CN112939417B - Activated sludge conditioner for wastewater biochemical treatment and preparation method thereof - Google Patents
Activated sludge conditioner for wastewater biochemical treatment and preparation method thereof Download PDFInfo
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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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- C02F11/02—Biological treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/00—Controlling or monitoring parameters in water treatment
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses an activated sludge conditioner for biochemical treatment of wastewater and a preparation method thereof, and relates to the technical field of biological treatment of sewage. The conditioner for the activated sludge comprises, by weight, 6-10 parts of modified beta-cyclodextrin, 8-12 parts of protease, 4-8 parts of cellulase, 3-5 parts of lipase and 2-4 parts of glucanase. The active sludge conditioner prepared by the invention has excellent conditioning performance, improves the dehydration performance of sludge, promotes the rapid propagation and growth of microorganisms in a sludge system, reduces the content of substances such as polysaccharide, protein and the like, and improves the wastewater treatment effect.
Description
Technical Field
The invention belongs to the technical field of biological sewage treatment, and particularly relates to an activated sludge conditioner for biochemical wastewater treatment and a preparation method thereof.
Background
For town sewage treatment plants mainly based on the activated sludge process, the construction investment of the sludge treatment system accounts for about 20-40% of the total investment of the sewage treatment plant, and the operation cost of the sludge treatment accounts for about 20-30% of the total operation cost of the sewage treatment plant. Research and practice have shown that even the dehydrated mud cake has the moisture content as high as about 80 percent, which brings difficulty to subsequent landfill or incineration disposal. Therefore, how to improve the dehydration performance of the sludge is always a difficult problem which troubles sewage treatment plants. In order to improve the dehydration performance of the sludge, the sludge must be conditioned before dehydration, and the tissue structure of the sludge is changed through conditioning, so that the Specific Resistance (SRF) of the sludge is reduced, and the dehydration performance of the sludge is improved, and the subsequent treatment and disposal are facilitated. The chemical conditioning effect of the sludge is reliable, the equipment is simple, the operation is convenient, and the chemical conditioning agent is widely adopted for a long time. In chemical conditioning, the inorganic salt flocculating agent has large dosage and is easy to generate secondary pollution. The synthetic organic polymer flocculant polyacrylamide PAM has the advantages of small using amount, high efficiency, high flocculation speed and the like, and related researches and applications are more, but residues of the polyacrylamide PAM are not easily biodegraded and have poor flocculation effect on microorganisms.
With the continuous and deep research of researchers on sludge conditioning technologies, a single conditioning technology cannot meet the actual needs of engineering, so that the researchers combine different technologies to make up for the deficiencies of the technologies and cooperate with each other to improve the efficiency and the degree of sludge dewatering. The combined conditioning methods are various, including chemical-chemical combined conditioning methods, physical-physical combined conditioning methods, biological-chemical combined conditioning methods, physical-biological combined conditioning methods and the like. A large number of researches show that when two or more conditioning methods are matched for use, not only can a better sludge conditioning effect be achieved, but also the dosage of chemical reagents can be reduced. Therefore, the combined conditioning method is more energy-saving and environment-friendly, and is the main development direction of sludge conditioning in the future.
Disclosure of Invention
The invention aims to provide an active sludge conditioner for biochemical treatment of wastewater and a preparation method thereof.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention discloses application of 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin in preparation of an activated sludge conditioner. The beta-cyclodextrin is nontoxic and easy to obtain, can convert sludge which is not easy to dehydrate into sludge with moderate dehydration performance, and can remarkably improve the dehydration performance of activated sludge by modifying the sludge by adopting 3- (aminomethyl) -N-methylbenzenesulfonamide; the existence of 3- (aminomethyl) -N-methylbenzenesulfonamide can increase the particle size of sludge floc, reduce the specific surface area, promote the flocculation of new domestic sludge and prevent the loss of new sludge along with effluent before flocculation; and under the condition that the sludge structure is compact, the pore volume is increased, and the dehydration performance is further improved.
