Anaerobic ammonia oxidation reactor carrier, preparation method thereof and anaerobic ammonia oxidation reactor

Abstract

The invention aims to provide an anaerobic ammonia oxidation reactor carrier, a preparation method thereof and an anaerobic ammonia oxidation reactor. The preparation method of the carrier comprises the following steps: A, preparing a polyvinylpyrrolidone aqueous solution with the mass ratio of (80-120): 1, adding carbon nanotubes into the polyvinylpyrrolidone aqueous solution, and uniformly dispersing to obtain a carbon nanotube dispersion liquid; b, adding the modified lepidolite slag into the carbon nanotube dispersion liquid, and performing ultrasonic dispersion to obtain composite dispersion liquid; c, adding methoxytrimethylsilane into an ethanol solution to obtain a treatment solution; and D, uniformly mixing polyurethane sponge and the composite dispersion liquid according to a mass ratio of 1: (40-60), adjusting the temperature to 70-90 DEG C, carrying out heat preservation stirring for 1-3 hours, then adding the treating fluid, continuously stirring for 3-5 hours, then filtering, placing in a drying oven, and drying to obtain the carrier. The carrier can promote growth and metabolism of microorganisms. The reactor provided by the invention can better treat wastewater with high ammonia nitrogen and high organic matter content.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of part disassembly, and particularly relates to an anaerobic ammonia oxidation reactor carrier and a preparation method thereof and an anaerobic ammonia oxidation reactor. BACKGROUND

[0002] In recent years, the clean utilization of coal has attracted widespread attention. Coal chemical work is one of the key ways for clean utilization of coal, which mainly includes coal gasification, coal coking, coal alcohol, coal olefin, etc. Among them, coal gasification has an energy conversion rate of more than 60%, which can effectively reduce the dependence on imported natural gas in China. Therefore, coal gasification has become an important direction of the development of coal chemical industry. The process of coal gasification is to convert coal into gas, liquid and solid products through coking, coal gasification, coal liquefaction, tar chemical industry, calcium carbide acetylene chemical industry, and chemical product recycling. A large amount of wastewater is generated in the whole process, which mainly comes from coking and gasification wastewater. Coking wastewater refers to the ammonia water generated after coal is pyrolyzed at high temperature, and the cooling water in the coal gas purification process. Gasification wastewater is the combustible gas generated by the gasification and decomposition of coal in the reaction furnace. After the vaporized gas is sprayed and cooled, the condensate and washing wastewater are generated. The wastewater generated by coal gasification has the characteristics of high turbidity, containing phenolic substances, and ammonia nitrogen content of more than 1500 mg / L. The large amount of coal gasification wastewater discharge seriously restricts the green development of the industry.

[0003] With the continuous progress of denitrification technology, the widely used processes derived from traditional nitrification and denitrification are: A / O process, A2 / O process, SBR, MBR, oxidation ditch process, etc. Compared with traditional biological denitrification process, the advantage of short-cut nitrification is that PN can save 25% of the aeration cost in the nitrification stage, and at least 40% of the carbon source dosage in the denitrification stage, while the sludge amount can also be greatly reduced; Compared with the traditional nitrification and denitrification process, the anaerobic ammonia oxidation process can reduce the oxygen consumption by 60%, only needs CO2 to provide carbon source, and the metabolic pathway will not produce N2O and other greenhouse gases, reducing the harm to the environment. Therefore, the combined process of short-cut nitrification-anaerobic ammonia oxidation has attracted widespread attention due to its advantages in high-strength ammonia wastewater treatment.

[0004] Short-cut nitrification coupled with anaerobic ammonia oxidation is an energy-saving and efficient biological denitrification technology for wastewater, mainly applied to the treatment of high-ammonia wastewater. The core principle is to oxidize part of the ammonia nitrogen to nitrite by short-cut nitrification, and then use anaerobic ammonia oxidation bacteria to directly convert nitrite and residual ammonia nitrogen into nitrogen, thereby achieving efficient denitrification. The goal of short-cut nitrification is to partially oxidize ammonia nitrogen (NH4 ⁺ ) in wastewater to nitrite (NO2 ⁻ ), rather than nitrate (NO3 ⁻). The key to achieve short-term nitrification lies in controlling environmental conditions to inhibit the second step of the nitrification process (oxidation of nitrite to nitrate), under anaerobic conditions, anaerobic ammonium oxidation bacteria (AnAOB) directly convert ammonia (NH4 ⁺ ) and nitrite (NO2 ⁻ ) to nitrogen (N2).

