Sludge domestication nutrient solution, autotrophic denitrification sludge as well as preparation method and application of autotrophic denitrification sludge

Abstract

The invention relates to the technical field of sewage treatment materials, and particularly discloses a sludge domestication nutrient solution, autotrophic denitrification sludge and a preparation method and application thereof. The sludge domestication nutrient solution provided by the invention contains various nutritional ingredients required by metabolism of different flora microorganisms, so that the problem of weakening of flora variety diversity caused by insufficient nutrient elements is avoided; the sludge domestication nutrient solution is rich in various trace elements and growth promoting factors, promotes the growth activity of various enzymes and microorganisms, also promotes the growth of microbial flora cells, enriches the types and abundance of the flora, and enhances the reproductive capacity and diversity of the flora. According to the method, thiobacillus denitrificans, pseudomonas and lysobacter in sludge are activated into dominant strains by selecting a specific sludge domestication nutrient solution, the dominant strains are applied to sewage, and the dual effects of nitrogen and phosphorus removal are achieved under the condition that no extra carbon source is added.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment materials, and in particular to a sludge acclimation nutrient solution, autotrophic denitrification sludge, and a preparation method and application thereof. Background Art

[0002] At present, the denitrification market mostly relies on the addition of organic carbon sources to achieve the purpose of denitrification. However, the use of organic carbon sources has problems such as large carbon source usage, high operating costs, high carbon emissions, large sludge production, and easy exceeding of effluent standards. Based on these pain points, a new autotrophic denitrification biotechnology that does not require external organic carbon sources, has high denitrification efficiency, avoids carbon emissions, has low operating costs, and effectively achieves the synergy of "denitrification and carbon reduction" will become a major demand for future industry market technology development and application.

[0003] Autotrophic denitrification biological denitrification technology is based on the action of sulfur autotrophic denitrifying microorganisms, which can utilize inorganic carbon sources (such as CO2, HCO3 - and CO3 2- ) and reduced inorganic substances (such as S, S - , S 2- 、S2O3 2- , Fe and Fe 2+ etc.) as energy and electron donors, converting nitrate nitrogen (NO3 - -N and NO2 - -N) is reduced to nitrogen (N2), and this reaction process achieves nitrogen removal. However, the current autotrophic denitrification biological denitrification technology consumes the alkalinity of sewage during actual application, resulting in a decrease in the pH of the effluent, which in turn reduces the denitrification efficiency of microorganisms and results in limited removal of total nitrogen content in sewage. Therefore, it is urgent to seek new biological denitrification processes for sewage. Summary of the invention

[0004] In view of this, the present invention provides a sludge acclimation nutrient solution, autotrophic denitrification sludge, and a preparation method and application thereof.

[0005] In order to solve the above technical problems, the technical solution provided by the present invention is: The first aspect of the present invention provides a nutrient solution for sludge acclimation, comprising the following raw material components by weight: NO3 - -N 0.05-0.07 parts, hydrogen phosphate 0.43-0.48 parts, soluble magnesium salt 0.01-0.03 parts, soluble calcium salt 0.005-0.007 parts, bicarbonate 0.8-1.0 parts, trace elements 0.00261-0.00275 parts, growth promoting factor 0.00465-0.00473 parts and water 1000 parts; The trace elements include the following raw material components in percentage by mass: molybdate 7.27%-8.43%, boric acid 3.64%-4.60%, soluble copper salt 7.27%-8.43%, soluble manganese salt 3.27%-3.83%, soluble cobalt salt 10.91%-11.88%, soluble zinc salt 3.64%-4.21%, soluble nickel salt 0.73%-1.15%, soluble iron salt 36.36%-39.08% and EDTA 21.82%-23.75%; The growth promoting factor comprises the following raw material components in percentage by weight: 4.23%-4.52% lysine, 2.11%-2.37% isoleucine, 2.11%-2.37% phenylalanine, 5.29%-5.59% threonine, 21.14%-21.72% cystine, 21.14%-21.72% yeast extract, 21.14%-21.72% beef extract and 21.14%-21.72% sorbitol.

