Embedded anaerobic ammonia oxidation granular sludge composite material as well as preparation method and application thereof

Through the core and shell structure of embedded anaerobic ammonia oxidized particle sludge composite material, N-acyl-homoserine lactone signal molecules are used to promote microbial growth, solving the problem of limiting the number of immobilized particles and improving pollutant removal Effect and stability achieve efficient application of anaerobic ammonia oxidation functional bacteria.

CN119161019AActive Publication Date: 2024-12-20JIANGSU GUOFENG ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD

Patent Information

Application Number
CN202411569991.5
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-06
Publication Date
2024-12-20
Estimated Expiration
2044-11-06

AI Technical Summary

Technical Problem

The microbial mass and activity in the fixed anaerobic ammonia oxidized particles are restricted by the number of fixed particles and cannot be adjusted in time, resulting in poor pollutant removal effect and easy loss, affecting the sewage treatment efficiency.

Method used

Embedded anaerobic ammonia oxidized particulate sludge composite material, through the core and shell structure, N-acyl-homoserine lactone signal molecules stimulate gene expression, promote rapid growth of microbial membranes, improve bacterial population size and activity, and A stable shell is formed by hydrophilic alcohol polymers and biodegradable polymer materials to prevent microbial loss.

Benefits of technology

The concentration and activity of anaerobic ammonia oxidation functional bacteria have been effectively adjusted, the pollutant removal effect has been improved, the settlement performance and the ability to prevent sludge loss have been enhanced, and the stability and efficiency of sewage treatment have been ensured.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention provides an embedded anaerobic ammonia oxidation granular sludge composite material as well as a preparation method and application thereof, and belongs to the technical field of biological sewage treatment. The embedded anaerobic ammonia oxidation granular sludge composite material provided by the invention consists of an inner core and a shell, wherein an inner core comprises anaerobic ammonia oxidation granular sludge and an embedding agent crosslinked with the anaerobic ammonia oxidation granular sludge, a shell comprises a carrier and N-acyl-homoserine lactone signal molecules loaded on the carrier, and preparation raw materials of the carrier comprise a hydrophilic alcohol polymer and a biodegradable high polymer material. In the initial stage of microbial culture, the quorum sensing mechanism of anaerobic ammonia oxidation granular sludge is utilized, and expression of related genes is stimulated through N-acyl-homoserine lactone signal molecules, so that a microbial film is promoted to grow quickly, and the number of florae is increased; meanwhile, the embedded anaerobic ammonia oxidation granular sludge is not easy to lose, and the anaerobic ammonia oxidation reaction activity can be maintained.
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Description

Technical Field

[0001] The invention belongs to the technical field of biological sewage treatment, and specifically relates to an embedded anaerobic ammonium oxidation granular sludge composite material and a preparation method and application thereof. Background Art

[0002] Anaerobic ammonium oxidation is a new green denitrification process with low energy consumption and high efficiency, and is one of the current research hotspots. Studies have shown that culturing anaerobic ammonium oxidizing functional bacteria to form granular sludge increases the density of anaerobic ammonium oxidizing functional bacteria, provides a good growth environment for anaerobic ammonium oxidizing microorganisms, and is conducive to the enrichment and function of anaerobic ammonium oxidizing microorganisms.

[0003] Immobilized microbial technology is a technology that uses chemical or physical means to locate free microbial cells in a limited spatial area so that they remain active and can be reused repeatedly. It has the advantages of high cell density, strong resistance to environmental toxicity, easy production and separation, and simple maintenance. After the anaerobic ammonium oxidation granular sludge is fixed by immobilized microbial technology, it has better sedimentation performance and the ability to prevent sludge loss than unfixed anaerobic ammonium oxidation granular sludge. However, its disadvantage is that the amount and activity of microorganisms in the fixed anaerobic ammonium oxidation granular sludge are greatly restricted by the number of immobilized particles. When the anaerobic ammonium oxidation functional bacteria have a poor effect on pollutant removal, their activity cannot be adjusted in time. Summary of the invention