[0005] Currently, the anaerobic ammonia oxidation reactor commonly used in the prior art needs to use anaerobic ammonia oxidation bacteria, which are a kind of autotrophic microorganisms, grow slowly, and need to adhere to the solid surface to better grow and reproduce, which has a higher requirement for the performance of the carrier in the anaerobic ammonia oxidation reactor. Therefore, it is of great significance to study a carrier capable of promoting the adhesion and aggregation of microorganisms. SUMMARY

[0006] The present application aims to provide an anaerobic ammonia oxidation reactor carrier and a preparation method thereof, and an anaerobic ammonia oxidation reactor, the carrier of the present application provides a relatively stable living environment for microorganisms, promotes the aggregation and growth of microorganisms, and can change the water flow state in the reactor to form local turbulence and vortex, increase the contact opportunity of microorganisms and substrates, and is beneficial to the mass transfer process of substrates to the surface of microbial cells, thereby promoting the growth and metabolism of microorganisms.

[0007] The present application also provides an anaerobic ammonia oxidation reactor using the carrier, which can better treat wastewater with high ammonia nitrogen and high organic matter content.

[0008] The preparation method of the anaerobic ammonia oxidation reactor carrier comprises the following steps: A. A polyvinylpyrrolidone aqueous solution with a mass ratio of 80-120:1 is configured, carbon nanotubes are added to the polyvinylpyrrolidone aqueous solution and uniformly dispersed to obtain a carbon nanotube dispersion liquid; in the carbon nanotube dispersion liquid, the concentration of carbon nanotubes is 0.03-0.04wt%; B. Modified lithium mica slag is added to the carbon nanotube dispersion liquid, and ultrasonic dispersion is performed to obtain a composite dispersion liquid; in the composite dispersion liquid, the mass ratio of modified lithium mica slag to carbon nanotube dispersion liquid is 1:150-160; C. Methoxytrimethylsilane is added to an ethanol solution to obtain a treatment liquid; in the treatment liquid, the mixed mass ratio of methoxytrimethylsilane to ethanol solution is 1:30-50; D. Polyurethane sponge and the composite dispersion liquid are uniformly mixed at a mass ratio of 1:40-60, the temperature is adjusted to 70-90 DEG C, and the mixture is stirred for 1-3 hours, then the treatment liquid is added, the mass ratio of the treatment liquid to the composite dispersion liquid is 1:15-18, and the stirring is continued for 3-5 hours, then filtration is performed, the mixture is placed in a drying box, the temperature is 110-130 DEG C, and the mixture is dried for 1-3 hours to obtain the carrier.

[0009] The preparation method of the carbon nanotube dispersion liquid in step A comprises the following steps: The carbon nanotube is added to the mixed solution obtained above, and stirred at a speed of 300-400 r / min for 1-3 hours, and then added to a high-speed homogenizer for homogenization treatment for 15-40 min, wherein the homogenization speed is 4000-5000 r / min, to obtain the carbon nanotube dispersion liquid.

[0010] In step D, the polyurethane sponge is cleaned with anhydrous ethanol, dried, and then mixed with the composite dispersion liquid in a mass ratio.

[0011] The drying condition of the polyurethane sponge cleaned with anhydrous ethanol is 40-60 DEG C for 3-5 hours.

[0012] In step C, the mass fraction of the ethanol solution is 45-55%.

[0013] The preparation method of the modified lepidolite slag comprises the following steps: The lepidolite slag is ultra-finely pulverized to obtain lepidolite slag powder with an average particle size of 20 microns; the lepidolite slag powder and nano-silicon dioxide are added to an ethanol solution with a mass fraction of 85-92%, stirred uniformly, and then subjected to ultrasonic dispersion for 10 min to obtain a lepidolite slag powder and nano-silicon dioxide dispersion liquid; wherein the mass ratio of the lepidolite slag powder, nano-silicon dioxide and the ethanol solution is 30-33:3:230-320; KH550 is added to an ethanol solution with a mass fraction of 90%, mixed uniformly, and configured into a KH550 dispersion liquid with a mass fraction of 10%; The KH550 dispersion liquid is added to the lepidolite slag powder and nano-silicon dioxide dispersion liquid in a volume ratio of 1:5-6, stirred at a speed of 400-600 r / min for 3-6 hours in a 50-70 DEG C water bath, and then subjected to vacuum impregnation treatment for 20-40 min, filtration, water washing, and drying at 90-100 DEG C for 1-3 hours to obtain the modified lepidolite slag.