Preferably, the preparation method of the 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin specifically comprises the following steps:
synthesizing mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, dissolving the beta-cyclodextrin in NaOH solution, slowly adding p-toluenesulfonyl chloride for reaction, filtering, recrystallizing and drying in vacuum to obtain a product M;
synthesizing 3- (aminomethyl) -N-methylbenzenesulfonamide-beta-cyclodextrin, adding a product M, 3- (aminomethyl) -N-methylbenzenesulfonamide and sodium carbonate into DMF, and heating to 80-85 ℃ for reaction; filtering and purifying after reaction to obtain the modified beta-cyclodextrin.
Preferably, during the synthesis process of the mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.3 to 0.5; adjusting the pH value to 6-7.
Preferably, in the synthesis process of the 3- (aminomethyl) -N-methylbenzenesulfonamide-beta-cyclodextrin, the mass ratio of the product M to the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.3-0.5: 0.3 to 0.4; the solid-liquid ratio of the product M to DMF is 1 g: 14-18 mL.
The conditioner for activated sludge comprises the modified beta-cyclodextrin.
The invention also discloses application of the conditioner in biochemical treatment of activated sludge in sewage, wherein the addition amount of the conditioner is 8-12 mg/g.
A conditioner for biochemical treatment of wastewater comprises, by weight, 6-10 parts of modified beta-cyclodextrin, 8-12 parts of protease, 4-8 parts of cellulase, 3-5 parts of lipase and 2-4 parts of glucanase. When the combined conditioning is carried out, the chemical reagent and the biological enzyme are mutually cooperated, and the COD of the supernatant is reduced through the adsorption and bridging action; the specific surface area of the sludge is rapidly reduced, small-particle-size particles are reduced, and the dispersity is reduced; the sludge floc structure is compact but still has partial pores, which is beneficial to the outflow of water, thereby improving the dehydration performance. The preparation method of the conditioner has mild reaction conditions, simple process and low preparation cost; can quickly stimulate the proliferation of microorganisms in the activated sludge and improve the treatment efficiency of the activated sludge.
The preparation method of the conditioner for the biochemical treatment of the activated sludge from the wastewater comprises the following steps:
preparing protease, cellulase, lipase and dextranase into a solution, mixing, and adjusting pH to obtain a compound enzyme solution; then adding the modified beta-cyclodextrin, and uniformly mixing to prepare the wastewater biochemical treatment activated sludge conditioner.
Preferably, the mass concentration of the protease, cellulase, lipase and glucanase solution is 0.1-0.5%.
Preferably, the pH value is 5.5-7.0.
The invention also discloses the application of the conditioner in the biochemical treatment of the activated sludge in the sewage, wherein the adding amount of the conditioner is 20-30 mg/L.
Preferably, the conditioner also comprises rhodiola rosea extract, and the mass of the rhodiola rosea extract is 5-8% of that of the modified beta-cyclodextrin. The rhodiola rosea extract can quickly stimulate the proliferation of microorganisms in the activated sludge and improve the treatment efficiency of the activated sludge; and the enzyme activity can be enhanced, so that various biochemical indexes of a sludge system are enhanced, the content of polysaccharide and protein and the total EPS amount are reduced, and organic matters such as EPS and the like can be degraded and utilized to a greater extent. And the compound is compounded with other components, and the effect of removing COD, nitrogen and phosphorus in the sewage is further enhanced under the synergistic effect; in addition, the dewatering performance of the sludge is also obviously enhanced.
Compared with the prior art, the invention has the following beneficial effects:
the beta-cyclodextrin is nontoxic and easy to obtain, and can be modified by 3- (aminomethyl) -N-methylbenzenesulfonamide, so that the dehydration performance of the activated sludge can be remarkably improved; the existence of 3- (aminomethyl) -N-methylbenzenesulfonamide can increase the grain diameter of sludge floc, promote the flocculation of new domestic sludge and improve the dewatering performance of the new domestic sludge. When the combined conditioning is carried out, the chemical reagent and the biological enzyme are mutually cooperated, so that the COD content is reduced; the specific surface area of the sludge is rapidly reduced, small-particle-size particles are reduced, and the dispersity is reduced; the sludge floc structure is compact but still has partial pores, which is beneficial to the outflow of water and further improves the dehydration performance. In addition, the rhodiola rosea extract can enhance the enzyme activity, strengthen various biochemical indexes of a sludge system, degrade to a greater extent and utilize organic matters such as EPS and the like; and the modified beta-cyclodextrin is compounded, so that COD, nitrogen and phosphorus in the sewage are further removed under the synergistic effect, and the dehydration performance of the sludge is enhanced. The preparation method of the conditioner has mild reaction conditions, simple process and low preparation cost; can quickly stimulate the proliferation of microorganisms in the activated sludge and improve the treatment efficiency of the activated sludge.