[0004] The purpose of the present invention is to provide an embedded anaerobic ammonium oxidation granular sludge composite material and its preparation method and application. The embedded anaerobic ammonium oxidation granular sludge composite material of the present invention realizes the embedding of anaerobic ammonium oxidation granular sludge and avoids the loss of anaerobic ammonium oxidation granular sludge; at the same time, N-acyl-homoserine lactone signal molecules can stimulate gene expression, promote the rapid growth of microbial film, increase the number of bacterial populations, effectively adjust the concentration and activity of anaerobic ammonium oxidation granular sludge in the system, and improve the removal effect of anaerobic ammonium oxidation functional bacteria on pollutants.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides an embedded anaerobic ammonium oxidation granular sludge composite material, which consists of an inner core and an outer shell; the inner core comprises anaerobic ammonium oxidation granular sludge and an embedding agent cross-linked with the anaerobic ammonium oxidation granular sludge; the outer shell comprises a carrier and an N-acyl-homoserine lactone signal molecule loaded on the carrier, and the raw materials for preparing the carrier comprise a hydrophilic alcohol polymer and a biodegradable high molecular material.

[0007] Preferably, the particle size of the anaerobic ammonium oxidation granular sludge is 3 to 8 mm.

[0008] Preferably, the embedding agent comprises polyvinyl alcohol, sodium alginate and iron powder; the mass ratio of the polyvinyl alcohol, sodium alginate and iron powder is 6-10:2-3:2-4.

[0009] Preferably, the mass ratio of the anaerobic ammonium oxidation granular sludge to the embedding agent is 1:1.8-2.2.

[0010] Preferably, the hydrophilic alcohol polymer includes at least one of polyvinyl alcohol and polyethylene glycol; and the biodegradable polymer material includes polycarboxylic acid glycolic acid copolymer.

[0011] Preferably, the N-acyl-homoserine lactone signal molecule includes at least one of C6-HSL, C8-HSL, C10-HSL, C12-HSL, C14-HSL, 3-oxo-C6-HSL, 3-oxo-C8-HSL, 3-oxo-C10-HSL, 3-oxo-C12-HSL and 3-oxo-C14-HSL.

[0012] Preferably, the particle size of the embedded anaerobic ammonium oxidation granular sludge composite material is 2 to 4 mm, and the mass content of N-acyl-homoserine lactone signal molecules in the embedded anaerobic ammonium oxidation granular sludge composite material is 0.03% to 0.06%.

[0013] The present invention provides a method for preparing the embedded anaerobic ammonium oxidation granular sludge composite material, comprising the following steps:

[0014] The anaerobic ammonium oxidation granular sludge and the embedding agent are mixed and cross-linked to obtain the inner core;

[0015] Mixing a hydrophilic alcohol polymer, a biodegradable polymer material, an N-acyl-homoserine lactone signal molecule and an organic solvent to obtain a dissolving solution;

[0016] The inner core is placed in the dissolving solution to carry out an esterification reaction to form an outer shell on the surface of the inner core, thereby obtaining the embedded anaerobic ammonium oxidation granular sludge composite material.

[0017] Preferably, the temperature of the cross-linking reaction is 0-5°C, and the time is 6-12 hours; the temperature of the esterification reaction is 60-70°C, and the time is 10-20 minutes.

[0018] The present invention provides the use of the embedded anaerobic ammonium oxidation granular sludge composite material described in the above technical solution or the embedded anaerobic ammonium oxidation granular sludge composite material obtained by the preparation method described in the above technical solution in sewage treatment.

[0019] The present invention provides an embedded anaerobic ammonium oxidation granular sludge composite material, which is composed of an inner core and an outer shell; the inner core includes anaerobic ammonium oxidation granular sludge and an embedding agent cross-linked with the anaerobic ammonium oxidation granular sludge; the outer shell includes a carrier and an N-acyl-homoserine lactone signal molecule loaded on the carrier, and the raw materials for preparing the carrier include a hydrophilic alcohol polymer and a biodegradable polymer material. In the early stage of microbial culture (when the cell concentration is low), the present invention utilizes the quorum sensing mechanism of anaerobic ammonium oxidation granular sludge to stimulate the expression of related genes through N-acyl-homoserine lactone signal molecules, thereby promoting the rapid growth of microbial film and increasing the number of bacterial colonies; at the same time, the embedded anaerobic ammonium oxidation granular sludge is not easy to be lost, ensuring that the anaerobic ammonium oxidation granular sludge in the system always maintains a certain concentration and maintains the activity of the anaerobic ammonium oxidation reaction.