[0014] The vacuum impregnation temperature is 50-60 DEG C, and the vacuum degree is 0.08-0.12 Pa.

[0015] The anaerobic ammonia oxidation reactor provided by the application also comprises a reactor cover arranged on the top of the reactor, a stirrer, and a water inlet pipe arranged at the bottom of the reactor.

[0016] The anaerobic ammonia oxidation reactor also comprises a reactor cover arranged on the top of the reactor, a stirrer, and a water inlet pipe arranged at the bottom of the reactor.

[0017] The reaction kettle is provided with a water bath insulation layer, and a transparent observation window is arranged on the cover at the top of the reaction kettle.

[0018] The beneficial effects of the present application are: The present application can provide microbial attachment points by filling the filler balls with carriers, and the autotrophic carriers provide a large specific surface area for anaerobic ammonia oxidation bacteria, which provides better attachment points for microorganisms, enables the microorganisms to better form a biofilm, increases the number and activity of the microorganisms, and improves the treatment efficiency of the reactor.

[0019] The polyurethane sponge is treated in the present application, and the special carrier prepared in this way can protect the microorganisms from the influence of hydraulic impact and provide a relatively stable living environment for the microorganisms; the presence of the carrier can change the water flow state in the reactor, form local turbulence and vortex, increase the contact opportunity of the microorganisms and the substrate, be beneficial to the mass transfer process of the substrate to the cell surface of the microorganisms, and thus promote the growth and metabolism of the microorganisms.

[0020] The specially prepared carrier of the present application can interact with the substances on the cell surface of the microorganisms, promote the attachment and aggregation of the microorganisms, and be beneficial to the formation of stable community structure of the microorganisms.

[0021] The carrier prepared in the present application can optimize the performance of the anaerobic ammonia oxidation reactor, and the carrier can increase the amount of microorganisms in the reactor, improve the volumetric loading of the reactor, enable the reactor to treat wastewater with higher concentration, effectively remove pollutants when treating wastewater with high ammonia nitrogen and high organic matter content, and improve the water quality of the effluent. Moreover, the presence of the carrier prepared in the present application can also improve the flow state in the reactor, make the water flow more uniform, avoid the occurrence of short flow and dead zones, improve the hydraulic efficiency of the reactor, and enable the reactor to operate more stably and efficiently.

[0022] The carrier of the present application can be widely applied in the field of biological denitrification of wastewater; greatly reduces the carbon source used in the denitrification process in the traditional biological denitrification process, also reduces the oxygen demand in the nitrification process, reduces the aeration amount, reduces the operation cost in the process of treating high-ammonia-nitrogen coal gas wastewater. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a structure schematic diagram of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system of Example 6.

[0024] The names and serial numbers of the parts in the figure are as follows: 1 is an inlet water bucket, 2 is a PN reactor, 3 is a lye bucket, 4 is an adjusting pool, 5 is an anaerobic ammonia oxidation reactor, and 6 is an aeration pipe. DETAILED DESCRIPTION Example 1