[0006] Compared with the prior art, the sludge acclimation nutrient solution provided by the present invention contains a variety of nutrients required for the metabolism of microorganisms of different bacterial communities, among which NO3 --N can provide the necessary electron acceptor for denitrifying Thiobacillus, promoting the growth and metabolism of Denitrifying Thiobacillus and Pseudomonas, thereby achieving the enrichment effect; hydrogen phosphate, as a phosphorus source, promotes the enrichment of Denitrifying Thiobacillus, Pseudomonas and Lysobacter by participating in cell composition and energy metabolism; soluble magnesium salts and soluble calcium salts, as enzyme activators, improve the utilization of nitrate nitrogen by Denitrifying Thiobacillus and Pseudomonas by increasing the activity of metabolic-related enzymes of Denitrifying Thiobacillus and Pseudomonas, thereby increasing the enrichment of Denitrifying Thiobacillus and Pseudomonas, and soluble magnesium salts and soluble calcium salts can also promote the cell wall synthesis and cell membrane stability of Lysobacter, thereby achieving the enrichment of Lysobacter; bicarbonate adjusts the pH of the sludge acclimation nutrient solution, Thus, the enrichment of denitrifying Thiobacillus, Pseudomonas and Lysobacter is ensured; at the same time, the sludge acclimation nutrient solution provided by the present invention is rich in various trace elements, amino acids and other microbial growth-promoting factors. The present invention selects specific contents of molybdate, boric acid, soluble copper salt, soluble manganese salt, soluble cobalt salt, soluble zinc salt, soluble nickel salt and soluble iron salt, which synergistically regulate the enzymes and metabolism-related enzymes of denitrifying Thiobacillus, Pseudomonas and Lysobacter during cell synthesis, thereby improving the enrichment of denitrifying Thiobacillus, Pseudomonas and Lysobacter; EDTA can chelate metal ions, so that denitrifying Thiobacillus, Pseudomonas and Lysobacter can stably absorb and utilize various metal ions, and by ensuring the normal activity of various enzymes and the denitrifying Thiobacillus The metabolic stability of microorganisms such as Bacillus, Pseudomonas and Lysobacter enables them to grow and enrich in sludge; the specific content of lysine, isoleucine, phenylalanine, threonine and cysteine ​​in the growth-promoting factor can provide energy for the denitrifying Thiobacillus, Pseudomonas and Lysobacter flora, promote the metabolic activity of the flora cells, enhance the absorption and utilization of nutrients by the flora, and thus increase the enrichment of denitrifying Thiobacillus, Pseudomonas and Lysobacter in sludge; the addition of yeast extract and beef extract further promotes the growth and division of cells in the denitrifying Thiobacillus, Pseudomonas and Lysobacter flora, and enhances their survival ability and competitiveness in sludge by accelerating the metabolic activity of bacteria, thereby achieving denitrifying Thiobacillus, Pseudomonas and Lysobacter. Enrichment of bacterial flora; on the one hand, sorbitol, as a carbon source, promotes the growth and reproduction of denitrifying Thiobacillus, Pseudomonas and Lysobacter flora; on the other hand, sorbitol can also regulate the intracellular osmotic pressure of denitrifying Thiobacillus, Pseudomonas and Lysobacter flora, prevent them from losing water, enhance the survival ability and adaptability of the flora in sludge, and achieve their enrichment; the present invention selects a specific sludge domestication nutrient solution as a necessary component of microbial cell structural material and an indispensable nutrient for microbial growth, promotes the growth activity of multiple enzymes and microorganisms, and also promotes the growth of microbial flora cells, enriches the species and abundance of the flora, strengthens the reproduction ability and diversity of the flora, and is conducive to the directional domestication and enrichment of denitrifying Thiobacillus, Pseudomonas and Lysobacter;The present invention activates denitrifying Thiobacillus, Pseudomonas and Lysobacter in the sludge into dominant strains by selecting a specific sludge acclimation nutrient solution, and applies it to sewage. Without adding an additional carbon source, it can achieve the dual effects of nitrogen removal and phosphorus removal, and also reduce the operating cost to a certain extent, and reduce the risk of secondary pollution of effluent water. ;

[0007] By the present invention Figure 1 It can be seen that at the genus level, the sludge acclimation nutrient solution provided by the present invention is used to acclimate the autotrophic denitrification system. After the acclimation is completed, the denitrifying Thiobacillus genus serving as an indicative autotrophic denitrifying bacteria Thiobacillus , the abundance increased from 1.64% to 37.176%, and Pseudomonas spp., which also has denitrification and denitrification effects Pseudomonas From 0.003% to 5.897%, the genus Lysobacterium, which has the function of removing phosphorus Lysobacter It increased from 0.662% to 4.442%, and the genera of denitrifying Thiobacillus, Pseudomonas and Lysobacter were significantly enriched, indicating that the autotrophic denitrifying microbial population had been enriched and domesticated.

[0008] Preferably, the NO3 - -N is added in the form of potassium nitrate.

[0009] Preferably, the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate.

[0010] Further preferably, the mass ratio of sodium hydrogen phosphate to potassium hydrogen phosphate in the hydrogen phosphate is (0.18-0.20): (0.25-0.28).

[0011] Preferably, the soluble magnesium salt is magnesium chloride.

[0012] Preferably, the soluble calcium salt is calcium chloride.

[0013] Preferably, the bicarbonate is sodium bicarbonate.

[0014] Preferably, the molybdate is sodium molybdate.

[0015] Preferably, the soluble copper salt is copper chloride.

[0016] Preferably, the soluble manganese salt is manganese chloride.

[0017] Preferably, the soluble cobalt salt is cobalt nitrate.

[0018] Preferably, the soluble zinc salt is zinc chloride.

[0019] Preferably, the soluble nickel salt is nickel sulfate.

[0020] Preferably, the soluble iron salt is ferric sulfate.

[0021] The preferred type of nutrient solution for sludge acclimation is beneficial to further direct the microbial flora in the autotrophic denitrification sludge, thereby improving the dual effects of nitrogen removal and phosphorus removal.

