High-organic-toxicity anaerobic digestion biogas slurry treatment system and method based on anaerobic ammonia oxidation split-flow detoxification

Abstract

The invention relates to a high-organic-toxicity anaerobic digestion biogas slurry treatment system and method based on anaerobic ammonia oxidation split-flow detoxification. The treatment system comprises an adjusting tank, a nitrosation reactor and an anaerobic ammonia oxidation reactor which are sequentially connected in the flowing direction of biogas slurry, and further comprises a bypass detoxification reactor arranged on a bypass. The bypass detoxification reactor is divided into a catalytic oxidation area and a biological treatment area along the liquid flowing direction; wherein the catalytic oxidation area is used for loading a Fe3O4 / polyacrylamide catalyst and a persulfate oxidant and carrying out oxidative degradation on organic matters in the biogas slurry, and the biological treatment area is used for loading short-cut nitrification-anaerobic ammonia oxidation co-embedded particles and carrying out biological treatment on the biogas slurry. Compared with the prior art, the method has the advantages that the concentration of toxic substances in the ANAMMOX stage in the PN / A process is remarkably reduced, the denitrification efficiency of the reactor is improved, the water treatment amount and the load of the reactor are increased, and efficient and stable high-organic-toxicity anaerobic digestion biogas slurry treatment is successfully realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water treatment, and in particular to a high-organic-toxicity anaerobic digestion biogas slurry treatment system and method based on anaerobic ammonium oxidation shunt detoxification. BACKGROUND

[0002] At present, there are many types of treatment technologies for organic solid waste (such as sludge) in China, including landfill, anaerobic digestion, incineration, land use, and building material utilization. Although these technologies have their own advantages, many sewage treatment plants still use land filling or open-air stacking, which can easily cause secondary pollution.

[0003] Among the many technologies, anaerobic digestion is attracting attention due to its energy recovery potential and lower environmental impact. Since the 1970s, anaerobic digestion technology has developed significantly and has become a mature technology for treating organic solid waste. Through biological degradation, anaerobic digestion not only produces biogas as an energy source, but also reduces sludge production, reduces operating costs, and effectively reduces greenhouse gas emissions. However, the biogas slurry produced by anaerobic digestion contains refractory organic matter and high concentrations of ammonia nitrogen, and if it is not properly treated before being discharged, it can cause water eutrophication. Therefore, it is particularly important to efficiently denitrify anaerobic digestion biogas slurry.

[0004] Traditional denitrification processes have the problems of high energy consumption and large greenhouse gas emissions. As an emerging high-efficiency biological technology, the anaerobic ammonia oxidation (ANAMMOX) process provides an autotrophic solution for denitrification with the advantages of low sludge production, low energy consumption, and no greenhouse gas emissions. In practical applications, the anaerobic ammonia oxidation process is often combined with the partial nitrification process (Partial Nitrification, PN) to form a partial nitrification-anaerobic ammonia oxidation (PN / A) process, which realizes autotrophic bypass detoxification. For example, CN109354185A discloses a combined denitrification method and device for sludge hydrolysis anaerobic digestion biogas slurry, which adopts a combined denitrification method of partial nitritation-denitrification-anaerobic ammonia oxidation, adjusts the pH value and alkalinity, and uses a nitritation reactor and an anaerobic ammonia oxidation reactor to treat sludge hydrolysis anaerobic digestion biogas slurry, respectively, to achieve efficient, high-load, and low-cost denitrification and COD removal.

[0005] According to the reaction stage of autotrophic denitrification, the PN / A process can be divided into two-stage and one-stage forms, the difference between which lies in whether short-cut nitrification and anaerobic ammonia oxidation reaction are carried out in the same reactor. However, both of the two processes are challenged in stable operation. On the one hand, the high concentration of organic matter in the anaerobic digestion effluent not only has organic toxicity to anaerobic ammonia oxidation bacteria, but also provides sufficient carbon source and energy for heterotrophic bacteria, resulting in competition between heterotrophic bacteria and anaerobic ammonia oxidation bacteria, which weakens the activity of anaerobic ammonia oxidation bacteria. On the other hand, although the two-stage process can remove part of toxic organic matter through the PN stage, thereby alleviating the inhibition of organic matter on the ANAMMOX stage, the nitrite nitrogen generated in the PN stage is easy to accumulate, and then the inhibition effect of free nitrite is produced; the one-stage process can effectively avoid the inhibition caused by nitrite accumulation, but the one-stage system is easy to be affected by load shock, and the running stability is poor.

[0006] Therefore, for the anaerobic digestion effluent containing high concentration of organic matter, a new type of biogas slurry treatment method needs to be developed. SUMMARY

[0007] The purpose of the present application is to overcome the defects of the short-cut nitrification-anaerobic ammonia oxidation technology that is not applicable to the treatment of high organic toxicity anaerobic digestion effluent, and to provide a high organic toxicity anaerobic digestion effluent treatment system and method based on anaerobic ammonia oxidation shunt detoxification.

[0008] The purpose of the present application is to set a bypass detoxification reactor coupled with persulfate catalytic oxidation and one-stage PN / A process after the PN stage of two-stage PN / A process, to selectively oxidize and detoxify the refractory organic matter in the biogas slurry, and to dilute the direct effluent of the PN stage and reduce the concentration of high toxicity organic matter and free nitrite in the ANAMMOX stage, thereby alleviating the inhibition effect. In addition, by setting the effluent backflow of the ANAMMOX stage, high flux and low concentration denitrification of the ANAMMOX stage can be realized, and the denitrification performance of the reactor is improved. The present application significantly reduces the concentration of toxic substances in the ANAMMOX stage of the PN / A process, improves the denitrification efficiency of the reactor, increases the treatment water volume and reactor load, and successfully realizes efficient and stable treatment of high organic toxicity anaerobic digestion effluent.

[0009] The purpose of the present application can be realized by the following technical solutions: The present application first provides a high organic toxicity anaerobic digestion effluent treatment system based on anaerobic ammonia oxidation shunt detoxification, which comprises a conditioning tank, a nitrosation reactor and an anaerobic ammonia oxidation reactor connected in sequence along the flow direction of the biogas slurry, and a bypass detoxification reactor arranged in the bypass. The outlet of the adjusting tank and the outlet of the nitrosation reactor are respectively connected with a branch and a bypass de-toxication reactor, and the outlet of the bypass de-toxication reactor is connected with an anaerobic ammonia oxidation reactor. The bypass de-toxication reactor is divided into a catalytic oxidation zone and a biological treatment zone along the liquid flow direction; the catalytic oxidation zone is used for loading Fe3O4 / polyacrylamide catalyst and persulfate oxidant and oxidizing and degrading organic matters in the biogas slurry, and the biological treatment zone is used for loading short-range nitrification-anaerobic ammonia oxidation co-embedded particles and biologically treating the biogas slurry.