Therefore, the activated sludge conditioner for wastewater biochemical treatment and the preparation method thereof provided by the invention have excellent strengthening performance, improve the dehydration performance of sludge, promote the rapid propagation and growth of microorganisms in a sludge system, reduce the content of substances such as polysaccharide and protein, and improve the sewage treatment effect.
Drawings
FIG. 1 shows the results of the infrared test in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the rhodiola rosea extract used in the embodiment of the invention is purchased from a direct grocery store of a reel biological factory, wherein the content of salidroside is more than or equal to 10 percent; the protease is purchased from Zhengzhou Junkai chemical products Co., Ltd, and the enzyme activity is more than or equal to 100U/mg; the cellulase is purchased from Bo-ao biotechnology limited of Shanghai, and the enzymatic activity is more than or equal to 15U/mg; the lipase is purchased from Shanghai Boao Biotechnology limited, and the enzyme activity is more than or equal to 32U/mg; the glucanase is purchased from Shandong Su Kehan bioengineering GmbH, and the enzyme activity is more than or equal to 40U/mg.
Example 1:
preparing modified beta-cyclodextrin:
synthesizing mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, dissolving the beta-cyclodextrin in 0.75mol/L NaOH solution, and stirring; slowly adding p-toluenesulfonyl chloride (the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.36) in ice bath, reacting for 4h, and filtering. Adjusting the pH value to 6 by using 1mol/L HCl solution, refrigerating for 12h in a refrigerator, filtering to obtain a crude product, recrystallizing for 2 times, and vacuum-drying the obtained solid at 60 ℃ to obtain a product M;
synthesizing 3- (aminomethyl) -N-methylbenzenesulfonamide-beta-cyclodextrin, putting a product M, 3- (aminomethyl) -N-methylbenzenesulfonamide, sodium carbonate (the mass ratio of the product M to the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.4: 0.36) and DMF (the solid-to-liquid ratio of the product M to the DMF is 1 g: 15mL) into a 100mL round-bottom flask, heating to 85 ℃ under the protection of nitrogen, and reacting for 12 hours. Filtering after reaction, pouring the filtrate into acetone solution to obtain white precipitate, and filtering. And (3) collecting solids, dissolving the solids in a DMF solution, separating by a Sephadex G25 gel chromatographic column, and collecting components which are developed under iodine fumigation by using DMF as an eluent to obtain the modified beta-cyclodextrin, wherein the yield is 85.4%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 8 parts of modified beta-cyclodextrin, 10 parts of protease, 6 parts of cellulase, 4 parts of lipase and 3 parts of glucanase.
The preparation method of the conditioner comprises the following steps:
preparing a solution with the mass concentration of 0.25% by taking protease, cellulase, lipase and glucanase, mixing and adjusting the pH value to 6.0 to prepare a compound enzyme solution; then adding the modified beta-cyclodextrin, and uniformly mixing to prepare the wastewater biochemical treatment activated sludge conditioner.
Example 2:
the modified beta-cyclodextrin was prepared differently from example 1 in that: the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.3; the mass ratio of the product M, the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.3: 0.34; the solid-liquid ratio of the product M to DMF is 1 g: 14 mL; the yield of modified beta-cyclodextrin was 79.3%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 9 parts of modified beta-cyclodextrin, 12 parts of protease, 7 parts of cellulase, 3 parts of lipase and 2 parts of glucanase.