[0022] The second aspect of the present invention provides a method for preparing the above-mentioned sludge acclimation nutrient solution, comprising the following steps: The weighed NO3 - -N, hydrogen phosphate, soluble magnesium salt, soluble calcium salt, bicarbonate, trace elements, growth promoting factors and water are evenly mixed to obtain sludge acclimation nutrient solution.

[0023] The third aspect of the present invention provides a method for preparing the above-mentioned autotrophic denitrification sludge, comprising the following steps: The sludge, sulfur source, reduced iron powder and the sludge acclimation nutrient solution are uniformly mixed, acclimated at 33.5° C.-34° C., and centrifuged and concentrated to obtain autotrophic denitrification sludge.

[0024] The relative abundance of denitrifying Thiobacillus, Pseudomonas and Lysobacter in the autotrophic denitrifying sludge obtained by the preparation method provided by the present invention is significantly improved compared with that before domestication, indicating that the preparation method provided by the present invention can achieve the domestication and enrichment of denitrifying Thiobacillus, Pseudomonas and Lysobacter, thereby achieving the dual effects of denitrification and phosphorus removal.

[0025] Preferably, the mass volume ratio of the sludge, sludge acclimation nutrient solution, sulfur source and reduced iron powder is (1-1.1) L: (1-1.1) L: (10-12) g: (2-4) g.

[0026] Preferably, the concentration of the sludge is 10 g / L-12 g / L.

[0027] By limiting the sludge concentration of the sludge, it is beneficial to further improve the growth of Pseudomonas, Denitrifying Thiobacillus and Lysobacter in the sludge.

[0028] Preferably, the acclimation time is 15d-16d.

[0029] Preferably, the sludge domestication nutrient solution is replaced every 3-4 days during the domestication.

[0030] Preferably, the sulfur source is sulfur powder.

[0031] Preferably, after the centrifugal concentration, the supernatant is discarded and the mud bottom is retained as the autotrophic denitrification sludge.

[0032] A fourth aspect of the present invention provides an autotrophic denitrification sludge prepared by the above-mentioned method for preparing the autotrophic denitrification sludge.

[0033] A fifth aspect of the present invention provides a method for preparing a filler, comprising the following steps: S1, adding carboxymethyl cellulose and polyethylene glycol into water to obtain a first mixed solution; S2, adding the autotrophic denitrification sludge to the first mixed solution, and then adding sulfur powder, calcium carbonate and reduced iron powder to obtain an autotrophic denitrification sludge mixture; S3, adding soluble calcium salt and hydrochloric acid into water, adjusting the pH to 6.5-7, and obtaining a second mixed solution; S4. Adding the autotrophic denitrification sludge mixture into the second mixed solution to obtain a filler.

[0034] Compared with the prior art, the preparation method of the filler provided by the present invention, wherein carboxymethyl cellulose can increase the mechanical strength of the filler, increase the pore size and improve the toughness, polyethylene glycol as the skeleton structure component of the filler, is a highly viscous organic polymer compound, and the two present a high-molecular polymer material with a three-dimensional network structure through physical cross-linking, which can be used as a carrier of the subsequent solid dispersant to promote the uniform dispersion of the autotrophic denitrification sludge mixture, thereby improving the service life of the filler and the denitrification and phosphorus removal effect; further, the present invention adds autotrophic denitrification sludge, wherein the specific microbial flora can greatly shorten the startup and construction cycle of the autotrophic denitrification system, and improve the efficiency of denitrification and phosphorus removal; calcium carbonate is used as an inorganic carbon source for the microbial flora in the autotrophic denitrification system in the filler, which is convenient for the microbial flora to utilize CO3 2- No x - -N is reduced to nitrogen gas, and at the same time, it can provide a certain alkalinity for the filler when treating sewage, thereby offsetting the alkalinity consumption caused by the autotrophic denitrification process, playing a role in balancing pH, which is beneficial to improving the service life of the filler and the denitrification and phosphorus removal effect; sulfur powder can act as an electron acceptor and can be used by the microbial flora in the filler to reduce nitrate nitrogen to nitrogen gas during sewage treatment, further improving the denitrification effect of the filler; the microbial flora in the filler uses reduced iron powder as an electron donor to reduce NO x --N is used as an electron acceptor for denitrification reaction, which can further improve the total nitrogen removal rate, and the iron ions generated by the reaction can also combine with phosphate ions in sewage to generate phosphate precipitation, thereby achieving the dual effects of denitrification and phosphorus removal; the sulfur powder, calcium carbonate and reduced iron powder in the filler of the present invention serve as multi-electron donors, which promote each other synergistically, further enhance the efficiency of denitrification and phosphorus removal during sewage treatment, and further improve the total nitrogen removal rate, phosphorus removal effect and service life of the filler; the aqueous solution containing soluble calcium salt and hydrochloric acid serves as an ion exchanger, which can provide charged ions, and the ions form new chemical bonds with the oppositely charged polymers in the autotrophic denitrification sludge mixture to form a filler with high strength and strong toughness, further improving the service life of the filler during sewage treatment, and further improving the efficiency and effect of denitrification and phosphorus removal.