[0020] Furthermore, the present invention detects the concentration of anaerobic ammonium oxidizing functional bacteria and stimulates their growth through N-acyl-homoserine lactone signal molecules and quorum sensing mechanisms, so that the microbial concentration of anaerobic ammonium oxidizing functional bacteria can be replenished in time. At the same time, the immobilization technology largely avoids the loss of anaerobic ammonium oxidizing functional bacteria, which is helpful for application in coupling systems. It can make up for the disadvantages of anaerobic ammonium oxidizing and other processes when coupled to a certain extent, which is beneficial to the stable operation of the process. The embedded anaerobic ammonium oxidizing granular sludge composite material thus cultivated can efficiently treat NO2-containing - and NH4 + of sewage. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0022] Figure 1 NH4 in the effluent of control group A and experimental group B + and NO2 - Concentration change results graph. DETAILED DESCRIPTION

[0023] The present invention provides an embedded anaerobic ammonium oxidation granular sludge composite material, which consists of an inner core and an outer shell; the inner core comprises anaerobic ammonium oxidation granular sludge and an embedding agent cross-linked with the anaerobic ammonium oxidation granular sludge; the outer shell comprises a carrier and an N-acyl-homoserine lactone signal molecule loaded on the carrier, and the raw materials for preparing the carrier comprise a hydrophilic alcohol polymer and a biodegradable high molecular material.

[0024] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art or are prepared by methods well known to those skilled in the art.

[0025] The embedded anaerobic ammonium oxidation granular sludge composite material of the present invention includes an inner core; the inner core includes anaerobic ammonium oxidation granular sludge and an embedding agent cross-linked with the anaerobic ammonium oxidation granular sludge. In the present invention, the anaerobic ammonium oxidation functional bacteria in the anaerobic ammonium oxidation granular sludge may include at least one of Candidatus Kuenenia, Candidatus Jettenia and Candidatus Brocadia. In the present invention, the particle size of the anaerobic ammonium oxidation granular sludge may be 3 to 8 mm, specifically 5 to 8 mm. In the present invention, the embedding agent may include polyvinyl alcohol, sodium alginate and iron powder; the mass ratio of the polyvinyl alcohol, sodium alginate and iron powder may be 6 to 10:2 to 3:2 to 4; in a specific embodiment, the mass ratio of the polyvinyl alcohol, sodium alginate and iron powder may be 6:3:2, 8:3:3 or 10:2:4. In the present invention, the particle size of the iron powder may be 5 to 100 μm, specifically 10 μm. The embedding agent of the present invention also includes an auxiliary agent, and the auxiliary agent includes calcium chloride and polyethyleneimine. In the present invention, the mass ratio of the anaerobic ammonium oxidation granular sludge and the embedding agent can be 1:1.8-2.2; in a specific embodiment, the mass ratio of the anaerobic ammonium oxidation granular sludge and the embedding agent can be 1:1.8, 1:1.9, 1:2, 1:2.1 or 1:2.2. In the present invention, polyvinyl alcohol can provide good support and protection, which helps to improve the stability of immobilized anaerobic ammonium oxidation functional bacteria; the gel property of sodium alginate enables it to provide certain mechanical strength and stability during the embedding process of anaerobic ammonium oxidation functional bacteria; iron powder has a promoting effect on the activity of anaerobic ammonium oxidation functional bacteria, can promote the growth of anaerobic ammonium oxidation functional bacteria, and can increase the adsorption effect on anaerobic ammonium oxidation functional bacteria and enhance the strength of the embedding structure; calcium chloride and polyethyleneimine are added as auxiliary agents to improve the stability of the obtained material.