The preparation method of the conditioner is different from that of the example 1 in that: the mass concentration of the protease, cellulase, lipase and dextranase solution is 0.36 percent.
Example 3:
the modified beta-cyclodextrin was prepared differently from example 1 in that: the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.4; the mass ratio of the product M, the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.38: 0.35; the solid-liquid ratio of the product M to DMF is 1 g: 16 mL; the yield of modified beta-cyclodextrin was 81.7%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 8 parts of modified beta-cyclodextrin, 9 parts of protease, 5 parts of cellulase, 4 parts of lipase and 2 parts of glucanase.
The preparation method of the conditioner is different from that of the example 1 in that: the mass concentration of the protease, cellulase, lipase and dextranase solution is 0.4 percent.
Example 4:
the modified beta-cyclodextrin was prepared differently from example 1 in that: the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.42; the mass ratio of the product M, the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.39: 0.4; the solid-liquid ratio of the product M to DMF is 1 g: 17 mL; the yield of modified beta-cyclodextrin was 76.9%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 6 parts of modified beta-cyclodextrin, 8 parts of protease, 6 parts of cellulase, 3 parts of lipase and 2 parts of glucanase.
The preparation method of the conditioner is different from that of the embodiment 1 in that: the mass concentration of the protease, the cellulase, the lipase and the dextranase solution is 0.2 percent.
Example 5:
the modified beta-cyclodextrin was prepared differently from example 1 in that: the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.45 of; the mass ratio of the product M, the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.4: 0.36; the solid-liquid ratio of the product M to DMF is 1 g: 16 mL; the yield of modified beta-cyclodextrin was 83.8%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 7 parts of modified beta-cyclodextrin, 11 parts of protease, 7 parts of cellulase, 4 parts of lipase and 4 parts of glucanase.
The preparation method of the conditioner is different from that of the embodiment 1 in that: the mass concentration of the protease, cellulase, lipase and dextranase solution is 0.15%.
Example 6:
the preparation of modified beta-cyclodextrin differed from example 1 in that: the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.48; the mass ratio of the product M, the 3- (aminomethyl) -N-methylbenzenesulfonamide to the sodium carbonate is 1: 0.5: 0.4; the solid-liquid ratio of the product M to DMF is 1 g: 14-18 mL; the yield of modified beta-cyclodextrin was 86.1%.
A conditioner for biochemically treating activated sludge by waste water comprises, by weight, 8 parts of modified beta-cyclodextrin, 10 parts of protease, 6 parts of cellulase, 5 parts of lipase and 3 parts of glucanase.
The preparation method of the conditioner is different from that of the example 1 in that: the mass concentration of the protease, cellulase, lipase and dextranase solution is 0.46 percent.
Example 7:
the modified beta-cyclodextrin was prepared as in example 1.
A conditioner for the biochemical treatment of activated sludge from wastewater was the same as in example 1.
The preparation method of the conditioner is different from that of the example 1 in that: adding rhodiola rosea extract, wherein the adding amount is 6 percent of the mass of the modified beta-cyclodextrin.
Example 8:
the modified beta-cyclodextrin was prepared as in example 1.
The conditioner of the activated sludge is modified beta-cyclodextrin.
Example 9:
the modified beta-cyclodextrin was prepared as in example 8.
The conditioner of the activated sludge is a mixture of modified beta-cyclodextrin and rhodiola rosea extract, and the quality of the rhodiola rosea extract is 6 percent of the quality of the modified beta-cyclodextrin.
Comparative example 1:
the difference between the conditioner for the biochemical treatment of the activated sludge by the wastewater and the conditioner in the embodiment 1 is that: beta-cyclodextrin is used to replace the modified beta-cyclodextrin.
The above conditioner was prepared in the same manner as in example 1.
Comparative example 2:
the difference between the conditioner for the biochemical treatment of the activated sludge by the wastewater and the conditioner in the embodiment 1 is that: PAM is used to replace modified beta-cyclodextrin.
The above conditioner was prepared in the same manner as in example 1.
Comparative example 3:
an activated sludge conditioner differs from example 8 in that: beta-cyclodextrin is used to replace the modified beta-cyclodextrin.