[0035] Preferably, in S1, the mass volume ratio of the carboxymethyl cellulose, polyethylene glycol and water is (5-7) g: (90-92) g: 1L.

[0036] By limiting the ratio of carboxymethyl cellulose, polyethylene glycol and water, the strength and toughness of the filler can be further improved, thereby increasing the service life of the filler during sewage treatment.

[0037] Preferably, in S2, the mass ratio of the autotrophic denitrification sludge to the first mixed solution is 1:(1-1.2).

[0038] Preferably, in S2, the amount of sulfur powder added is 15%-18% of the mass of the autotrophic denitrification sludge.

[0039] Preferably, in S2, the amount of calcium carbonate added is 3%-5% of the mass of the autotrophic denitrification sludge.

[0040] Preferably, in S2, the amount of the reduced iron powder added is 0.5%-0.8% of the mass of the autotrophic denitrification sludge.

[0041] By limiting the usage of sulfur powder, calcium carbonate and reduced iron powder, the service life of the filler in sewage treatment can be further prolonged, and the denitrification and phosphorus removal efficiency and effect of the filler can be improved.

[0042] Specifically, in S2, the autotrophic denitrification sludge is added to the mixed solution, and then sulfur powder, carbonate and reduced iron powder are added, and the mixture is uniformly stirred by high-speed shearing to obtain a gel-like autotrophic denitrification sludge mixture.

[0043] Preferably, in S3, the soluble calcium salt is calcium chloride.

[0044] Preferably, in S3, the mass ratio of the soluble calcium salt, hydrochloric acid and water is (5-7): (1-3): (90-94).

[0045] It should be noted that the sum of the masses of the soluble calcium salt, hydrochloric acid and water is 100%.

[0046] Preferably, in S4, the volume ratio of the autotrophic denitrification sludge mixture to the second mixed solution is 1:(5-7).

[0047] By limiting the mass concentrations of soluble calcium salts, hydrochloric acid and water and the ratio range of the autotrophic denitrification sludge mixture and the second mixed solution, it is beneficial to further improve the strength and toughness of the filler, thereby increasing the service life of the filler in sewage treatment.

[0048] Further preferably, the specific steps of S4 are: dripping the autotrophic denitrification sludge mixture into the second mixed solution drop by drop at a rate of 0.1 mL / s-0.2 mL / s, stirring at a rate of 100 r / min-120 r / min while dripping, and then cross-linking and fixing at 4°C-6°C, washing, filtering, and drying to obtain the filler.

[0049] Preferably, the cross-linking and fixing time is 25h-30h.

[0050] A sixth aspect of the present invention provides a filler prepared by the above filler preparation method.

[0051] Compared with the prior art, the present invention has the following effects: (1) The filler provided by the present invention utilizes the principle of autotrophic denitrification process. In the process of treating nitrogen-containing sewage, it can completely get rid of the external carbon source, avoid the emission of greenhouse gases such as CO2 and N2O, and promote the positive consumption of CO2, thereby achieving the synergy of high-standard denitrification and low-carbon emission reduction processes in the sewage industry, and promoting the synergistic effect of "pollution reduction and carbon reduction" in the sewage treatment field; (2) The filler provided by the present invention utilizes a specific sludge acclimation nutrient solution to acclimate a microbial flora enriched with denitrifying Thiobacillus, Pseudomonas and Lysobacter, thereby eliminating the need for directional cultivation of autotrophic denitrifying flora in the early stage, and quickly realizing the startup and construction of an autotrophic denitrification system, which helps to improve the stability and treatment efficiency of the filler itself; (3) The filler provided by the present invention uses calcium carbonate as an inorganic carbon source to ensure that autotrophic denitrifying bacteria can effectively utilize CO3 2- No x - -N is reduced to N2; secondly, calcium carbonate can also effectively provide part of the alkalinity, which can prevent the problem of lowering the effluent pH due to excessive consumption of alkalinity during the autotrophic denitrification reaction, and has the effect of stabilizing the water pH and ensuring the effluent quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1This is a diagram of the domestication of microbial strains in the autotrophic denitrification sludge prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0053] The technical solution of the present invention will be described clearly and completely below. It should be understood that the specific embodiments described herein can enable those skilled in the art to have a more comprehensive understanding of the present invention, but the present invention is not limited to the scope of the embodiments.