[0010] Further, the catalytic oxidation zone and the biological treatment zone are in communication through a valve.

[0011] Further, the volume ratio of the catalytic oxidation zone to the biological treatment zone is 1: (1.5-2.5).

[0012] Further, the Fe3O4 / polyacrylamide catalyst is a catalytic microsphere with a particle size ranging from 0.5 mm to 2.0 mm.

[0013] Further, the Fe3O4 / polyacrylamide catalyst specifically consists of polyacrylamide hydrogel and Fe3O4 nanoparticles loaded in the polyacrylamide hydrogel.

[0014] Further, the short-range nitrification-anaerobic ammonia oxidation co-embedded particles consist of anaerobic ammonia oxidation bacteria embedded particles and a nitrosation bacteria embedded gel layer wrapped outside the anaerobic ammonia oxidation bacteria embedded particles.

[0015] Further, the surface of the nitrosation bacteria embedded gel layer is negatively charged after phosphatization treatment.

[0016] Further, the nitrosation bacteria embedded gel layer forms a molecular sieve structure with a pore size less than 5 nm.

[0017] Further, the short-range nitrification-anaerobic ammonia oxidation co-embedded particles are prepared by the following method: Anaerobic ammonia oxidation bacteria sludge is added to a solution containing polyvinyl alcohol and sodium alginate and stirred uniformly, and the mixture is injected into a solution containing saturated boric acid and calcium ions for cross-linking to obtain anaerobic ammonia oxidation bacteria embedded particles, which are then subjected to phosphatization treatment for standby; Anaerobic ammonia oxidation bacteria sludge and nitrosation bacteria embedded particles are sequentially added to another solution containing polyvinyl alcohol and sodium alginate and stirred uniformly to form a nitrosation bacteria embedded gel layer on the surface of the anaerobic ammonia oxidation bacteria embedded particles; the particles are added to a solution containing saturated boric acid and calcium ions for cross-linking, and are again subjected to phosphatization treatment to obtain short-range nitrification-anaerobic ammonia oxidation co-embedded particles.

[0018] The application also provides a high-organic-toxicity anaerobic digestion biogas slurry treatment method based on anaerobic ammonium oxidation shunt detoxification, which adopts any one of the treatment systems. The treatment method specifically comprises the following steps: S1: inputting the anaerobic digestion biogas slurry to be treated into a conditioning tank to obtain reaction influent water through pretreatment; S2: inputting 20%-50% of the reaction influent water in S1 into a nitrosation reactor to perform short-cut nitrification reaction and obtain nitrosation effluent water; S3: inputting 20%-50% of the nitrosation effluent water in S2 and the remaining reaction influent water in S1 into a bypass detoxification reactor to perform short-cut nitrification-anaerobic ammonium oxidation reaction and oxidize refractory organic matter, and obtain bypass detoxification effluent water; S4: inputting the remaining nitrosation effluent water in S2 and the bypass detoxification effluent water in S3 into an anaerobic ammonium oxidation reactor to perform anaerobic ammonium oxidation reaction, and obtain anaerobic ammonium oxidation effluent water; S5: refluxing the anaerobic ammonium oxidation effluent water in S4 into the anaerobic ammonium oxidation reactor at a reflux ratio of 1: (1-20) to continue reaction, and discharging the remaining anaerobic ammonium oxidation effluent water.

[0019] Further, in step S1, the specific operation of the pretreatment is as follows: adjusting the pH of the anaerobic digestion biogas slurry to 7.5-8.3, adjusting the alkalinity of the biogas slurry to 4500-6000 mg CaCO3 / L, pre-precipitating for 2-4 h after the influent water is input, and removing the precipitated sludge to obtain the reaction influent water.

[0020] Further, in step S2, the nitrosation reactor is operated by using the SBR process, and the specific operation method comprises: (1) Start-up stage Inoculate the sludge used for the nitrosation reaction, operate by using the SBR process, the sludge concentration in the reactor is 4-5 mg / L, the pH is controlled at 7.5-8.3, and the temperature is 33-35 ℃; phase gradient increase the reactor load, the concentration of NH4 + -N in the influent water is increased from 200-400 mg / L to 900-1100 mg / L, the dissolved oxygen DO is controlled to be reduced from 0.8-1.5 mg / L to 0.3-0.7 mg / L, and the HRT is 10-15 h; (2) Stable operation stage In the stable operation stage, the drainage ratio of the nitrosation reactor is 50%, the NH4 + -N in the reaction influent water is 1000-1500 mg / L, the COD is 1500-2000 mg / L, and the HRT is maintained at 10-15 h.

[0021] Furthermore, in step S3, the bypass detoxification reactor is operated using the SBR process, and the specific operation method includes: (1) Catalytic oxidation stage The biogas slurry wastewater to be treated is passed into the catalytic oxidation zone, and Fe3O4 / polyacrylamide catalyst is added at a ratio of 0.1-1 g / L. Persulfate oxidant is added at a final concentration of 0.5-5 mM to catalytically oxidize and degrade the recalcitrant organic matter. (2) Biological treatment stage The effluent from the catalytic oxidation process is introduced into the biological treatment zone to initiate the biological treatment process. The pH is controlled at 7.5-8.3, and the temperature at 33-35℃. The reactor load is gradually increased in stages, increasing the NH4+ content of the influent. + The concentration of -N was increased from 250-350 mg / L to 900-1000 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.6-1.0 mg / L to 0.2-0.5 mg / L, with a hRT of 10-15 h; (3) Carrier recycling stage The effluent from the bypass detoxification reaction is discharged, and the Fe3O4 / polyacrylamide catalyst is recovered and reused.

[0022] Furthermore, in step S4, the anaerobic ammonia oxidation reactor is operated using the UASB process, and the specific operation method includes: (1) Start-up phase The sludge used for inoculation in the anaerobic ammonium oxidation reaction was operated using the UASB process, with pH controlled at 7.0-7.5 and temperature at 33-35 ℃; the reactor load was increased in stages using a gradient, increasing the influent NH4+. + The concentration of -N was increased from 80-120 mg / L to 280-320 mg / L, the reflux ratio was increased from 1:1 to 5:1, and the HRT was maintained for 10-15 h; (2) Stable operation phase NH4 in the influent + The concentration of -N was further increased to 550-650 mg / L, the reflux ratio was further increased to 20:1, and the HRT was maintained for 10-15 h.

[0023] Compared with the prior art, the present invention has the following technical advantages: (1) This invention sets up a bypass detoxification reactor after the PN stage of the two-stage PN / A process, which couples the persulfate catalytic oxidation with the one-stage PN / A process, to perform highly selective oxidation and detoxification of the recalcitrant organic matter in the biogas slurry. This improves the denitrification performance of the reactor, while also increasing the treated water volume and reactor load, thus achieving efficient and stable PN / A process treatment of highly organically toxic anaerobic biogas slurry.