Test example 1:
1. infrared Spectrometry (FT-IR)
After a sample is subjected to water removal treatment in a constant-temperature drying oven, a small amount of sample and potassium bromide are uniformly mixed in an agate mortar, ground and tabletted, and then the mixture is placed on a TENSOR 27 type infrared spectrometer for testing, wherein the scanning wave number range is 4000-500 cm -1 Scanning resolution of 6cm -1 The number of scans was 18.
The above tests were performed on beta-cyclodextrin and the modified beta-cyclodextrin obtained in example 1, and the results are shown in fig. 1. As can be seen from the figure, the peak shape and the position of the main peak are basically not changed compared with the beta-cyclodextrin, which indicates that the main framework of the modified cyclodextrin is not changed, and the modified beta-cyclodextrin is 3120cm -1 A characteristic absorption peak appears nearby, which is a characteristic absorption peak of amide groups and is 1610cm -1 The absorption peak of amide I band is 1400-1500 cm -1 The peak is a vibration absorption peak of a benzene ring skeleton, 1360cm -1 Is characterized by an S-O characteristic absorption peak of 1320cm -1 The vicinity is a C-N bond stretching vibration absorption peak. The above results demonstrate the success of the preparation of modified beta-cyclodextrin.
2. Protease activity assay
Preparing protease into 0.25% solution, adding 0.05% radix Rhodiolae extract (experimental group), and not adding as control group; the enzyme activity was measured by shaking in a constant temperature shaker at (25. + -. 1) ° C for 1 day at 150 r/min.
The test method comprises the following steps: preparing a substrate casein into a 10mg/mL casein solution by using a Tris-HCl buffer solution (0.05mol/L, pH value of 8.5), adding 1mL of the solution into 1mL of the filtrate respectively, carrying out water bath reaction at 37 ℃ for 30min, and repeating the treatment for 3 times; terminating the reaction with 2mL of 0.4mol/L trichloroacetic acid and filtering, detecting the remained filtrate by Folin-phenol reagent, adding 400 mu L of filtrate into each tube, standing and reacting 2mL of A, B mixed liquor (prepared according to the proportion of 1: 50) such as Folin at room temperature for 10min, adding 200 mu L of phenol reagent, standing for 30min, measuring the absorbance at the wavelength of 650nm, using the enzyme amount which is catalyzed and decomposed for 1min to generate 1 mu g of tyrosine as 1 activity unit (U/mL), and preparing a standard curve by using tyrosine standard solution so as to determine the activity of extracellular protease. The results were characterized as the rate of increase of enzyme activity.
The test and calculation show that the enzyme activity increase rate of the protease solution added with the rhodiola rosea extract is 20.6 percent, which shows that the existence of the rhodiola rosea extract can effectively improve the enzyme activity and further improve the conditioning effect on activated sludge.
Test example 2
1. Determination of specific resistance SRF
The difficulty of sludge dewatering is generally measured by the sludge specific resistance SRF, which reflects the amount of resistance experienced by the water passing through the cake layer during the entire filtration process. In general, the smaller the specific resistance SRF, the better the sludge dewatering performance; on the contrary, the worse the sludge dewatering performance. The calculation formula of the sludge specific resistance is as follows:
R＝2pA 2 b/(μω)
in the formula, R-specific resistance is m/kg; p-filtration pressure, N/m 2 (ii) a A-filtration area, m 2 (ii) a b-ratio of filtration time to the square of the filtrate volume, s/m 6 (ii) a Mu-dynamic viscosity of the filtrate, N.s/m 2 (ii) a Omega-mass of solid retained per unit of filter medium, kg/m 3 。
2. Sludge Conditioning test
The sludge is taken from the outlet of a concentration tank of a certain sewage treatment plant, and the specific indexes of the sludge are shown in table 1:
TABLE 1 main indices of sludge used in the experiment
| Index (I) | MLSS(mg/L) | MLVSS(mg/L) | SV | SRF(×10 13 m/kg) |
| Numerical value | 4980 | 3020 | 58 | 5.83 |
The test method comprises the following steps: 250mL of raw sludge is taken in a 1000mL beaker, a conditioner (the adding amount of the conditioner without the biological enzyme is 10 mg/g. dry sludge, the adding amount of the conditioner with the biological enzyme is 25mg/L) is added, the mixture is placed on a six-joint constant-temperature (25 ℃) electric stirrer to be quickly stirred for 1min, then the mixture is slowly stirred for 5min, and the stirrer is closed. After completion of conditioning, 100mL of conditioned sludge was taken and subjected to SRF measurement.