[0054] Example 1 This embodiment provides a method for preparing a filler, comprising the following steps: S1. Add carboxymethyl cellulose and polyethylene glycol to water, and stir rapidly at 500 r / min for 3 h at a water bath temperature of 95° C. until they are completely dissolved, to obtain a first mixed solution, wherein the mass volume ratio of carboxymethyl cellulose, polyethylene glycol and water is 5 g:90 g:1 L; S2, adding the autotrophic denitrification sludge to the first mixed solution, and then adding sulfur powder, calcium carbonate and reduced iron powder, and uniformly obtaining a gel-like autotrophic denitrification sludge mixture by high-speed shear stirring, wherein the mass ratio of the autotrophic denitrification sludge to the first mixed solution is 1:1, the amount of sulfur powder added is 15% of the mass of the autotrophic denitrification sludge, the amount of calcium carbonate added is 3% of the mass of the autotrophic denitrification sludge, and the amount of reduced iron powder added is 0.8% of the mass of the autotrophic denitrification sludge; S3, adding calcium chloride and hydrochloric acid to water, adjusting the pH to 6.5 with a small amount of sodium hydroxide, to obtain a second mixed solution, wherein the mass concentration of calcium chloride in water is 5%, and the mass concentration of hydrochloric acid in water is 3%; S4, dripping the autotrophic denitrification sludge mixture into the second mixed solution drop by drop at a rate of 0.1 mL / s, stirring at a rate of 120 r / min while dripping, and then cross-linking and fixing at 4° C. for 25 h, washing, filtering, and drying to obtain a filler, wherein the volume ratio of the autotrophic denitrification sludge to the second mixed solution is 1:5; The method for preparing the autotrophic denitrification sludge comprises the following steps: The sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution with a concentration of 10g / L were mixed evenly, and acclimated at 33.5℃ for 15 days. During acclimation, the sludge acclimation nutrient solution was replaced every 4 days, and the mixture was concentrated by centrifugation. The supernatant was poured out, and the mud bottom was retained as autotrophic denitrification sludge. The mass volume ratio of sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution was 1L:1L:10g:2g; The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 --N 0.05 parts, hydrogen phosphate 0.43 parts, magnesium chloride 0.03 parts, calcium chloride 0.007 parts, sodium bicarbonate 0.8 parts, trace elements 0.002 parts, growth factor 0.004 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.18:0.25; The trace elements include the following raw material components in mass percentage: sodium molybdate 7.27%, boric acid 4.60%, copper chloride 7.27%, manganese chloride 3.83%, cobalt nitrate 11.88%, zinc chloride 3.67%, nickel sulfate 0.9%, iron sulfate 37.5% and EDTA 23.08%; The growth promoting factor comprises the following raw material components in percentage by weight: 4.23% of lysine, 2.32% of isoleucine, 2.31% of phenylalanine, 5.36% of threonine, 21.62% of cystine, 21.35% of yeast extract, 21.42% of beef extract and 21.39% of sorbitol.

[0055] Example 2 This embodiment provides a method for preparing a filler, comprising the following steps: S1. Add carboxymethyl cellulose and polyethylene glycol to water, and stir rapidly at 500 r / min for 3 h at a water bath temperature of 95° C. until they are completely dissolved, to obtain a first mixed solution, wherein the mass volume ratio of carboxymethyl cellulose, polyethylene glycol and water is 7 g:92 g:1 L; S2, adding the autotrophic denitrification sludge to the first mixed solution, and then adding sulfur powder, calcium carbonate and reduced iron powder, and stirring by high-speed shearing to obtain a gel-like autotrophic denitrification sludge mixture, wherein the mass ratio of the autotrophic denitrification sludge to the first mixed solution is 1:1.2, the amount of sulfur powder added is 18% of the mass of the autotrophic denitrification sludge, the amount of calcium carbonate added is 3% of the mass of the autotrophic denitrification sludge, and the amount of reduced iron powder added is 0.5% of the mass of the autotrophic denitrification sludge; S3, adding calcium chloride and hydrochloric acid to water, adjusting the pH to 7 with a small amount of sodium hydroxide, to obtain a second mixed solution, wherein the mass concentration of calcium chloride in water is 7%, and the mass concentration of hydrochloric acid in water is 1%; S4, dripping the autotrophic denitrification sludge mixture into the second mixed solution drop by drop at a rate of 0.2 mL / s, stirring at a rate of 100 r / min while dripping, and then cross-linking and fixing at 6° C. for 30 h, washing, filtering, and drying to obtain a filler, wherein the volume ratio of the autotrophic denitrification sludge to the second mixed solution is 1:7; The method for preparing the autotrophic denitrification sludge comprises the following steps: The sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution with a concentration of 12g / L were mixed evenly, and acclimated at 34°C for 16 days. During acclimation, the sludge acclimation nutrient solution was replaced every 3 days, and the mixture was centrifuged and concentrated. The supernatant was poured out, and the mud bottom was retained as autotrophic denitrification sludge, wherein the mass volume ratio of sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution was 1.1L:1.1L:12g:4g; The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 - -N 0.07 parts, hydrogen phosphate 0.48 parts, magnesium chloride 0.01 parts, calcium chloride 0.005 parts, sodium bicarbonate 1.0 parts, trace elements 0.003 parts, growth factor 0.005 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.20:0.28; The trace elements include the following raw material components in mass percentage: sodium molybdate 7.86%, boric acid 3.82%, copper chloride 7.31%, manganese chloride 3.83%, cobalt nitrate 11.21%, zinc chloride 4.02%, nickel sulfate 0.95%, iron sulfate 38.4% and EDTA 22.6%; The growth promoting factor comprises the following raw material components in percentage by weight: 4.4% lysine, 2.24% isoleucine, 2.32% phenylalanine, 5.3% threonine, 21.6% cystine, 21.3% yeast extract, 21.7% beef extract and 21.14% sorbitol.