[0024] (2) By coupling the two-stage and one-stage PN / A processes, the present invention adjusts the nitrite concentration in the two-stage ANOMMOX stage, enhances the system's ability to resist the inhibition of oxyammonia-oxidizing bacteria by nitrite, increases the total nitrogen removal rate, and makes the system operation more stable.

[0025] (3) Compared with the one-stage PN / A process, this invention avoids the problem of inhibition of functional bacteria by anaerobic digestion liquid with high organic toxicity; compared with the two-stage PN / A process, this process avoids the problem of inhibition of free nitrite nitrogen, is simple to operate, and the system is more stable.

[0026] (4) Compared with traditional denitrification processes, this process reduces carbon source addition by 100%, aeration by 40%, and sludge volume by 90%, resulting in an overall operating cost saving of 84%, significantly reducing operating expenses. Furthermore, this invention achieves a removal rate of up to 85% for recalcitrant organic matter in biogas slurry, a total nitrogen removal rate of up to 96%, and a nitrogen removal load of up to 2.65 kgN / (m³). 3 ·d). Attached Figure Description

[0027] Figure 1 This is a process flow diagram of the method for treating highly organically toxic anaerobic digestion slurry based on anaerobic ammonia oxidation diversion and detoxification according to the present invention.

[0028] Figure 2 This is a schematic diagram of the bypass detoxification reactor of the present invention.

[0029] Figure 3 This is a schematic diagram of the structure of the short-range nitration-anaerobic ammonium oxidation co-encapsulated particles of the present invention.

[0030] Figure 4 This is a physical image of the short-path nitration-anaerobic ammonium oxidation co-encapsulated particles of the present invention.

[0031] Explanation of markings in the diagram: 1-Equalization tank; 2-Nitrification reactor; 3-Anaerobic ammonia oxidation reactor; 4-Bypass detoxification reactor, 4.1-Catalytic oxidation zone, 4.2-Biological treatment zone. Detailed Implementation

[0032] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0033] In this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings and are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention; the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance; furthermore, unless otherwise explicitly specified and limited, the terms "installed," "connected," and "linked" should be interpreted broadly, for example, they can be fixed connections, detachable connections, or integral connections; they can be mechanical connections or electrical connections; they can be direct connections or indirect connections through an intermediate medium; they can be internal connections between two elements. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0034] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0035] This invention proposes a bypass detoxification reactor coupled with persulfate catalytic oxidation and a one-stage PN / A process. By diverting the effluent from the PN stage of the two-stage PN / A process in the main pipeline to the bypass detoxification reactor, a method for treating highly organically toxic anaerobic digestate slurry based on anaerobic ammonia oxidation and detoxification is developed. This method effectively avoids the inhibitory effect of highly toxic nitrogenous slurry on anaerobic ammonia-oxidizing bacteria, while also mitigating the inhibitory effect of free nitrite nitrogen, thereby achieving rapid reactor start-up and stable operation.

[0036] Specifically, the first aspect of the present invention provides a treatment system for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The treatment system includes an equalization tank 1, a nitrification reactor 2, and an anaerobic ammonia oxidation reactor 3 connected sequentially along the slurry flow direction. It also includes a bypass detoxification reactor 4 located in a bypass path. The outlets of the equalization tank 1 and the nitrification reactor 2 are respectively connected to the bypass detoxification reactor 4 via branch paths, and the outlet of the bypass detoxification reactor 4 is connected to the anaerobic ammonia oxidation reactor 3.

[0037] The bypass detoxification reactor 4 is divided into a catalytic oxidation zone and a biological treatment zone 4.1 and 4.2 along the liquid flow direction; wherein, the catalytic oxidation zone 4.1 is used to load Fe3O4 / polyacrylamide catalyst and persulfate oxidant to oxidize and degrade organic matter in the biogas slurry, and the biological treatment zone 4.2 is used to load short-cut nitrification-anaerobic ammonium oxidation co-encapsulated particles to biologically treat the biogas slurry.

[0038] In some specific embodiments, the catalytic oxidation zone and the biological treatment zone are connected by a valve.

[0039] In some specific embodiments, the volume ratio of the catalytic oxidation zone to the biological treatment zone is 1:(1.5-2.5).

[0040] In some specific embodiments, the Fe3O4 / polyacrylamide catalyst is a catalytic microsphere with a particle size ranging from 0.5 to 2.0 mm.

[0041] In some specific embodiments, the Fe3O4 / polyacrylamide catalyst is specifically composed of polyacrylamide hydrogel and Fe3O4 nanoparticles supported within the polyacrylamide hydrogel.

[0042] In some specific embodiments, the short-range nitrification-anaerobic ammonium oxidation co-embedded particles consist of anaerobic ammonium oxidizing bacteria embedded particles and a nitrite-oxidizing bacteria embedded gel layer wrapped around the outer layer of the anaerobic ammonium oxidizing bacteria embedded particles.

[0043] In some specific embodiments, the surface of the nitrifying bacteria-embedded gel layer is phosphorylated to carry a negative charge.

[0044] In some specific embodiments, the nitrifying bacteria-encapsulated gel layer has a molecular sieve structure with a pore size of less than 5 nm.

[0045] In some specific embodiments, the short-path nitration-anaerobic ammonium oxidation co-encapsulated particles are prepared by the following method: Add anaerobic ammonia-oxidizing bacteria sludge to a solution containing polyvinyl alcohol and sodium alginate and stir evenly. Inject the mixture into a solution containing saturated boric acid and calcium ions for cross-linking to obtain anaerobic ammonia-oxidizing bacteria encapsulated particles, which are then phosphorylated for later use. Nitrifying bacteria sludge and anaerobic ammonia oxidizing bacteria encapsulated particles were added sequentially to another solution containing polyvinyl alcohol and sodium alginate and stirred evenly to form a nitrifying bacteria encapsulated gel layer on the surface of the anaerobic ammonia oxidizing bacteria encapsulated particles. The particles were then added to a solution containing saturated boric acid and calcium ions for cross-linking, and then subjected to phosphorylation treatment again to obtain short-cut nitrification-anaerobic ammonia oxidation co-encapsulated particles.

[0046] The bypass detoxification reactor of this invention is filled with short-range nitrification-anaerobic ammonium oxidation co-embedded particles. The inner layer encapsulates anaerobic ammonium oxidizing bacteria (AMX), and the outer layer encapsulates nitrite-oxidizing bacteria (AOB), forming a multi-layered spatial structure similar to granular sludge. This achieves the fixation of AOB and AMX, alleviating the inhibitory effect of biogas slurry. The porous structure of the co-embedded particles has a certain selectivity, allowing small-molecule dissolved ions to provide nutrients to AOB and AMX while preventing large-molecule organic matter with molecular weights much higher than inorganic ions from entering the interior. This ensures effective transport of substrate and product while mitigating the inhibitory effects of organic toxic substances. Simultaneously, the presence of the carrier material increases mass transfer resistance, thus creating a dissolved oxygen gradient within the carrier material, forming aerobic and anoxic zones, promoting the growth and reproduction of the outer AOB and inner AMX layers.

