auxiliary agent are selected, the addition amounts of the raw materials and the auxiliary agent are improved, the functional monomer is added, the chain transfer agent and the trace cross-linking agent are introduced into the auxiliary agent, and the excellent performance of the polymer flocculant in the sludge dewatering aspect is enhanced.
Description of the drawings:
FIG. 1 shows the data of the construction process in Pima county, Arizona in comparison sample 1 and example 3.
The specific implementation mode is as follows:
the following examples further illustrate embodiments of the present invention, but are not intended to limit the scope of the invention.
Example 1
The preparation method of the flocculant comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 20% of acrylamide, 8% of acryloyloxyethyl trimethyl ammonium chloride, 4% of methacryloyloxyethyl trimethyl ammonium chloride, 0.05% of functional monomer pentaerythritol, 3% of monomer additive ammonium sulfate and 64.95% of deionized water; adjusting the pH value of the whole solution to 3.5 by using sulfuric acid and sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 80ppm of chelating agent diethylene triamine pentaacetic acid pentasodium salt (Versenex80), adding 50ppm of active agent zinc sulfate, 200ppm of chain transfer agent sodium formate and 5ppm of cross-linking agent N, N-dimethyl acryloyl ethylene diamine at an interval of 5-8min, and adding 3ppm of oxidant Sodium Persulfate (SPS) and 3ppm of reducing agent ferrous ammonium sulfate (MS) at an interval of 5-8 min; after the reaction is initiated, taking out the nitrogen blower, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain a flocculant colloid;
(3) and (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
Example 2
The preparation method of the flocculant comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 20% of acrylamide, 14.4% of acryloyloxyethyl trimethyl ammonium chloride, 2.6wt% of methacryloyloxyethyl trimethyl ammonium chloride and 0.05% of functional monomer trimethylolpropane triacrylate (TMPTA), 4% of monomer additive ammonium sulfate and 58.95% of deionized water, wherein the total mass of the monomer additive ammonium sulfate and the total mass of the deionized water are mixed together, and regulating the pH of the whole solution to be 3.5 by using sulfuric acid and a sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 80ppm of chelating agent diethylenetriamine pentaacetic acid pentasodium (Versenex80), adding 50ppm of active agent zinc sulfate and 220ppm of chain transfer agent S-1-dodecyl-S '- (alpha, alpha' -dimethyl-alpha '-acetoxy trithiocarbonate (DDAT) and 5ppm of cross-linking agent N, N' - [ oxybis (methylene) ] diacrylamide at intervals of 5-8min, adding 3ppm of oxidant tert-butyl hydroperoxide (TBHP) and 3ppm of reducing agent ferrous ammonium sulfate (MS) after reaction initiation, taking out the nitrogen blower, reacting for 4-10 hours, preserving heat for 2-3 hours, obtaining flocculating agent colloid
(3) And (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
Example 3
The preparation method of the flocculant comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 15% of acrylamide, 24% of acryloyloxyethyl trimethyl ammonium chloride, 1.175% of methacryloyloxyethyl trimethyl ammonium chloride, 0.05% of trimethylolpropane tri-n-propenyl ether serving as a functional monomer, 4% of ammonium sulfate serving as a monomer additive and 55.775% of deionized water serving as the total mass; adjusting the pH value of the whole solution to 3.5 by using sulfuric acid and sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 50ppm of chelating agent diethylene triamine pentaacetic acid pentasodium (Versenex80), adding 20ppm of active agent zinc sulfate, 500ppm of chain transfer agent sodium Hypophosphite (HYPO) and 5ppm of cross-linking agent N, N-Methylene Bisacrylamide (MBA) at intervals of 5-8min, and adding 4ppm of oxidant tert-butyl hydroperoxide (TBHP) and 4ppm of reducing agent ferrous ammonium sulfate (MS) at intervals of 5-8 min; after the reaction is initiated, taking out the nitrogen blower, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain a flocculant colloid;
(3) and (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
Example 4
The preparation method of the flocculant comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 12.5 percent of acrylamide, 32 percent of acryloyloxyethyl trimethyl ammonium chloride, 2.25 percent of methacryloyloxyethyl trimethyl ammonium chloride, 0.05 percent of functional monomer pentaerythritol triacrylate (PETA), 5 percent of monomer additive ammonium sulfate and 48.2 percent of deionized water; adjusting the pH value of the whole solution to 3.5 by using sulfuric acid and sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 50ppm of chelating agent diethylene triamine pentaacetic acid pentasodium salt (Versenex80), adding 10ppm of active agent zinc sulfate, 500ppm of chain transfer agent S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetoxy trithiocarbonate (DDAT) and 5ppm of cross-linking agent pentaerythritol triallyl ether at an interval of 5-8min, and then separating for 5-8min, 4ppm of an oxidant tert-butyl hydroperoxide (TBHP) and 3ppm of a reducing agent ammonium ferrous sulfate (MS) are added; after the initiation of the reaction, the reaction mixture is, and taking out the nitrogen blower, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain the flocculant colloid.