[0056] Example 3 This embodiment provides a method for preparing a filler, comprising the following steps: S1. Add carboxymethyl cellulose and polyethylene glycol to water, and stir rapidly at 500 r / min for 3 h at a water bath temperature of 95° C. until they are completely dissolved, to obtain a first mixed solution, wherein the mass volume ratio of carboxymethyl cellulose, polyethylene glycol and water is 6 g:91 g:1 L; S2, adding the autotrophic denitrification sludge to the first mixed solution, and then adding sulfur powder, calcium carbonate and reduced iron powder, and uniformly obtaining a gel-like autotrophic denitrification sludge mixture by high-speed shear stirring, wherein the mass ratio of the autotrophic denitrification sludge to the first mixed solution is 1:1.1, the amount of sulfur powder added is 16% of the mass of the autotrophic denitrification sludge, the amount of calcium carbonate added is 4% of the mass of the autotrophic denitrification sludge, and the amount of reduced iron powder added is 0.6% of the mass of the autotrophic denitrification sludge; S3, adding calcium chloride and hydrochloric acid to water, adjusting the pH to 6.8 with a small amount of sodium hydroxide, to obtain a second mixed solution, wherein the mass concentration of calcium chloride in water is 6%, and the mass concentration of hydrochloric acid in water is 2%; S4, dripping the autotrophic denitrification sludge mixture into the second mixed solution drop by drop at a rate of 0.2 mL / s, stirring at a rate of 110 r / min while dripping, and then cross-linking and fixing at 5° C. for 28 h, washing, filtering, and drying to obtain a filler, wherein the volume ratio of the autotrophic denitrification sludge to the second mixed solution is 1:6; The method for preparing the autotrophic denitrification sludge comprises the following steps: The sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution with a concentration of 11g / L were mixed evenly, and acclimated at 34°C for 15 days. During acclimation, the sludge acclimation nutrient solution was replaced every 3 days, and the mixture was concentrated by centrifugation. The supernatant was poured out, and the mud bottom was retained as autotrophic denitrification sludge. The mass volume ratio of sludge, sulfur powder, reduced iron powder and sludge acclimation nutrient solution was 1L:1.1L:11g:3g. The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 - -N 0.06 parts, hydrogen phosphate 0.45 parts, magnesium chloride 0.02 parts, calcium chloride 0.006 parts, sodium bicarbonate 0.9 parts, trace elements 0.0025 parts, growth factor 0.0046 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.19:0.26; The trace elements include the following raw material components in mass percentage: sodium molybdate 8.21%, boric acid 3.92%, copper chloride 7.65%, manganese chloride 3.62%, cobalt nitrate 11.02%, zinc chloride 3.85%, nickel sulfate 1.02%, iron sulfate 37.4% and EDTA 23.4%; The growth promoting factor comprises the following raw material components in percentage by weight: 4.39% lysine, 2.21% isoleucine, 2.23% phenylalanine, 5.49% threonine, 21.37% cystine, 21.19% yeast extract, 21.42% beef extract and 21.7% sorbitol.

[0057] Comparative Example 1 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that calcium chloride is replaced by an equal amount of magnesium chloride; The other operation steps are the same as those in Example 1.

[0058] Comparative Example 2 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that: sodium bicarbonate is replaced with an equal amount of calcium chloride; The other operation steps are the same as those in Example 1.

[0059] Comparative Example 3 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that: cobalt nitrate is replaced by an equal amount of sodium molybdate; The trace elements include the following raw material components in mass percentage: sodium molybdate 19.15%, boric acid 4.60%, copper chloride 7.27%, manganese chloride 3.83%, zinc chloride 3.67%, nickel sulfate 0.9%, iron sulfate 37.5% and EDTA 23.08%; The other operation steps are the same as those in Example 1.

[0060] Comparative Example 4 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that sorbitol is replaced with an equal amount of beef extract; The growth-promoting factor includes the following raw material components in percentage by weight: lysine 4.23%, isoleucine 2.32%, phenylalanine 2.31%, threonine 5.36%, cystine 21.62%, yeast extract 21.35%, and beef extract 42.81%; The other operation steps are the same as those in Example 1.

[0061] Comparative Example 5 This comparative example provides a method for preparing a filler. Compared with Example 1, the difference between this comparative example and Example 1 is that the amount of sodium bicarbonate is reduced, as follows: The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 - -N 0.05 parts, hydrogen phosphate 0.43 parts, magnesium chloride 0.03 parts, calcium chloride 0.007 parts, sodium bicarbonate 0.4 parts, trace elements 0.002 parts, growth factor 0.004 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.18:0.25; The trace elements include the following raw material components in mass percentage: sodium molybdate 7.27%, boric acid 4.60%, copper chloride 7.27%, manganese chloride 3.83%, cobalt nitrate 11.88%, zinc chloride 3.67%, nickel sulfate 0.9%, iron sulfate 37.5% and EDTA 23.08%; The growth-promoting factor includes the following raw material components in percentage by weight: lysine 4.23%, isoleucine 2.32%, phenylalanine 2.31%, threonine 5.36%, cystine 21.62%, yeast extract 21.35%, beef extract 21.42% and sorbitol 21.39%; The other operation steps are the same as those in Example 1.