[0047] A second aspect of this invention provides a method for treating highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification, employing any of the aforementioned treatment systems. The treatment method specifically includes the following steps: S1: The anaerobic digester slurry to be treated is fed into the equalization tank, and after pretreatment, it becomes the reaction influent; S2: Input 20%-50% of the reaction influent from S1 into the nitrification reactor for short-cut nitrification to obtain nitrification effluent. S3: 20%-50% of the nitrification reaction effluent from S2 and the remaining reaction influent from S1 are fed into the bypass detoxification reactor to carry out short-cut nitrification-anaerobic ammonium oxidation reaction and oxidize recalcitrant organic matter to obtain bypass detoxification reaction effluent; S4: The remaining nitrification reaction effluent from S2 and the bypass detoxification reaction effluent from S3 are fed into the anaerobic ammonia oxidation reactor for anaerobic ammonia oxidation reaction to obtain anaerobic ammonia oxidation effluent. S5: The anaerobic ammonia oxidation effluent from S4 is returned to the anaerobic ammonia oxidation reactor at a reflux ratio of 1:(1-20) to continue the reaction, and the remaining anaerobic ammonia oxidation effluent is discharged.

[0048] In some specific implementations, the pretreatment in step S1 involves adjusting the pH of the anaerobic digester slurry to 7.5-8.3, adjusting the alkalinity of the slurry to 4500-6000 mg CaCO3 / L, pre-sedimenting for 2-4 hours after water inlet, removing the deposited sludge, and obtaining the reaction inlet water.

[0049] In some more specific embodiments, the pH value of the biogas slurry is adjusted using NaHCO3 and HCl.

[0050] In some more specific embodiments, the alkalinity of the biogas slurry is adjusted using NaHCO3.

[0051] In some specific implementations, in step S2, the nitrification reactor is operated using the SBR process, and the specific operation method includes: (1) Start-up phase The sludge used for the inoculation part of the nitrification reaction is operated using the SBR process. The sludge concentration in the reactor is 4-5 mg / L, the pH is controlled at 7.5-8.3, and the temperature is 33-35 ℃. The reactor load is increased in stages and gradients to increase the influent NH4+. + The concentration of -N was increased from 200-400 mg / L to 900-1100 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.8-1.5 mg / L to 0.3-0.7 mg / L, with a hRT of 10-15 h.

[0052] (2) Stable operation phase During the stable operation phase, the effluent ratio of the nitrification reactor is set to 50%, and the NH4+ in the reactor influent... + -N is 1000-1500 mg / L, COD is 1500-2000 mg / L, and HRT is maintained for 10-15 h.

[0053] In some specific implementations, in step S3, the bypass detoxification reactor is operated using the SBR process, and the specific operation method includes: (1) Catalytic oxidation stage The biogas slurry wastewater to be treated is passed into the catalytic oxidation zone, and Fe3O4 / polyacrylamide catalyst is added at a ratio of 0.1-1 g / L. Persulfate oxidant is added at a final concentration of 0.5-5 mM to catalytically oxidize and degrade the recalcitrant organic matter.

[0054] (2) Biological treatment stage The effluent from the catalytic oxidation process is introduced into the biological treatment zone to initiate the biological treatment process. The pH is controlled at 7.5-8.3, and the temperature at 33-35℃. The reactor load is gradually increased in stages, increasing the NH4+ content of the influent. + The concentration of -N was increased from 250-350 mg / L to 900-1000 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.6-1.0 mg / L to 0.2-0.5 mg / L, with a hRT of 10-15 h.

[0055] (3) Carrier recycling stage The effluent from the bypass detoxification reaction is discharged, and the Fe3O4 / polyacrylamide catalyst is recovered and reused.

[0056] In some more specific embodiments, the catalytic oxidation degradation reaction is carried out under stirring and aeration to promote full contact between the catalyst and the wastewater.

[0057] In some more specific embodiments, the catalytic oxidation reaction time is 1-2 h, which is used to fully degrade recalcitrant organic matter and generate easily biodegradable small molecules.

[0058] In some more specific embodiments, magnetic field separation devices such as magnets or electromagnetic coils are used to recover the Fe3O4 / polyacrylamide catalyst.

[0059] The persulfate (PDS, mainly referring to permonosulfate S2O8) used in this invention 2- Potassium unsymmetrical disulfate (KHSO5) catalytic oxidation technology is an advanced oxidation technology (AOPs) that activates persulfate through a catalyst to generate highly reactive free radicals (such as sulfate radicals SO4·). - It is used to degrade recalcitrant organic matter. It has excellent reactivity, high selectivity, and strong ability to oxidize organic matter, but has little impact on ammonia nitrogen and nitrite nitrogen, and has significant advantages in treating complex wastewater.

[0060] Furthermore, this invention employs a horizontal two-compartment SBR reactor design, dividing the bypass detoxification reactor into two functional units: a catalytic oxidation zone and a biological treatment zone. In the catalytic oxidation zone, by adding Fe3O4 / polyacrylamide catalyst and persulfate oxidant, a catalytic oxidation reaction is carried out for 1-2 hours under pH 3.0-5.0 conditions, which can effectively degrade recalcitrant organic matter in biogas slurry.

[0061] This oxidation process is primarily achieved through the activation of generated sulfate radicals (SO4·-). Under the influence of active sites on the catalyst surface, persulfate (PMS) undergoes an electron transfer reaction, producing highly oxidizing SO4·- (redox potential +2.5~+3.1 V). These radicals attack unstable structures in organic molecules, initiating a chain reaction through an electron-withdrawing mechanism, causing large organic molecules to gradually break down into smaller intermediate products. The oxidation process exhibits distinct two-stage kinetics: a rapid initial stage (0-30 minutes) followed by a slower reaction stage (30-120 minutes), demonstrating selective removal characteristics for different types of organic compounds.

[0062] The biological treatment zone is filled with specially designed short-range nitrification-anaerobic ammonium oxidation co-encapsulated particles. By controlling parameters such as dissolved oxygen at 0.2-0.5 mg / L, temperature at 33-35 ℃, and HRT at 12 hours, it achieves deep removal of organic toxins and partial denitrification. The co-encapsulated particles resist external oxidants and organic toxicity through a triple mechanism of physical barriers, chemical protection, and biological detoxification. The outer layer of PVA / SA gel forms a molecular sieve structure with a pore size of less than 5 nm, selectively blocking the intrusion of large molecular organic toxins and oxidants. The carrier surface is phosphorylated and carries a negative charge, which electrostatically repels anionic oxidants. At the same time, the outer layer of AOB bacteria preferentially consumes dissolved oxygen, forming an anaerobic microenvironment in the inner layer to protect the anaerobic ammonium oxidizing bacteria. The aerobic-anaerobic gradient space constructed inside the particles enables the outer AOB and inner AMX bacteria to form a synergistic metabolic chain, achieving preliminary nitrogen conversion while degrading small molecular organic matter.