[0026] The embedded anaerobic ammonium oxidation granular sludge composite material of the present invention comprises an outer shell; the outer shell comprises a carrier and an N-acyl-homoserine lactone signal molecule loaded on the carrier.

[0027] In the present invention, the carrier includes a hydrophilic alcohol polymer and a biodegradable high molecular material. The hydrophilic alcohol polymer of the present invention may include at least one of polyvinyl alcohol and polyethylene glycol; in a specific embodiment, the hydrophilic alcohol polymer may be polyvinyl alcohol or polyethylene glycol. The biodegradable high molecular material of the present invention may include a polycarboxylic acid glycolic acid copolymer. In the present invention, sodium polyacrylate and / or polycaprolactone may also be added when preparing the carrier, wherein sodium polyacrylate may significantly improve the water retention of the carrier and provide a suitable and stable growth environment for the anaerobic ammonia oxidizing functional bacteria. At the same time, the cross-linked structure of sodium polyacrylate may increase the stability and hydrolysis resistance of the shell, prolong the survival time and activity of the embedded bacteria; polycaprolactone may be used as a component of the biodegradable shell, and release carbon dioxide therein for use by the anaerobic ammonia oxidizing functional bacteria.

[0028] The N-acyl-homoserine lactone signal molecule of the present invention may include at least one of C6-HSL, C8-HSL, C10-HSL, C12-HSL, C14-HSL, 3-oxo-C6-HSL, 3-oxo-C8-HSL, 3-oxo-C10-HSL, 3-oxo-C12-HSL and 3-oxo-C14-HSL; in a specific embodiment, the N-acyl-homoserine lactone signal molecule may be C6-HSL, C8-HSL, 3-oxo-C6-HSL or 3-oxo-C8-HSL. In the present invention, the mass content of N-acyl-homoserine lactone signal molecules on the embedded anaerobic ammonium oxidation granular sludge composite material can be 0.03% to 0.06%; in a specific embodiment, the mass content of N-acyl-homoserine lactone signal molecules on the embedded anaerobic ammonium oxidation granular sludge composite material can be 0.03%, 0.04%, 0.05% or 0.06%.

[0029] In the present invention, the particle size of the embedded anaerobic ammonium oxidation granular sludge composite material may be 2 to 4 mm; in a specific embodiment, the particle size of the embedded anaerobic ammonium oxidation granular sludge composite material may be 2 mm, 3 mm or 4 mm.

[0030] The present invention also provides a method for preparing the embedded anaerobic ammonium oxidation granular sludge composite material, comprising the following steps:

[0031] The anaerobic ammonium oxidation granular sludge and the embedding agent are mixed and cross-linked to obtain the inner core;

[0032] Mixing a hydrophilic alcohol polymer, a biodegradable polymer material, an N-acyl-homoserine lactone signal molecule and an organic solvent to obtain a dissolving solution;

[0033] The inner core is placed in the dissolving solution to carry out an esterification reaction to form an outer shell on the surface of the inner core, thereby obtaining the embedded anaerobic ammonium oxidation granular sludge composite material.