[0062] Comparative Example 6 This comparative example provides a method for preparing a filler. Compared with Example 1, the difference between this comparative example and Example 1 is that the amount of sodium molybdate used is reduced, as follows: The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 - -N 0.05 parts, hydrogen phosphate 0.43 parts, magnesium chloride 0.03 parts, calcium chloride 0.007 parts, sodium bicarbonate 0.8 parts, trace elements 0.002 parts, growth factor 0.004 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.18:0.25; The trace elements include the following raw material components in percentage by mass: sodium molybdate 6.85%, boric acid 3.7%, copper chloride 7.27%, manganese chloride 3.33%, cobalt nitrate 11.2%, zinc chloride 3.72%, nickel sulfate 1.10%, iron sulfate 39.08% and EDTA 23.75%; The growth-promoting factor includes the following raw material components in percentage by weight: lysine 4.23%, isoleucine 2.32%, phenylalanine 2.31%, threonine 5.36%, cystine 21.62%, yeast extract 21.35%, beef extract 21.42% and sorbitol 21.39%; The other operation steps are the same as those in Example 1.

[0063] Comparative Example 7 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that the amount of lysine is reduced, as follows: The nutrient solution for sludge acclimation includes the following raw material components by weight: NO3 - -N 0.05 parts, hydrogen phosphate 0.43 parts, magnesium chloride 0.03 parts, calcium chloride 0.007 parts, sodium bicarbonate 0.8 parts, trace elements 0.002 parts, growth factor 0.004 parts and water 1000 parts, wherein the hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate in a mass ratio of 0.18:0.25; The trace elements include the following raw material components in mass percentage: sodium molybdate 7.27%, boric acid 4.60%, copper chloride 7.27%, manganese chloride 3.83%, cobalt nitrate 11.88%, zinc chloride 3.67%, nickel sulfate 0.9%, iron sulfate 37.5% and EDTA 23.08%; The growth-promoting factor includes the following raw material components in percentage by weight: 3.25% lysine, 2.32% isoleucine, 2.31% phenylalanine, 5.41% threonine, 21.7% cystine, 21.62% yeast extract, 21.68% beef extract and 21.71% sorbitol; The other operation steps are the same as those in Example 1.

[0064] Comparative Example 8 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that: calcium carbonate in S2 is replaced by sodium carbonate; The other operation steps are the same as those in Example 1.

[0065] Comparative Example 9 This comparative example provides a method for preparing a filler. Compared with Example 1, this comparative example is different from Example 1 in that: calcium chloride in S3 is replaced by an equal amount of sodium chloride; The other operation steps are the same as those in Example 1.

[0066] Application Examples The fillers prepared in Examples 1-3 and Comparative Examples 1-9 of the present invention were placed in a continuous flow reactor, and the effluent from the aerobic pool of a certain urban sewage treatment plant was taken. x - -N concentration is 36mg / L, NH4 + -N concentration was 0.3 mg / L, total nitrogen concentration was 38 mg / L, total phosphorus concentration was 1 mg / L, and pH was 7.1; The residence time of sewage in the packing bed of the reactor was set to 2h, and water was continuously fed for treatment. During operation, the inlet water temperature was controlled at 25℃-30℃. NO in the water was detected. x - -N concentration, NH4 + -N concentration, total phosphorus concentration, effluent pH and total nitrogen concentration; After 120 days of stable operation, NO x - -N concentration, NH4 + -N concentration, total phosphorus concentration, effluent pH and total nitrogen concentration; Specifically, the total nitrogen detection method refers to the standard HJ 636-2012 Determination of total nitrogen in water quality Alkaline potassium persulfate digestion UV spectrophotometry; NO x - -N concentration detection method refers to HJ-T 346-2007 Water quality nitrate nitrogen determination ultraviolet spectrophotometry, GB-T 7493-1987 Water quality nitrite nitrogen determination spectrophotometry; NH4 + -N concentration detection method refers to standard HJ 535-2009 Water quality determination of ammonia nitrogen Nessler's reagent spectrophotometry; The detection method of total phosphorus concentration refers to the standard GB / T 11893-1989 Determination of total phosphorus in water quality by ammonium molybdate spectrophotometry; See Table 1-2 for specific test results: Table 1 Test results after 2 hours of sewage treatment

[0067] Table 2 Test results after 120 days of stable operation

[0068] By utilizing the filler provided in the embodiment of the present invention and applying it to sewage treatment, not only can the pH value of the effluent be ensured to be unaffected, but also sulfate ions and total phosphorus content in the sewage can be removed without adding an additional carbon source, and an excellent total nitrogen removal rate can be achieved, thereby reducing the operating cost to a certain extent and reducing the risk of secondary pollution of the effluent.