[0063] In some specific implementations, in step S4, the anaerobic ammonia oxidation reactor is operated using the UASB process, and the specific operation method includes: (1) Start-up phase The sludge used for inoculation in the anaerobic ammonium oxidation reaction was operated using the UASB process, with pH controlled at 7.0-7.5 and temperature at 33-35 ℃; the reactor load was increased in stages using a gradient, increasing the influent NH4+. + The concentration of -N was increased from 80-120 mg / L to 280-320 mg / L, the reflux ratio was increased from 1:1 to 5:1, and the HRT was maintained for 10-15 h; (2) Stable operation phase NH4 in the influent + The concentration of -N was further increased to 550-650 mg / L, the reflux ratio was further increased to 20:1, and the HRT was maintained for 10-15 h.

[0064] In some specific embodiments, the start-up time of the nitrification reactor is 20-30 days, and the HRT is preferably 12 h.

[0065] In some specific embodiments, the start-up time of the bypass detoxification reactor is 50 to 60 days, and the HRT is preferably 12 hours.

[0066] In some specific embodiments, the start-up time of the anaerobic ammonia oxidation reactor is 30 to 50 days, and the HRT is preferably 12 hours.

[0067] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0068] Unless otherwise specified, the Fe3O4 / polyacrylamide catalysts in the following examples and comparative examples were prepared using the following methods: Dissolve 2.70 g FeCl3·6H2O and 1.39 g FeSO4·7H2O in 100 mL of deionized water. Purge the solution with nitrogen gas for 10-15 minutes to remove dissolved oxygen and prevent Fe from being released. 2+ Oxidation. Under stirring conditions, add NaOH solution (e.g., 1 M) or ammonia water dropwise to adjust the pH to 10-11, at which point Fe3O4 nanoparticles will be generated. Place the mixed solution in a constant temperature water bath and stir at 65 °C for 2 hours under nitrogen protection to prevent Fe3O4 oxidation. Separate the Fe3O4 nanoparticles using a magnet and wash them 3-5 times with deionized water to remove unreacted ions and impurities.

[0069] PAM powder was dissolved in deionized water to prepare a 10 wt% PAM solution. 0.2% w / w of crosslinking agent N,N'-methylenebisacrylamide (MBA) and 0.2% w / w of initiator ammonium persulfate were added to the PAM solution, and the mixture was stirred until homogeneous. The mixture was placed in a constant temperature water bath and reacted at 70 °C for approximately 2 hours to form a PAM hydrogel.

[0070] The prepared Fe3O4 nanoparticles were dispersed in deionized water and added to a PAM hydrogel, then stirred until homogeneous. The mixture was placed in a constant temperature water bath and reacted at 70 °C for 2 hours to form a stable composite material between Fe3O4 and PAM. The Fe3O4 / PAM composite material was washed with deionized water 3-5 times to remove unreacted substances. Finally, it was dried in a 70 °C oven for 6-12 hours to obtain the final Fe3O4 / polyacrylamide catalyst.

[0071] Unless otherwise specified, the short-path nitrification-anaerobic ammonium oxidation co-encapsulated particles in the following examples and comparative examples were prepared using the following methods: Take 100 mL of 12% PVA (polyvinyl alcohol), swell it in deionized water at room temperature for 2 h, and then dissolve it by heating in a 90 ℃ water bath. Then add 20 mL of 2% SA (sodium alginate), stir until completely mixed, and then sterilize in an autoclave at 121 ℃ for 30 min.

[0072] After cooling to room temperature, add 30 mL of Anammox sludge and stir well. Using a syringe, slowly drip the embedded bacterial gel solution into a saturated boric acid and 1 wt% CaCl2 solution, and crosslink for 1 h. Remove the embedded particles, rinse three times with deionized water, and then phosphorylate in 0.5 mol / L KH2PO4 solution for 1 h. Rinse three more times with deionized water and store in anaerobic ammonia oxidation medium at 4 ℃ for later use.

[0073] Take 80 mL of 6% PVA and swell it in deionized water at room temperature for 2 h, then dissolve it by heating in a 90 ℃ water bath. Add 20 mL of 4% SA and stir until completely mixed. Then, autoclave at 121 ℃ for 30 min. After cooling to room temperature, add 4 mL of AOB sludge and stir well.

[0074] Anammox-encapsulated particles were added to the mixture, immersing them in the mixture to form an AOB gel layer on the surface. The particles were then removed and added to a saturated boric acid and 1 wt% CaCl2 solution for crosslinking for 1 h. The encapsulated particles were then removed, rinsed three times with deionized water, and phosphorylated in a 0.5 mol / L KH2PO4 solution for 1 h. After rinsing three more times with deionized water, micron-sized short-path nitrification-anaerobic ammonium oxidation co-encapsulated particles were obtained.

[0075] A schematic diagram of the structure of the short-range nitration-anaerobic ammonium oxidation co-encapsulated particles prepared by this invention is shown below. Figure 3 As shown in the picture, the actual product is as follows. Figure 4 As shown.

[0076] Each of the above embodiments can be implemented individually, or in any combination of two or more. The following detailed description of specific examples will further illustrate these embodiments.

[0077] Example 1: This embodiment provides a treatment system and method for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The treatment system specifically consists of an equalization tank, a nitrification reactor, an anaerobic ammonia oxidation reactor, and a bypass detoxification reactor.

[0078] In this embodiment, both the nitrification reactor and the anaerobic ammonia oxidation reactor are made of plexiglass, with an effective volume of 6 L, a reaction volume of 4.8 L, and a precipitation volume of 1.2 L. The bypass detoxification reactor is also made of plexiglass, with an effective volume of 3 L in the catalytic oxidation zone and 6 L in the biological treatment zone, and a reaction volume of 4.8 L and a precipitation volume of 1.2 L.