[0034] The present invention mixes anaerobic ammonium oxidation granular sludge and an embedding agent, and performs a cross-linking reaction to obtain the inner core. In the present invention, the embedding agent includes polyvinyl alcohol, sodium alginate, iron powder, calcium chloride and polyethyleneimine, and also includes water. In an embodiment of the present invention, specifically, a polyvinyl alcohol aqueous solution, sodium alginate, iron powder and water are mixed and heat-treated to obtain a first mixed solution; a polyethyleneimine aqueous solution is mixed with a calcium chloride aqueous solution to obtain a second mixed solution; the anaerobic ammonium oxidation granular sludge is rinsed with a phosphate buffer, and solid materials are collected after centrifugation; the solid materials are mixed with the first mixed solution to obtain a third mixed solution; the third mixed solution is mixed with an equal volume of the second mixed solution to perform a cross-linking reaction. In an embodiment of the present invention, the mass fraction of the polyvinyl alcohol aqueous solution can be 6-10%, specifically 6%, 8% or 10%. In an embodiment of the present invention, the temperature of the heat treatment may be 100-150°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C or 150°C; the time of the heat treatment may be 10-40min, specifically 10min, 20min, 30min or 40min. In an embodiment of the present invention, the mass fraction of the calcium chloride aqueous solution may be 4-6%, specifically 4%, 5% or 6%. In an embodiment of the present invention, the mass fraction of the polyethyleneimine aqueous solution may be 20-50%, specifically 20%, 30%, 35%, 40% or 50%. In an embodiment of the present invention, the volume ratio of the polyethyleneimine aqueous solution to the calcium chloride aqueous solution may be 1-5:100, specifically 1:100, 2:100, 3:100, 4:100 or 5:100. In an embodiment of the present invention, the composition of the phosphate buffer may include 8.0g NaCl, 0.2g KCl, 1.44g Na2HPO4, 0.24gKH2PO4 and 800mL distilled water. In an embodiment of the present invention, the number of flushings may be 3 times. In an embodiment of the present invention, the speed of the centrifugation may be 4000rpm. In the present invention, the temperature of the cross-linking reaction may be 0 to 5°C; in a specific embodiment, the temperature of the cross-linking reaction may be 3°C or 4°C; the time of the cross-linking reaction may be 6 to 12h; in a specific embodiment, the time of the cross-linking reaction may be 6h, 8h, 10h or 12h. In the present invention, the cross-linking reaction may be carried out under light-proof and sealed conditions.

[0035] The present invention mixes a hydrophilic alcohol polymer, a biodegradable polymer material, an N-acyl-homoserine lactone signal molecule and an organic solvent to obtain a dissolving solution. In an embodiment of the present invention, the biodegradable polymer material is specifically mixed with an organic solvent, and N-acyl-homoserine lactone signal molecules are added thereto to obtain a fourth mixed solution; and an aqueous solution of a hydrophilic alcohol polymer is added to the fourth mixed solution to obtain the dissolving solution. In an embodiment of the present invention, the organic solvent may be dichloromethane; the mass ratio of the organic solvent to the biodegradable polymer material may be 70-100:1-30, specifically 70:30, 80:20 or 90:10. In an embodiment of the present invention, the concentration of the N-acyl-homoserine lactone signal molecule in the fourth mixed solution may be 0.2-1.0 mg / L. In an embodiment of the present invention, the mass concentration of the aqueous solution of the hydrophilic alcohol polymer may be 10-30%, specifically 10%, 20% or 30%.

[0036] After obtaining the inner core and the dissolving solution, the present invention places the inner core in the dissolving solution to perform an esterification reaction to form a shell on the inner core surface to obtain the embedded anaerobic ammonium oxidation granular sludge composite material. In the present invention, the temperature of the esterification reaction can be 60 to 70°C; in a specific embodiment, the temperature of the esterification reaction can be 60°C, 65°C or 70°C; the time of the esterification reaction can be 10 to 20 minutes; in a specific embodiment, the time of the esterification reaction can be 10 minutes, 15 minutes or 20 minutes.

[0037] The present invention also provides the use of the embedded anaerobic ammonium oxidation granular sludge composite material described in the above technical solution or the embedded anaerobic ammonium oxidation granular sludge composite material obtained by the preparation method described in the above technical solution in sewage treatment.

[0038] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The anaerobic ammonium oxidation granular sludge used in the examples was derived from anaerobic ammonium oxidation sludge cultured in the laboratory, wherein the abundance of anaerobic ammonium oxidation functional bacteria was about 7.23%, and specific species included Candidatus Kuenenia, Candidatus Jettenia and Candidatus Brocadia, and the particle size of the anaerobic ammonium oxidation granular sludge was 3 to 8 mm.