The results of the above tests on comparative examples 1 to 3 and examples 1 to 9 are shown in Table 2:
TABLE 2 specific resistance SRF test results
As can be seen from the table 2, the rhodiola rosea extract has a certain conditioning effect on the dehydration performance of activated sludge, and the specific resistance SRF value is reduced by 36.0%; the specific resistance SRF value of the conditioner prepared in the embodiment 8 is obviously lower than that of the conditioner prepared in the comparative example 3, which shows that the dehydration performance of the conditioner on activated sludge can be effectively improved by adopting 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin; the effect of example 9 is significantly higher than that of comparative example 3 and example 8, which shows that the modified beta-cyclodextrin and rhodiola rosea extract are compounded to play a role in synergistic enhancement. The specific resistance SRF value of the conditioner prepared in the example 1 after being conditioned is obviously lower than that of the comparative example 1 and the comparative example 2, and is lower than that of the example 8, the combined conditioning effect of the modified beta-cyclodextrin and the biological enzyme is better than that of the unmodified beta-cyclodextrin and the modified beta-cyclodextrin and the biological enzyme, the conditioning effect of the conditioner on the activated sludge is obviously enhanced due to the existence of the 3- (aminomethyl) -N-methylbenzenesulfonamide, and the combined conditioning effect is obviously better than that of single conditioning. The effect of example 7 is significantly better than that of example 1, indicating that the presence of rhodiola rosea extract has a synergistic effect.
3. Particle size distribution test
The particle size distribution is detected by a Malvern MS 3000 laser particle size analyzer. And (3) filling a circulating sample injector of the particle size analyzer with deionized water, slowly dripping the sludge sample until the shading degree is maintained between 15 and 85 percent, starting to measure, and automatically and continuously measuring for 5 times by each group of sludge sample instruments. The method adopts deionized water as a dispersing agent. Untreated sludge was used as a control. For more intuitive reaction of the particle size variation process, the test selects a representative median diameter D V [50]The particle size of (1) is changed.
The results of the above tests on the conditioner-treated sludge obtained in comparative example 1 and example 1 are shown in Table 3:
TABLE 3 influence of specific surface area and particle size of sludge
| Sample (I) | Specific surface area (m) 2 /kg) | D V [50](μm) |
| Control sample | 810.1 | 17.8 |
| Comparative example 1 | 786.4 | 19.4 |
| Example 1 | 757.3 | 22.3 |
From the analysis in table 3, it can be seen that the specific surface area of the sludge treated by the conditioner prepared in example 1 is rapidly reduced, which is significantly lower than that of the control sample and comparative example 1, and the small-particle-size particles are reduced, which indicates that the 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin can effectively reduce the dispersion degree of the sludge, the sludge floc structure is compact, but the pores formed inside are increased, and the dewatering performance is greatly improved. The presence of 3- (aminomethyl) -N-methylbenzenesulfonamide has an enhancing effect.
4. Sludge bioactivity test
Diluting original sludge (sludge for testing specific resistance SRF) with distilled water until the sludge concentration MLSS is about 3500mg/L, adding 10mg/L of conditioner (drug group), not adding a control group, oscillating the sludge mixed liquor of all the drug groups and the control group at 25 ℃ at 80-120 r/min for 7d, and measuring the content of polysaccharide and protein in EPS.
EPS determination
Preparing an extracting solution: centrifuging an appropriate amount of sludge mixed liquor for 5min at 5000r/min, filtering with 0.45 μm filter membrane, storing, adding deionized water to the original volume, mixing, heating at 60 deg.C for 20min, centrifuging at 12000r/min for 10min, filtering with 0.45 μm filter membrane, and mixing with the above step.