[0079] The process parameters for the nitrification SBR reactor are as follows: the reaction cycle includes an anaerobic stirring stage and an aeration stirring stage, with anaerobic stirring lasting 3-8 hours and aeration stirring lasting 5-8 hours; the aeration rate is 0.8-2 L air / min·L reactor. The process parameters for the bypass detoxification SBR reactor are as follows: the reaction cycle includes a catalytic oxidation stage, a biological treatment stage, and a carrier recovery stage, with catalytic oxidation lasting 2 hours and biological treatment lasting 10 hours; the aeration rate is 0.3-0.8 L air / min·L reactor. In the anaerobic ammonia oxidation UASB reactor, the influent is drawn into the reactor from the bottom using a peristaltic pump. The influent contacts the sludge from bottom to top and reacts fully. Gas, liquid, and solid phases are separated in a three-phase separator at the top of the reactor. The effluent is discharged from the effluent outlet, and the generated gas is discharged from the top vent. The reactor is wrapped with black sponge, which serves both to block light and to provide insulation.

[0080] In this embodiment, the nitrification sludge was taken from a pilot-scale nitrification reactor at a sludge treatment plant in Changsha, and the anammox sludge was also taken from a pilot-scale anammox reactor at the same plant. The pilot-scale reactor was operated to simulate wastewater, and the sludge was repeatedly washed and settled. 1.2 L of settled sludge was added to a 6 L reactor for operation. The short-cut nitrification-anammox co-encapsulated particles and Fe3O4 / polyacrylamide catalyst were prepared in the laboratory. The typical recalcitrant organic matter in the anammox digestate was mainly phenol, with an initial concentration of approximately 200 mg / L.

[0081] In this embodiment, the flowchart of the method for treating highly organically toxic anaerobic digestion slurry is as follows: Figure 1 As shown, the specific steps include: (1) Anaerobic digestion slurry enters the equalization tank. NaHCO3 and HCl are used to adjust the pH of the anaerobic digestion slurry to 7.5-8.3, and NaHCO3 is used to adjust the alkalinity of the slurry to about 5000 mg CaCO3 / L. After the water is influent, it is pre-sedied for 2 hours to remove the deposited sludge and provide ideal influent for the subsequent process section. The effluent enters the nitrification reactor. (2) Add 40% of the reaction influent from step (1) to the nitrification reactor for short-cut nitrification to obtain nitrification effluent. The sludge concentration in the reactor is 4-5 mg / L, the pH is controlled at 7.5-8.3, and the temperature is 33-35 ℃. During the start-up phase, the reactor load is gradually increased in stages, and the influent NH4+ is increased. + The concentration of -N was increased from 300 mg / L to 1000 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.8-1.5 mg / L to 0.3-0.7 mg / L, with a hRT of 12 h.

[0082] During the stable operation phase, the effluent ratio of the nitrification reactor is set to 50%, and the NH4+ in the influent to the reaction water is... +-N is 1000-1500 mg / L, COD is 1500-2000 mg / L, and HRT is maintained for 12 h. Effluent NH4 + -N concentration is 800-900 mg / L, NO2 - With a nitrogen concentration of 150-450 mg / L, the ammonia nitrogen removal load can reach 1.41-2.02 kgN / (m³). 3 ·d), the COD of the effluent is 623-1129 mg / L.

[0083] (3) 20% of the effluent from the nitrification reaction in step (2) and the remaining 60% of the influent were added to the bypass detoxification reactor for persulfate catalytic oxidation and short-cut nitrification-anaerobic ammonium oxidation reactions to obtain bypass detoxification effluent. The dosage of Fe3O4 / polyacrylamide catalyst was 0.5 g / L, and the dosage of persulfate was 1 mM. The dosage of the short-cut nitrification-anaerobic ammonium oxidation co-encapsulated particles was 30 g / L.

[0084] In the catalytic oxidation stage, the wastewater to be treated is injected into the SBR reactor, and Fe3O4 / polyacrylamide catalyst and persulfate are added. Stirring and aeration are started to promote full contact between the catalyst and the wastewater. Catalytic oxidation is carried out for 2 hours to degrade recalcitrant organic matter and generate easily biodegradable small molecules.

[0085] During the biological treatment stage, the addition of catalyst and persulfate is stopped. The effluent from the catalytic oxidation is then introduced into the biological treatment zone, and aeration continues to initiate the biological treatment process. The pH is controlled at 7.5-8.3, and the temperature at 33-35 ℃. The reactor load is gradually increased in stages, increasing the influent NH4+. + The concentration of -N was increased from 300 mg / L to 1000 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.6-1.0 mg / L to 0.2-0.5 mg / L, with a hRT of 12 h.

[0086] During the stable operation phase, the effluent ratio of the bypass detoxification reactor is set to 50%, and the NH4+ in the reaction influent is... + -N is 1000-1500 mg / L, COD is 1500-2000 mg / L, and HRT is maintained for 12 h. Effluent NH4 + -N concentration is 200-300 mg / L, NO2 - When the ammonia nitrogen concentration is 300-500 mg / L, the ammonia nitrogen removal load can reach 1.53-2.36 kgN / (m³). 3 ·d).

[0087] During the carrier recovery stage, the treated biogas slurry is discharged, and the Fe3O4 / polyacrylamide catalyst is recovered using magnetic field separation devices such as magnets. The recovered catalyst is then cleaned and reused.

[0088] The technical solution in this embodiment demonstrates stable treatment efficiency during continuous operation. The catalytic oxidation stage achieves a phenol degradation rate of 92-98%, the biological treatment stage removes more than 60% of COD, and the overall system maintains a phenol removal efficiency of 85-90%.

[0089] Furthermore, the co-encapsulated particles enable the reactor to withstand 5 mM persulfate shocks and 200 mg / L phenol loads, and no decline in functional bacterial activity was observed during 180 days of long-term operation. The effluent from this detoxification treatment reactor creates favorable conditions for efficient nitrogen removal in the subsequent anaerobic ammonia oxidation reactor. The oxidation system exhibits differentiated removal characteristics for typical recalcitrant organic matter; the degradation rate of phenols containing electron-donating groups is significantly higher than that of compounds containing electron-withdrawing groups. This selectivity complements the protective effect of the co-encapsulated particles, jointly ensuring the stability of the system's treatment performance.

[0090] (4) Add 80% of the effluent from the nitrification reaction in step (2) and the bypass detoxification effluent from step (3) to the anaerobic ammonia oxidation reactor for anaerobic ammonia oxidation reaction to obtain anaerobic ammonia oxidation effluent; during the start-up phase, the pH is controlled at 7.0-7.5 and the temperature is 33-35 ℃; gradually increase the reactor load in stages, and increase the influent NH4+. + The concentration of -N was increased from 100 mg / L to 300 mg / L, the reflux ratio was increased from 1:1 to 5:1, and the HRT was maintained for 12 h.

[0091] During the stable operation phase, NH4 will be introduced into the water. + The concentration of -N was increased from 300 mg / L to 600 mg / L, the reflux ratio was increased from 5:1 to 20:1, and the HRT was maintained for 12 h. The effluent NH4... + -N concentration is 30 mg / L, NO2 in effluent - With a nitrogen concentration of 30 mg / L, the maximum nitrogen removal load can reach 2.65 kgN / (m³). 3 ·d).