[0025] The carrier preparation method is: Deionized water and polyvinylpyrrolidone were mixed together in turn, stirred at 500 r / min for 40 min to obtain a mixed solution; the mass ratio of deionized water to polyvinylpyrrolidone was 100:1; Carbon nanotubes were added to the above-obtained mixed solution, stirred at 350 r / min for 2 hours, and then added to a high-speed homogenizer for homogenization treatment for 20 min, wherein the homogenization speed was 4500 r / min, to obtain a carbon nanotube dispersion liquid; the concentration of carbon nanotubes in the carbon nanotube dispersion liquid was 0.03wt%; The modified lepidolite slag was added to the above carbon nanotube dispersion liquid, and ultrasonic dispersion was performed to obtain a composite dispersion liquid; the mass ratio of modified lepidolite slag to carbon nanotube dispersion liquid was 1:150; The polyurethane sponge was soaked and cleaned with anhydrous ethanol for 15 min, and then dried at 50°C for 4 hours; Methoxytrimethylsilane was added to the ethanol solution to obtain a treatment liquid; the mass ratio of methoxytrimethylsilane to ethanol solution was 1:40; the mass fraction of the ethanol solution was 50%; The polyurethane sponge was added to the composite dispersion liquid at a mass ratio of 1:50, the temperature was adjusted to 80°C, and the mixture was stirred for 2 hours, then the treatment liquid was added, the mass ratio of the treatment liquid to the composite dispersion liquid was 1:15, and the stirring was continued for 4 hours, then filtration was performed, and the mixture was placed in a drying box at 120°C for 2 hours to obtain the carrier.

[0026] The modified lepidolite slag preparation method is: The lepidolite slag was ultra-finely pulverized to obtain lepidolite slag powder with an average particle size of 20μm; The lepidolite slag powder and nanosilica were added to an ethanol solution with a mass fraction of 90%, and then subjected to magnetic stirring at a stirring speed of 150 r / min for 40 min, followed by ultrasonic dispersion for 10 min to obtain a lepidolite slag powder and nanosilica dispersion liquid; The mass ratio of the lepidolite slag powder to nanosilica to ethanol solution was 30g:3g:300mL; KH550 was added to an ethanol solution with a mass fraction of 90%, and then stirred at a speed of 200 r / min for 40 min to obtain a KH550 dispersion liquid with a mass fraction of 10%; The KH550 dispersion liquid was added to the lepidolite slag powder and nanosilica dispersion liquid at a volume ratio of 1:5, and then stirred at a speed of 500 r / min for 4 hours in a water bath at 60°C, and then placed in a vacuum impregnation reactor for vacuum impregnation treatment for 30 min, and finally subjected to suction filtration, water washing, and drying at 100°C for 2 hours to obtain the modified lepidolite slag. The vacuum impregnation temperature is 55°C, and the vacuum degree is 0.1 Pa. The anaerobic ammonia oxidation reactor 5 mainly provides a reaction area for the Anammox denitrification process. The anaerobic ammonia oxidation bacteria convert NH4 + -N and the generated NO2 - -N into N2, which escapes, and the process does not require the addition of a carbon source, saving costs, and there is no large amount of sludge discharge.

[0027] The outlet water bucket is a 50L plastic bucket, and its main function is to ensure the clarity of the process outlet water.

[0028] The anaerobic ammonia oxidation reactor 5 of the present embodiment includes a reaction kettle, a reaction kettle cover arranged on the top of the reaction kettle, a stirrer arranged in the reaction kettle, and a water inlet pipe arranged at the bottom of the reaction kettle. The reaction kettle is provided with a water bath insulation layer. A round opening is arranged on the reaction kettle cover for convenient observation of the internal conditions. The reaction kettle is filled with a plurality of packing spheres and carriers. The packing spheres are equipped with a plurality of carriers. The main volume of the reaction kettle 5 is 32L, and the maximum can simultaneously process 24L of water inside. The reaction kettle 41 is provided with a 7.0cm thick water bath insulation layer, and the entire reaction kettle is wrapped with 2.5cm of insulation cotton. The filling rate of the packing spheres in the reaction kettle is 55%, and the packing spheres are filled with carriers, which occupy 70% of the internal space of the packing spheres. Example 2