(3) And (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
Example 5
The preparation method of the flocculant comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 5% of acrylamide, 48% of acryloyloxyethyl trimethyl ammonium chloride, 2.25% of methacryloyloxyethyl trimethyl ammonium chloride, 0.05% of functional monomer trimethylolethane or trimethylolpropane, 5% of monomer additive ammonium sulfate and 39.7% of deionized water; adjusting the pH value of the whole solution to 3.5 by using sulfuric acid and sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 50ppm of chelating agent diethylene triamine pentaacetic acid pentasodium salt (Versenex80), adding 20ppm of active agent zinc sulfate and 600ppm of chain transfer agent S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetoxy trithiocarbonate (DDAT) and 5ppm of cross-linking agent or triallyl isocyanurate at an interval of 5-8min, adding 7ppm of oxidant Sodium Persulfate (SPS) and 5ppm of reducer ammonium ferrous sulfate (MS); after the initiation of the reaction, the reaction mixture is, and taking out the nitrogen blower, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain the flocculant colloid.
(3) And (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
The preparation method of the flocculant without using the functional monomer comprises the following steps:
(1) firstly, preparing a reaction solution, namely uniformly mixing 5% of acrylamide, 48% of acryloyloxyethyl trimethyl ammonium chloride, 2.25% of methacryloyloxyethyl trimethyl ammonium chloride, 3% of ammonium sulfate serving as a monomer additive and 41.75% of deionized water in the total mass; adjusting the pH value of the whole solution to 3.5 by using sulfuric acid and sodium hydroxide solution; putting into a refrigerator, and cooling to-5 ℃;
(2) pouring the solution cooled in the step (1) into a heat preservation reaction device, inserting a thermometer and a nitrogen blower, adding 1000ppm of azo initiator Azobisisobutyronitrile (AZDN) and 80ppm of chelating agent diethylenetriamine pentaacetic acid pentasodium salt (Versenex80), adding 50ppm of active agent zinc sulfate and 5ppm of chain transfer agent (HYPO) at intervals of 5-8min, and adding 3ppm of oxidant Sodium Persulfate (SPS) and 3ppm of reducing agent ferrous ammonium sulfate (MS) at intervals of 5-8 min; after the reaction is initiated, taking out the nitrogen blower, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain a flocculant colloid;
and (3) finally, crushing the colloid in the step (2), drying at high temperature, and crushing and sieving the colloid into powder with the particle size of less than 0.5 mm.
Aiming at the above embodiment, the following experimental tests are carried out in the invention:
1. and (3) testing the water filtering speed of the sludge dewatering bench test:
the experimental procedure was: 1) the powders of the above examples and comparative examples were formulated into 2 g/l solutions; 2) taking a sludge sample from a sludge storage tank, wherein the volume of the sludge sample is about 15 liters; 3) taking a 200ml sludge sample to a plastic beaker; adding a suitable amount of flocculant; 4) reacting for 16 times in a mode of mutually falling beakers; 5) the mud water mixture was poured into a funnel and the computer would automatically record the amount of drainage per 0.5 second. 6) The same experiment was carried out with different products and dosages; 7) the optimum flocculant is the product which gives the optimum amount of filtrate at the same dosage. Note: the sludge sewage comes from a wastewater treatment plant in Lunan.
The following table is the drainage rate test data:
the foregoing illustrates the general principles, principal features, and advantages of the invention. It can be seen that examples 1-5 have superior drainage rates and drainage amounts to the conventional sample, control 1. When the solution ratio of the flocculant dosage to the sludge dosage is 1:100, the water filtration amount (ml) in the first 5s does not exceed 100 ml; as the best embodiment 3, when the dosage ratio reaches more than 3:200, the first 5s filtered water amount (ml) exceeds 100ml, compared with the comparative example in which the dosage adjustment of the flocculating agent can not exceed 100ml all the time, the dewatering effect is higher, and when the dosage ratio reaches 1:25, the best dosage ratio is reached, compared with the traditional high dosage, the dosage is low, and the dewatering effect and the use cost are both favorably considered.
2. As can be seen from the data chart of the field work process for comparative sample 1 and example 3 of FIG. 1 in Pima county, Arizona, using the example 3 sample, it can be seen that the polymer usage is reduced by 11.2%, while the centrifuge has a 18.2% lower torque and an 11.6% increase in cake. The invention has the advantages of less usage amount of the product, good sludge treatment effect and the like.