[0092] Example 2: This embodiment provides a treatment system and method for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The nitrification reactor, bypass detoxification reactor, and anaerobic ammonia oxidation reactor are the same as in Embodiment 1, the difference being that this embodiment uses a water distribution operation, and the effluent NH4... + -N concentration is 10 mg / L, NO2 in effluent - With a nitrogen concentration of 20 mg / L, the maximum nitrogen removal load can reach 5.03 kgN / (m³). 3 ·d).

[0093] Example 3: This embodiment provides a treatment system and method for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The nitrification reactor, bypass detoxification reactor, and anaerobic ammonia oxidation reactor are the same as in Embodiment 1, except that in this embodiment, the diversion ratio is set to 40% of the nitrification effluent is fed into the bypass detoxification reactor and 60% into the anaerobic ammonia oxidation reactor. The effluent NH4... + -N concentration is 40 mg / L, NO2 in effluent - -N concentration is 50 mg / L.

[0094] Example 4: This embodiment provides a treatment system and method for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The nitrification reactor, bypass detoxification reactor, and anaerobic ammonia oxidation reactor are the same as in Embodiment 1. The difference is that in this embodiment, the diversion ratio is set so that 50% of the nitrification effluent is fed into the bypass detoxification reactor and 50% into the anaerobic ammonia oxidation reactor. The effluent NH4... + -N concentration is 70 mg / L, NO2 in effluent - -N concentration is 90 mg / L.

[0095] Example 5: This embodiment provides a treatment system and method for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification. The nitrification reactor, bypass detoxification reactor, and anaerobic ammonia oxidation reactor are the same as in Example 1, except that in this embodiment, the Fe3O4 / PAM catalyst dosage in the bypass detoxification reactor is 0.1 g / L, the persulfate dosage is 0.5 mM, and the effluent NH4... + -N concentration is 100 mg / L, effluent NO2 - -N concentration is 160 mg / L.

[0096] Comparative Example 1: This comparative example only uses a two-stage PN / A process (nitrification reactor + anaerobic ammonia oxidation reactor), without setting up a bypass detoxification reactor, and without using co-encapsulated particles and persulfate catalytic oxidation.

[0097] However, this comparative example exhibited the following problems during operation: high concentrations of organic matter directly entered the ANAMMOX section, leading to inhibited activity of anaerobic ammonia-oxidizing bacteria (denitrification efficiency decreased by more than 30%). Nitrite nitrogen (NOx) accumulated in the PN section... 2- -N>600 mg / L), causing inhibition of free nitrite nitrogen. The system operation is unstable, requiring frequent parameter adjustments (pH / DO fluctuations reach ±0.5). The total nitrogen removal rate is only 65-75%, and the nitrogen removal load is <1.8 kgN / (m³). 3·d), which is much lower than the nitrogen removal load in the above embodiments.

[0098] Comparative Example 2: This comparative example uses a bypass detoxification reactor but employs ordinary activated sludge (i.e., sludge without co-encapsulated particles), and other conditions are the same as in Example 1.

[0099] However, this comparative example exhibited the following problems during operation: the catalyst Fe3O4 / PAM became toxic to microorganisms, resulting in a 40% decrease in sludge activity. The oxidant caused the death of free bacteria, reducing the sludge concentration from 4 g / L to 1.5 g / L. Significant loss of denitrifying bacteria occurred, with the AOB / AMX ratio decreasing from 60% to 20%; fresh sludge needed to be replenished weekly, increasing maintenance costs by 200%.

[0100] Comparative Example 3: This comparative example uses a bypass detoxification reactor but does not add persulfate, relying solely on biological treatment, with other conditions the same as in Example 1.

[0101] However, the comparative example had the following problems during operation: the removal rate of phenol, a recalcitrant organic compound, was <30%; the detoxification effect was poor, and the ANAMMOX stage was still inhibited by organic toxicity, resulting in a 45% reduction in the denitrification rate; the system had weak resistance to shock loads, with COD fluctuations >200 mg / L, leading to a 50% decrease in denitrification efficiency.

[0102] In summary, this invention relates to a method for treating highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation (ANAMMOX) detoxification, belonging to the field of water treatment technology. This method involves setting up a bypass detoxification reactor coupled with persulfate catalytic oxidation and a single-stage PN / A process after the short-cut nitrification (PN) stage of a two-stage short-cut nitrification-anaerobic ammonia oxidation (PN / A) process. This reactor selectively oxidizes and detoxifies the recalcitrant organic matter in the digester slurry. The effluent from the bypass detoxification reactor, along with the direct effluent from the PN stage, enters the anaerobic ammonia oxidation (ANAMMOX) stage of the two-stage PN / A process. This dilutes the direct effluent from the PN stage while reducing the concentration of highly toxic organic matter and free nitrite in the ANAMMOX stage, mitigating the inhibitory effect. Furthermore, by incorporating effluent recirculation from the ANAMMOX stage, high-flux, low-concentration denitrification is achieved, improving the reactor's denitrification performance.

[0103] This invention significantly reduces the concentration of toxic substances in the ANAMMOX stage of the PN / A process, improves reactor denitrification efficiency, increases treated water volume and reactor load, and successfully achieves efficient and stable treatment of highly organically toxic anaerobic digestion slurry. Compared with traditional denitrification processes, this process reduces carbon source addition by 100%, aeration by 40%, sludge volume by 90%, saves 76% on overall operating costs, achieves a total nitrogen removal rate of 91.3%-95.6%, and a nitrogen removal load of 2.03-2.65 kgN / (m³). 3 ·d).

[0104] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A treatment system for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification, characterized in that, The treatment system includes an equalization tank, a nitrification reactor, and an anaerobic ammonia oxidation reactor connected in sequence along the flow direction of the biogas slurry, and also includes a bypass detoxification reactor located in the bypass. The outlet of the equalization tank and the outlet of the nitrification reactor are also connected to the bypass detoxification reactor via branch lines, and the outlet of the bypass detoxification reactor is connected to the anaerobic ammonia oxidation reactor. The bypass detoxification reactor is divided into a catalytic oxidation zone and a biological treatment zone along the liquid flow direction; wherein, the catalytic oxidation zone is used to load Fe3O4 / polyacrylamide catalyst and persulfate oxidant to oxidize and degrade organic matter in the biogas slurry, and the biological treatment zone is used to load short-cut nitrification-anaerobic ammonium oxidation co-encapsulated particles to biologically treat the biogas slurry.

2. The high organic toxicity anaerobic digestion slurry treatment system based on anaerobic ammonia oxidation diversion and detoxification according to claim 1, characterized in that, The catalytic oxidation zone and the biological treatment zone are connected by a valve; The volume ratio of the catalytic oxidation zone to the biological treatment zone is 1:(1.5-2.5).