And (3) determination of polysaccharide: taking 2mL of the extracting solution, adding 4mL of anthrone reagent (used in preparation) and shaking uniformly, and measuring the absorbance value at 610 nm;
determination of protein: the extract was mixed with Coomassie brilliant blue reagent and the absorbance was measured at 595 nm.
The results of the above tests on the conditioners prepared in comparative example 1, example 1 and example 7 are shown in Table 4.
TABLE 4 test results
| Sample (I) | Polysaccharide (mg/L) | Protein (mg/L) | EPS(mg/L) |
| Control group | 33.6 | 37.3 | 71.9 |
| Comparative example 1 | 24.3 | 25.3 | 49.6 |
| Example 1 | 20.9 | 24.9 | 45.8 |
| Example 7 | 10.3 | 16.4 | 26.7 |
From the analysis in table 4, it can be seen that after the conditioner prepared in example 7 is added, the content of polysaccharide and protein is lower than that of the control group and that of example 1, the total amount of EPS is significantly lower than that of the control group and that of example 1, while the effect of example 1 is not significantly different from that of comparative example 1, which indicates that after the conditioner is added, the degradation of polysaccharide and protein is enhanced, and the presence of the rhodiola rosea extract can effectively enhance the enzymatic activity, degrade to a greater extent and utilize organic matters such as EPS.
Test example 3:
simulated sewage treatment test
Experimental device
The reactor size: 0.5 is 0.9m by 0.9m, the effective volume is 0.5 is 0.7 is 175L, the position of one side of the reactor, which is 30mm, 100mm, 300mm and 600mm away from the bottom of the tank, is perforated for discharging mud and water, the aperture phi is 25mm, the reactor is made of a 7mm thick PVC plate, one side of the reactor adopts a transparent plate and is marked with scales, and the scale lines are 100mm, 200mm, 300mm, 400mm, 500mm, 600mm, 700mm and 800mm away from the bottom of the reactor respectively, thereby being convenient for observing the water inlet and outlet height and the sludge layer height. The type of the small fan is as follows: ACQ-005, 220-240V, 50Hz, 85W of power and 60L/min of air volume.
Source of sludge
The inoculated sludge is taken from the outlet of a concentration tank of a sewage treatment plant. For the convenience of comparison test, the concentration of the sludge after inoculation of the drug adding group (the adding amount of the conditioner without the biological enzyme is 10 mg/g. dry sludge, the adding amount of the conditioner with the biological enzyme is 25mg/L) and the control group is as much as possible. Inoculating sludge for acclimatization and culture for 10 days, and adding the microbial inoculum into the dosing group. Specific sludge indexes are shown in table 5:
TABLE 5 main indices of sludge used in the experiment
| Index (es) | MLSS(mg/L) | MLVSS(mg/L) | SV |
| Numerical value | 4980 | 3020 | 58 |
The main water quality indexes of the self-prepared simulated sewage are shown in table 6:
TABLE 6 quality of influent water
| Index (es) | pH | COD(mg/L) | TN(mg/L) | TP(mg/L) |
| Numerical value | 6.8 | 563 | 32 | 6.1 |
The water is drained from the position 0.7m of the height of the reactor to 0.3m in each period, and the water is fed from 0.3m to 0.7m, namely the water inlet and outlet amount is 100L in each period.
The device operates: 6 in the morning: 00 stopping aeration by an aerator, entering a precipitation stage, precipitating for 1h, 7: 00 draining for 1h, standing for 30min, 8: 30 water inflow to start a cycle of treatment, 30min water inflow, 9: and 00, starting aerobic aeration reaction for 300min after water inflow is finished, and 14: 00, stopping aeration by an aerator, precipitating for 1h, and 15: 00 draining for 1h, standing for 30min, 16: 30 begin to fill with water for a new cycle and so on. A Coriolis timer (model: TW-K11) is adopted for automatic control, and the switches are started at fixed time. 3 cycles per day, one cycle of 8 h. The operation is limited to one month. During the operation of the experimental device, when MLSS is more than 4000mg/L, sludge is discharged from the reactor, and the sludge discharge amount is standard for reducing the sludge concentration in the reactor to about 4000 mg/L.