[0029] The technical solution of the present embodiment is the same as that of Example 1, and the difference is that: The carrier preparation method is as follows: Deionized water and polyvinylpyrrolidone were mixed together at a mixing speed of 500r / min for 40min to obtain a mixed solution. The mixing mass ratio of deionized water to polyvinylpyrrolidone was 100:1. Carbon nanotubes were added to the above obtained mixed solution, stirred at a speed of 350r / min for 2 hours, and then added to a high-speed homogenizer for homogenization treatment for 20min. The homogenization speed was 4500r / min. A carbon nanotube dispersion liquid was obtained. The carbon nanotube concentration in the carbon nanotube dispersion liquid was 0.035wt%. Modified lepidolite slag was added to the above carbon nanotube dispersion liquid, and ultrasonic dispersion was performed to obtain a composite dispersion liquid. The mixing mass ratio of modified lepidolite slag to carbon nanotube dispersion liquid was 1:152. Polyurethane sponge was soaked and cleaned with anhydrous ethanol for 15min, and then dried at 50°C for 4 hours. Methoxytrimethylsilane was added to the ethanol solution to obtain a treatment liquid. The mixing mass ratio of methoxytrimethylsilane to ethanol solution was 1:40. The mass fraction of the ethanol solution was 50%. The polyurethane sponge is added into the composite dispersion liquid at a mass ratio of 1:50, the temperature is adjusted to 80 DEG C, and the mixture is stirred for 2 hours, then the treatment liquid is added, the mass ratio of the treatment liquid to the composite dispersion liquid is 1:16, the stirring is continued for 4 hours, then the mixture is filtered, and the mixture is placed in a drying box, dried at 120 DEG C for 2 hours to obtain the carrier.

[0030] The preparation method of the modified lepidolite slag is as follows: The lepidolite slag is ultra-finely pulverized to obtain lepidolite slag powder with an average particle size of 20 microns; The lepidolite slag powder and nano-silicon dioxide are added into an ethanol solution with a mass fraction of 90%, the mixture is stirred by magnetic force for 40 minutes at a stirring speed of 150 r / min, and then the mixture is ultrasonically dispersed for 10 minutes to obtain a lepidolite slag powder and nano-silicon dioxide dispersion liquid; The mixing ratio of the lepidolite slag powder, nano-silicon dioxide and the ethanol solution is 32 g:3 g:300 mL; The KH550 is added into an ethanol solution with a mass fraction of 90%, and the mixture is stirred at a speed of 200 r / min for 40 minutes to obtain a KH550 dispersion liquid with a mass fraction of 10%; The KH550 dispersion liquid is added into the lepidolite slag powder and nano-silicon dioxide dispersion liquid at a volume ratio of 1:5.4, the mixture is stirred at a speed of 500 r / min for 4 hours in a water bath at 60 DEG C, and then the mixture is filtered and washed with water, and the mixture is dried at 100 DEG C for 2 hours to obtain the modified lepidolite slag. Example 3

[0031] The same as the technical solution of Example 1, the difference is that: The preparation method of the carrier is as follows: The deionized water and the polyvinylpyrrolidone are sequentially mixed together, and the mixture is stirred at a speed of 500 r / min for 40 minutes to obtain a mixed liquid; the mixing mass ratio of the deionized water to the polyvinylpyrrolidone is 100:1; The carbon nanotubes are added into the above-obtained mixed liquid, and the mixture is stirred at a speed of 350 r / min for 2 hours, and then the mixture is added into a high-speed homogenizer for homogenization treatment for 20 minutes, wherein the homogenization speed is 4500 r / min, to obtain a carbon nanotube dispersion liquid; the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.04 wt%; The modified lepidolite slag is added into the above-obtained carbon nanotube dispersion liquid, and the mixture is ultrasonically dispersed to obtain a composite dispersion liquid; the mixing mass ratio of the modified lepidolite slag to the carbon nanotube dispersion liquid is 1:160; The polyurethane sponge is soaked and cleaned with anhydrous ethanol for 15 minutes, and then the sponge is dried at 50 DEG C for 4 hours; Add methoxytrimethylsilane to the ethanol solution to obtain a treatment solution; the mass ratio of methoxytrimethylsilane to the ethanol solution is 1:40; the mass fraction of the ethanol solution is 50%; Add the polyurethane sponge to the composite dispersion liquid at a mass ratio of 1:50, adjust the temperature to 80 DEG C, and keep stirring for 2 hours, then add the treatment solution, the mass ratio of the treatment solution to the composite dispersion liquid is 1:17, continue to stir for 4 hours, then filter, and place in a drying box, 120 DEG C, dry for 2 hours, to obtain the carrier.