[0040] Example 1

[0041] (1) Weigh 4 g of an 8 wt % aqueous solution of polyvinyl alcohol, 1.5 g of sodium alginate and 1.5 g of iron powder (particle size of 10 μm) respectively, mix the three, add 100 mL of water, and heat at 110° C. for 30 min to prepare a mixed solution I; mix 3 mL of a 35 wt % aqueous solution of polyethyleneimine with 100 mL of a 5 wt % aqueous solution of calcium chloride to prepare a mixed solution II. The bacterial solution of the anaerobic ammonium oxidation granular sludge after 30 days of enrichment culture (based on the removal rate of nitrite nitrogen and ammonia nitrogen, the removal rate can reach more than 90% after 30 days of enrichment culture) was washed three times with a phosphate buffer solution with a pH value of 7.0-7.5 (containing 8.0g NaCl, 0.2g KCl, 1.44g Na2HPO4, 0.24gKH2PO4 and 800mL distilled water), and then the obtained bacterial solution was centrifuged at 4000rpm, the supernatant was discarded, the precipitate was collected and the precipitate was mixed evenly with the mixed solution I to obtain a mixed solution III. Subsequently, the mixed solution III was added to an equal volume of mixed solution II, and immobilized and cross-linked for 12 hours at 4°C under the condition of light-proof sealing, and after the end, a small ball with an anaerobic ammonium oxidation granular sludge core embedded was obtained.

[0042] (2) 20 mL of polycarboxylic acid hydroxyacetic acid copolymer was dissolved in 80 mL of dichloromethane, 0.02 mg of 3-oxo-C6-HSL signal molecule was added thereto, and a viscous liquid was obtained after uniform mixing. A 20 wt% polyethylene glycol aqueous solution was added to the viscous liquid, and magnetic stirring was continuously performed at 65° C. The inner core prepared in step (1) was added under stirring, and an esterification reaction was carried out for 10 min. As the esterification reaction proceeded, a shell was gradually formed on the surface of the inner core. After the reaction, an embedded anaerobic ammonium oxidation granular sludge composite material was obtained (the particle size was 4 mm, and the mass content of the 3-oxo-C6-HSL signal molecule on the embedded anaerobic ammonium oxidation granular sludge composite material was 0.03%).

[0043] Example 2

[0044] (1) The inner core was prepared according to step (1) of Example 1.

[0045] (2) An embedded anaerobic ammonium oxidation granular sludge composite material was prepared according to step (2) of Example 1, except that the signal molecule was replaced by a C6-HSL signal molecule, and the polyethylene glycol aqueous solution was replaced by polyvinyl alcohol of the same concentration to prepare an embedded anaerobic ammonium oxidation granular sludge composite material (particle size was 4 mm, wherein the loading amount of the C6-HSL signal molecule on the embedded anaerobic ammonium oxidation granular sludge composite material was 0.03%).

[0046] Application Example 1

[0047] 700 g of the embedded anaerobic ammonia oxidation granular sludge composite material prepared in Example 1 was placed in an upflow anaerobic sludge blanket reactor (UASB reactor), and 5 L of nutrient solution was added to culture and operate the anaerobic ammonia oxidation functional bacteria. The nutrient solution composition was as follows: 200 mg / L NH4Cl, 240 mg / L NaNO2, 419 mg / L NaHCO3, 180 mg / L CaCl2, 245 mg / L MgSO4·7H2O, 27 mg / L KH2PO4, 2.5 mg / L FeSO4·7H2O and 1 ml / L trace elements (wherein the composition of the trace elements was 20 g / L ETA, 0.43 g / L ZnSO4·7H2O, 0.24 g / L CoCl2·6H2O, 0.99 g / L MnCl2·4H2O, 0.25 g / L CuSO4·5H2O, 0.22 g / L NaMoO4·2H2O, 0.19g / LNiCl2·6H2O and 0.014g / L H3BO3. The initial hydraulic retention time (HRT) was 24h. The load was increased by reducing the hydraulic retention time to cultivate anaerobic ammonia-oxidizing functional bacteria. The load increase node was based on the stabilization of the effluent ammonia nitrogen concentration.

[0048] A control group A and an experimental group B with the embedded anaerobic ammonium oxidation granular sludge composite material prepared in Example 1 were set up for comparison, and three parallel experiments were set up in each group. The results are as follows: Figure 1 shown.