3. The high organic toxicity anaerobic digestion slurry treatment system based on anaerobic ammonia oxidation diversion and detoxification according to claim 1, characterized in that, The Fe3O4 / polyacrylamide catalyst is a catalytic microsphere with a particle size range of 0.5-2.0 mm, specifically composed of polyacrylamide hydrogel and Fe3O4 nanoparticles supported within the polyacrylamide hydrogel.

4. The high organic toxicity anaerobic digestion slurry treatment system based on anaerobic ammonia oxidation diversion and detoxification according to claim 1, characterized in that, The short-range nitrification-anaerobic ammonium oxidation co-embedded particles consist of anaerobic ammonium oxidizing bacteria embedded particles and a nitrite-oxidizing bacteria embedded gel layer wrapped around the outer layer of the anaerobic ammonium oxidizing bacteria embedded particles. The surface of the nitrifying bacteria-embedded gel layer is phosphorylated and carries a negative charge, and the nitrifying bacteria-embedded gel layer forms a molecular sieve structure with a pore size of less than 5 nm.

5. A treatment system for highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation diversion and detoxification according to claim 4, characterized in that, The short-path nitration-anaerobic ammonium oxidation co-encapsulated particles were prepared by the following method: Add anaerobic ammonia-oxidizing bacteria sludge to a solution containing polyvinyl alcohol and sodium alginate and stir evenly. Inject the mixture into a solution containing saturated boric acid and calcium ions for cross-linking to obtain anaerobic ammonia-oxidizing bacteria encapsulated particles, which are then phosphorylated for later use. Nitrifying bacteria sludge and anaerobic ammonia oxidizing bacteria encapsulated particles were added sequentially to another solution containing polyvinyl alcohol and sodium alginate and stirred evenly to form a nitrifying bacteria encapsulated gel layer on the surface of the anaerobic ammonia oxidizing bacteria encapsulated particles. The particles were then added to a solution containing saturated boric acid and calcium ions for cross-linking, and then subjected to phosphorylation treatment again to obtain short-cut nitrification-anaerobic ammonia oxidation co-encapsulated particles.

6. A method for treating highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation and diversion detoxification, characterized in that, The processing system described in any one of claims 1-5 is used; The processing method specifically includes the following steps: S1: The anaerobic digester slurry to be treated is fed into the equalization tank, and after pretreatment, it becomes the reaction influent; S2: Input 20%-50% of the reaction influent from S1 into the nitrification reactor for short-cut nitrification to obtain nitrification effluent. S3: 20%-50% of the nitrification reaction effluent from S2 and the remaining reaction influent from S1 are fed into the bypass detoxification reactor to carry out short-cut nitrification-anaerobic ammonium oxidation reaction and oxidize recalcitrant organic matter to obtain bypass detoxification reaction effluent; S4: The remaining nitrification reaction effluent from S2 and the bypass detoxification reaction effluent from S3 are fed into the anaerobic ammonia oxidation reactor for anaerobic ammonia oxidation reaction to obtain anaerobic ammonia oxidation effluent. S5: The anaerobic ammonia oxidation effluent from S4 is returned to the anaerobic ammonia oxidation reactor at a reflux ratio of 1:(1-20) to continue the reaction, and the remaining anaerobic ammonia oxidation effluent is discharged.

7. The method for treating highly organically toxic anaerobic digester slurry based on anaerobic ammonia oxidation diversion and detoxification according to claim 6, characterized in that, In step S1, the specific preprocessing operation is as follows: Adjust the pH of the anaerobic digestion slurry to 7.5-8.3 and the alkalinity of the slurry to 4500-6000 mg CaCO3 / L. After influent, pre-sedimentation is carried out for 2-4 hours to remove the deposited sludge and obtain the reaction influent.

8. The method for treating highly organically toxic anaerobic digestate slurry based on anaerobic ammonia oxidation diversion and detoxification according to claim 6, characterized in that, In step S2, the nitrification reactor is operated using the SBR process, and the specific operation method includes: (1) Start-up phase The sludge used for the inoculation part of the nitrification reaction is operated using the SBR process. The sludge concentration in the reactor is 4-5 mg / L, the pH is controlled at 7.5-8.3, and the temperature is 33-35 ℃. The reactor load is increased in stages with a gradient, and the influent NH4+ is increased. + The concentration of -N was increased from 200-400 mg / L to 900-1100 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.8-1.5 mg / L to 0.3-0.7 mg / L, with a hRT of 10-15 h. (2) Stable operation phase During the stable operation phase, the effluent ratio of the nitrification reactor is set to 50%, and the NH4+ in the reactor influent... + -N is 1000-1500 mg / L, COD is 1500-2000 mg / L, and HRT is maintained for 10-15 h.

9. The method for treating highly organically toxic anaerobic digestate slurry based on anaerobic ammonia oxidation diversion and detoxification according to claim 6, characterized in that, In step S3, the bypass detoxification reactor is operated using the SBR process, and the specific operation method includes: (1) Catalytic oxidation stage The biogas slurry wastewater to be treated is passed into the catalytic oxidation zone, and Fe3O4 / polyacrylamide catalyst is added at a ratio of 0.1-1 g / L. Persulfate oxidant is added at a final concentration of 0.5-5 mM to catalytically oxidize and degrade the recalcitrant organic matter. (2) Biological treatment stage The effluent from the catalytic oxidation process is introduced into the biological treatment zone to initiate the biological treatment process. The pH is controlled at 7.5-8.3, and the temperature at 33-35℃. The reactor load is gradually increased in stages, increasing the influent NH4+. + The concentration of -N was increased from 250-350 mg / L to 900-1000 mg / L, and the dissolved oxygen (DO) was controlled to decrease from 0.6-1.0 mg / L to 0.2-0.5 mg / L, with a hRT of 10-15 h; (3) Carrier recycling stage The effluent from the bypass detoxification reaction is discharged, and the Fe3O4 / polyacrylamide catalyst is recovered and reused.

10. The method for treating highly organically toxic anaerobic digestate slurry based on anaerobic ammonia oxidation diversion and detoxification according to claim 6, characterized in that, In step S4, the anaerobic ammonia oxidation reactor is operated using the UASB process, and the specific operation method includes: (1) Start-up phase The sludge used for inoculation in the anaerobic ammonium oxidation reaction was operated using the UASB process, with pH controlled at 7.0-7.5 and temperature at 33-35 ℃; the reactor load was increased in stages using a gradient, increasing the influent NH4+. + The concentration of -N was increased from 80-120 mg / L to 280-320 mg / L, the reflux ratio was increased from 1:1 to 5:1, and the HRT was maintained for 10-15 h; (2) Stable operation phase NH4 in the influent + The concentration of -N was further increased to 550-650 mg / L, the reflux ratio was further increased to 20:1, and the HRT was maintained for 10-15 h.

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