3. Testing the sludge dewatering performance in a laboratory:
preparing a 2 g/L coagulant dissolving agent solution, adding 200ml sludge into 2ml flocculant solution, and testing the turbidity of filtrate, the water content of filter cake and the specific resistance of sludge. Note: the sludge comes from the bottom sludge of the concentration tank in the sewage treatment station of the factory, the water content is 98.56 percent, and the dried ash content is black and yellow.
TABLE 2 laboratory sludge dewatering Performance test data
The foregoing illustrates the general principles, principal features, and advantages of the invention. In general, the water content (%) of the cake, the turbidity (NTU) of the filtrate and the specific resistance (m.kg) of the sludge were measured-1) The data show that the product developed by the invention has good effect in sludge dewatering compared with the comparative sample 1, and especially, the turbidity of the filtrate in the example 3 is reduced by 91.5% under the condition of lower flocculant adding amount ratio of 1:100, so that the product has more obvious excellent effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The micro-crosslinked star-shaped flocculant for sludge dewatering is characterized in that: comprises the following monomer and auxiliary components:
the mass fraction of the monomers is as follows: acrylamide accounts for 5-25% of the total mass; 4-48% of acryloyloxyethyl trimethyl ammonium chloride in the total mass; methacryloyloxyethyltrimethyl ammonium chloride (75 wt% aqueous solution) accounts for 0-4% of the total mass; the functional monomer accounts for 0.035-0.35% of the total mass; the monomer additive accounts for 2.5-5% of the total mass; deionized water accounts for 30-88% of the total mass;
the mass fraction of the auxiliary agent is as follows: the concentration of the chelating agent is 50-200ppm of the total mass; the concentration of the azo initiator is 500-1500ppm of the total mass; the concentration of the active agent is 10-100ppm of the total mass; the concentration of the chain transfer agent is 200-600ppm of the total mass; the concentration of the cross-linking agent is 0-50ppm of the total mass; the concentration of the oxidant is 1-10ppm of the total mass; the concentration of the reducing agent is 0.5-8.0ppm of the total mass.
2. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the functional monomer is one or more of trimethylolpropane triacrylate (TMPTA), trimethylolpropane tri-N-propenyl ether, pentaerythritol triacrylate (PETA), pentaerythritol, trimethylolethane or trimethylolpropane and N- [ tri (hydroxymethyl) methyl ] acrylamide.
3. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the monomer additive is one or more of ammonium sulfate, citric acid, succinic acid, sebacic acid, adipic acid, pimelic acid or azelaic acid.
4. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the chelating agent is one or two of diethylene triamine pentaacetic acid pentasodium (Versenex80) and diethylene triamine penta methylene phosphonic acid sodium (DTPMP. Nax).
5. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the active agent is one or two of zinc sulfate or copper sulfate.
6. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the chain transfer agent is one or more of sodium Hypophosphite (HYPO), Sodium Bisulfite (SBS), S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -acetoxy) trithiocarbonate (DDAT) or sodium formate (HCOONa).
7. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the azo initiator is one or more of Azodiisobutyronitrile (AZDN), azodiisobutylimidazoline hydrochloride (VA044) or azodiisobutyl amidine hydrochloride (AIBI).
8. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the cross-linking agent is one or more of N, N-Methylene Bisacrylamide (MBA), N-dimethylacryloylethylene diamine, N' - [ oxybis (methylene) ] bisacrylamide (CASNO: 169581-71-7), pentaerythritol triallyl ether (APE) or triallyl isocyanurate (TAIC).
9. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the oxidant is one or two of tert-butyl hydroperoxide (TBHP) and Sodium Persulfate (SPS).
10. The micro-crosslinked star-shaped flocculant for sludge dewatering according to claim 1, characterized in that: the reducing agent is one or two of sodium Metabisulfite (MBS) and ferrous ammonium sulfate (MS).
11. A preparation method of a micro-crosslinked star-shaped flocculant for sludge dewatering is characterized by comprising the following steps: firstly, preparing a reaction solution; uniformly mixing acrylamide, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, a functional monomer, a monomer additive and deionized water, and then adjusting the pH of the whole solution to 3-4 by using sulfuric acid and a sodium hydroxide solution; putting the mixture into a refrigerator, cooling to-5 ℃, injecting the mixture into a reaction device, blowing nitrogen to remove oxygen, sequentially adding an azo initiator, a chelating agent, an active agent, a chain transfer agent, a crosslinking agent, an oxidant and a reducing agent, taking out the nitrogen blower after reaction initiation, reacting for 4-10 hours, and then preserving heat for 2-3 hours to obtain a flocculant colloid; then the colloid is crushed, dried at the high temperature of 60-80 ℃, and then crushed and sieved to obtain flocculant powder with the particle size of less than 0.5 mm.
12. The application of the micro-crosslinked star-shaped flocculant for sludge dewatering is characterized in that: use of a micro-crosslinked star-shaped flocculant according to any one of claims 1 to 11 in a sludge dewatering process.
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