[0069] The above-described embodiments are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nutrient solution for sludge acclimation, characterized in that: The raw material components include the following parts by mass: NO3 - -N 0.05-0.07 parts, hydrogen phosphate 0.43-0.48 parts, soluble magnesium salt 0.01-0.03 parts, soluble calcium salt 0.005-0.007 parts, bicarbonate 0.8-1.0 parts, trace elements 0.002-0.003 parts, growth promoting factor 0.004-0.005 parts and water 1000 parts; The trace elements include the following raw material components in percentage by mass: molybdate 7.27%-8.43%, boric acid 3.64%-4.60%, soluble copper salt 7.27%-8.43%, soluble manganese salt 3.27%-3.83%, soluble cobalt salt 10.91%-11.88%, soluble zinc salt 3.64%-4.21%, soluble nickel salt 0.73%-1.15%, soluble iron salt 36.36%-39.08% and EDTA 21.82%-23.75%; The growth promoting factor comprises the following raw material components in percentage by weight: 4.23%-4.52% lysine, 2.11%-2.37% isoleucine, 2.11%-2.37% phenylalanine, 5.29%-5.59% threonine, 21.14%-21.72% cystine, 21.14%-21.72% yeast extract, 21.14%-21.72% beef extract and 21.14%-21.72% sorbitol.

2. The sludge acclimation nutrient solution according to claim 1, characterized in that: The hydrogen phosphate is a mixture of sodium hydrogen phosphate and potassium hydrogen phosphate; and / or The soluble magnesium salt is magnesium chloride; and / or The soluble calcium salt is calcium chloride; and / or The bicarbonate is sodium bicarbonate; and / or The molybdate is sodium molybdate; and / or The soluble copper salt is copper chloride; and / or The soluble manganese salt is manganese chloride; and / or The soluble cobalt salt is cobalt nitrate; and / or The soluble zinc salt is zinc chloride; and / or The soluble nickel salt is nickel sulfate; and / or The soluble iron salt is ferric sulfate.

3. A method for preparing the sludge acclimation nutrient solution according to claim 1 or 2, characterized in that: The steps include: The weighed NO3 - -N, hydrogen phosphate, soluble magnesium salt, soluble calcium salt, bicarbonate, trace elements, growth promoting factors and water are evenly mixed to obtain sludge acclimation nutrient solution.

4. A method for preparing autotrophic denitrification sludge, characterized in that: The steps include: The sludge, sulfur source, reduced iron powder and the sludge acclimation nutrient solution according to claim 1 or 2 are uniformly mixed, acclimated at 33.5° C.-34° C., and centrifuged and concentrated to obtain autotrophic denitrification sludge.

5. The method for preparing autotrophic denitrification sludge according to claim 4, characterized in that: The mass volume ratio of the sludge, sludge acclimation nutrient solution, sulfur source and reduced iron powder is (1-1.1) L: (1-1.1) L: (10-12) g: (2-4) g; and / or The concentration of the sludge is 10g / L-12g / L; and / or The acclimatization time is 15d-16d; and / or The sulfur source is sulfur powder.

6. An autotrophic denitrification sludge, characterized in that: The sludge is prepared by the method for preparing the autotrophic denitrification sludge according to claim 4 or 5.

7. A method for preparing a filler, characterized in that: The steps include: S1, adding carboxymethyl cellulose and polyethylene glycol into water to obtain a first mixed solution; S2. adding the autotrophic denitrification sludge according to claim 6 to the first mixed solution, and then adding sulfur powder, calcium carbonate and reduced iron powder to obtain an autotrophic denitrification sludge mixture; S3, adding soluble calcium salt and hydrochloric acid into water, adjusting the pH to 6.5-7, and obtaining a second mixed solution; S4. Adding the autotrophic denitrification sludge mixture into the second mixed solution to obtain a filler.

8. The method for preparing a filler according to claim 7, characterized in that: In S1, the mass volume ratio of the carboxymethyl cellulose, polyethylene glycol and water is (5-7) g: (90-92) g: 1 L; and / or In S2, the mass ratio of the autotrophic denitrification sludge to the first mixed solution is 1:(1-1.2); and / or In S2, the added amount of the sulfur powder is 15%-18% of the mass of the autotrophic denitrification sludge.

9. The method for preparing a filler according to claim 7, characterized in that: In S2, the amount of calcium carbonate added is 3%-5% of the mass of the autotrophic denitrification sludge; and / or In S2, the amount of reduced iron powder added is 0.5%-0.8% of the mass of the autotrophic denitrification sludge; and / or In S3, the soluble calcium salt is calcium chloride; and / or In S3, the mass ratio of the soluble calcium salt, hydrochloric acid and water is (5-7): (1-3): (90-94); and / or In S4, the volume ratio of the autotrophic denitrification sludge mixture to the second mixed solution is 1:(5-7).

10. A filler, characterized in that: The filler is prepared by the preparation method of any one of claims 7 to 9.

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