[0049] Depend on Figure 1 It can be seen that after adding the embedded anaerobic ammonium oxidation granular sludge composite material prepared in Example 1, the cultivation speed of anaerobic ammonium oxidation functional bacteria was significantly accelerated. The time required for groups A and B to reduce HRT from 24h to 4h was 78 days and 58 days respectively. + and NO2 - The concentration changes show that when the load was increased for the first time on day 6, the NO2 - and NH4 + The concentration increased rapidly to 60.9 mg / L and 29.8 mg / L, while the maximum concentration of experimental group B was only 43.8 mg / L and 21.1 mg / L, and the NH4 +The concentration fluctuated greatly from day 16 to day 20, but it did not occur in experimental group B, which was more stable in comparison. The same phenomenon also occurred in the subsequent load increase process. Although experimental group B also fluctuated to a certain extent when it was impacted by the load increase, it can be clearly observed that its stability was better than that of control group A. It can be seen that during the operation of the system, after the embedded anaerobic ammonia oxidation granular sludge composite material prepared in Example 1 was added, the anaerobic ammonia oxidation functional bacteria had a strong adaptability when subjected to nitrogen load shock, and the effluent NH4 + and NO2 - The influence of concentration change is smaller. Although the above embodiment has made a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments, and people can also obtain other embodiments based on this embodiment without creativity, and these embodiments all belong to the protection scope of the present invention.

Claims

1. An embedded anaerobic ammonium oxidation granular sludge composite material, characterized in that: It consists of an inner core and an outer shell; the inner core includes anaerobic ammonium oxidation granular sludge and an embedding agent cross-linked with the anaerobic ammonium oxidation granular sludge; the outer shell includes a carrier and an N-acyl-homoserine lactone signal molecule loaded on the carrier, and the raw materials for preparing the carrier include a hydrophilic alcohol polymer and a biodegradable high molecular material.

2. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The particle size of the anaerobic ammonium oxidation granular sludge is 3 to 8 mm.

3. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The embedding agent comprises polyvinyl alcohol, sodium alginate and iron powder; the mass ratio of the polyvinyl alcohol, sodium alginate and iron powder is 6-10:2-3:2-4.

4. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The mass ratio of the anaerobic ammonium oxidation granular sludge to the embedding agent is 1:1.8-2.

2.

5. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The hydrophilic alcohol polymer includes at least one of polyvinyl alcohol and polyethylene glycol; the biodegradable polymer material includes polycarboxylic acid glycolic acid copolymer.

6. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The N-acyl-homoserine lactone signal molecule includes at least one of C6-HSL, C8-HSL, C10-HSL, C12-HSL, C14-HSL, 3-oxo-C6-HSL, 3-oxo-C8-HSL, 3-oxo-C10-HSL, 3-oxo-C12-HSL and 3-oxo-C14-HSL.

7. The embedded anaerobic ammonium oxidation granular sludge composite material according to claim 1, characterized in that: The particle size of the embedded anaerobic ammonium oxidation granular sludge composite material is 2-4 mm, and the mass content of N-acyl-homoserine lactone signal molecules in the embedded anaerobic ammonium oxidation granular sludge composite material is 0.03%-0.06%.

8. The method for preparing the embedded anaerobic ammonium oxidation granular sludge composite material according to any one of claims 1 to 7, comprising the following steps: The anaerobic ammonium oxidation granular sludge and the embedding agent are mixed and cross-linked to obtain the inner core; Mixing a hydrophilic alcohol polymer, a biodegradable polymer material, an N-acyl-homoserine lactone signal molecule and an organic solvent to obtain a dissolving solution; The inner core is placed in the dissolving solution to carry out an esterification reaction to form an outer shell on the surface of the inner core, thereby obtaining the embedded anaerobic ammonium oxidation granular sludge composite material.

9. The preparation method according to claim 8, characterized in that: The temperature of the cross-linking reaction is 0-5°C and the time is 6-12 hours; the temperature of the esterification reaction is 60-70°C and the time is 10-20 minutes.

10. Use of the embedded anaerobic ammonium oxidation granular sludge composite material according to any one of claims 1 to 7 or the embedded anaerobic ammonium oxidation granular sludge composite material obtained by the preparation method according to any one of claims 8 to 9 in sewage treatment.

Citation Information

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