The conventional detection indexes and analysis methods are shown in table 7:
TABLE 7 test items and analysis methods
| Detecting items | Analytical method |
| COD | Potassium dichromate process |
| TN | Potassium persulfate oxidation process |
| TP | Ammonium molybdate spectrophotometry |
| MLSS | Drying and weighing method |
| MLVSS | Muffle furnace firing method |
The test is carried out on the conditioners prepared in the comparative examples 1-3, 1 and 7-9, and the detection results of the effluent quality are shown in the following table 8:
TABLE 8 detection results of various indexes of effluent quality
As can be seen from Table 8, the specific resistance SRF value of the conditioner prepared in example 1 after conditioning is obviously lower than that of comparative example 1 and comparative example 2, and is lower than that of example 8, which shows that the combined conditioning effect of the modified beta-cyclodextrin and the biological enzyme is better than that of the unmodified beta-cyclodextrin, the removal effect of COD, nitrogen and phosphorus is obviously enhanced by the presence of 3- (aminomethyl) -N-methylbenzenesulfonamide, and the combined conditioning effect is obviously better than that of single conditioning. The effect of example 7 is significantly better than that of example 1, indicating that the presence of rhodiola rosea extract has a synergistic effect. Similarly, example 8 was more effective than comparative example 3, and example 9 was more effective than example 8, consistent with the results of the foregoing analyses.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A conditioner for the biochemical treatment of activated sludge by wastewater is characterized in that: the modified beta-cyclodextrin cellulase comprises, by weight, 6-10 parts of 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin, 8-12 parts of protease, 4-8 parts of cellulase, 3-5 parts of lipase and 2-4 parts of glucanase;
the preparation method of the 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin specifically comprises the following steps:
synthesizing mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, dissolving beta-cyclodextrin in NaOH solution, slowly adding p-toluenesulfonyl chloride for reaction, filtering, recrystallizing and drying in vacuum to obtain a product M;
synthesizing 3- (aminomethyl) -N-methylbenzenesulfonamide-beta-cyclodextrin, adding a product M, 3- (aminomethyl) -N-methylbenzenesulfonamide and sodium carbonate into DMF, and heating to 80-85 ℃ for reaction; filtering and purifying after reaction to obtain modified beta-cyclodextrin;
the conditioner also comprises a rhodiola rosea extract, and the mass of the rhodiola rosea extract is 5-8% of that of the 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin.
2. The conditioner for the biochemical treatment of activated sludge of wastewater according to claim 1, wherein: in the synthesis process of the mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, the mass ratio of the beta-cyclodextrin to the p-toluenesulfonyl chloride is 1: 0.3 to 0.5; adjusting the pH value to 6-7.
3. The conditioner for the biochemical treatment of activated sludge of wastewater according to claim 1, wherein: in the synthesis process of the 3- (aminomethyl) -N-methylbenzenesulfonamide-beta-cyclodextrin, the mass ratio of a product M to 3- (aminomethyl) -N-methylbenzenesulfonamide to sodium carbonate is 1: 0.3-0.5: 0.3 to 0.4; the solid-liquid ratio of the product M to DMF is 1 g: 14-18 mL.
4. The method for preparing a conditioner of activated sludge for biochemical treatment of wastewater according to claim 1, comprising:
preparing protease, cellulase, lipase and dextranase into a solution, mixing, and adjusting pH to obtain a compound enzyme solution; then adding the 3- (aminomethyl) -N-methylbenzenesulfonamide modified beta-cyclodextrin and the rhodiola rosea extract in the claim 1, and mixing uniformly to obtain the wastewater biochemical treatment activated sludge conditioner.
5. The method for preparing the conditioner of the activated sludge for the biochemical treatment of the wastewater according to claim 4, wherein: the pH value is 5.5-7.0.
6. The use of the conditioner in the biochemical treatment of activated sludge in sewage according to claim 1, wherein the dosage of the conditioner is 8-12 mg/g dry sludge.
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