[0032] The preparation method of the modified lepidolite slag is as follows: Ultrafine grind the lepidolite slag to obtain lepidolite slag powder with an average particle size of 20 microns; Add the lepidolite slag powder and nano-silicon dioxide to an ethanol solution with a mass fraction of 90%, and stir magnetically for 40 min at a stirring speed of 150 r / min, then ultrasonically disperse for 10 min to obtain a lepidolite slag powder and nano-silicon dioxide dispersion liquid; The mixing ratio of the lepidolite slag powder, nano-silicon dioxide, and ethanol solution is 33 g:3 g:300 mL; Add KH550 to an ethanol solution with a mass fraction of 90%, and stir at a speed of 200 r / min for 40 min to obtain a KH550 dispersion liquid with a mass fraction of 10%; Add the KH550 dispersion liquid to the lepidolite slag powder and nano-silicon dioxide dispersion liquid at a volume ratio of 1:6, stir at a speed of 500 r / min for 4 hours in a 60 DEG C water bath, then filter, wash with water, and dry at 100 DEG C for 2 hours to obtain the modified lepidolite slag. Example 4

[0033] The preparation method of the anaerobic ammonia oxidation reactor carrier comprises the following steps: A. Prepare a polyvinylpyrrolidone aqueous solution with a mass ratio of 80:1, add carbon nanotubes to the polyvinylpyrrolidone aqueous solution, and disperse uniformly to obtain a carbon nanotube dispersion liquid; the concentration of the carbon nanotubes in the carbon nanotube dispersion liquid is 0.03wt%; The preparation method of the carbon nanotube dispersion liquid comprises the following steps: Add the carbon nanotubes to the above-obtained mixed solution, stir at a speed of 300 r / min for 1 hour, then add to a high-speed homogenizer for homogenization treatment for 15 min, wherein the homogenization speed is 4000 r / min, to obtain the carbon nanotube dispersion liquid; B. Add the modified lepidolite slag to the carbon nanotube dispersion liquid, and ultrasonically disperse to obtain a composite dispersion liquid; the mass ratio of the modified lepidolite slag to the carbon nanotube dispersion liquid in the composite dispersion liquid is 1:150; C. Add methoxytrimethylsilane to the ethanol solution to obtain a treatment solution; in the treatment solution, the mass ratio of methoxytrimethylsilane to the ethanol solution is 1:30; the mass fraction of the ethanol solution is 45% D. Clean the polyurethane sponge with anhydrous ethanol, dry at 40°C for 3 hours, then mix the polyurethane sponge and the composite dispersion liquid uniformly at a mass ratio of 1:40, adjust the temperature to 70°C, and keep stirring for 1 hour, then add the treatment solution, the mass ratio of the treatment solution to the composite dispersion liquid is 1:18, continue stirring for 3 hours, then filter, place in a drying box, dry at 110°C for 1 hour, to obtain the carrier.

[0034] The preparation method of the modified lepidolite slag includes the following steps: The lepidolite slag is ultra-finely pulverized to obtain lepidolite slag powder with an average particle size of 20 μm; the lepidolite slag powder and nano-silicon dioxide are added to an ethanol solution with a mass fraction of 85%, stirred uniformly, and then ultrasonically dispersed for 10 min to obtain a lepidolite slag powder and nano-silicon dioxide dispersion liquid; wherein the mass ratio of the lepidolite slag powder to the nano-silicon dioxide and the ethanol solution is 30:3:230; KH550 is added to an ethanol solution with a mass fraction of 90%, mixed uniformly, and configured into a KH550 dispersion liquid with a mass fraction of 10%; The KH550 dispersion liquid is added to the lepidolite slag powder and nano-silicon dioxide dispersion liquid at a volume ratio of 1:5, stirred at a speed of 400 r / min for 3 hours under water bath at 50°C, then vacuum-impregnated at 50°C and a vacuum degree of 0.08 Pa for 20 min, filtered, washed with water, and dried at 90°C for 1 hour to obtain the modified lepidolite slag. The vacuum-impregnation temperature is.

[0035] The anaerobic ammonia oxidation reactor 5 of the embodiment includes a reaction kettle, a reaction kettle cover arranged at the top of the reaction kettle, a stirrer arranged in the reaction kettle, and a water inlet pipe arranged at the bottom of the reaction kettle. The reaction kettle is provided with a water bath insulation layer. A round opening for conveniently observing the internal condition is arranged on the reaction kettle cover. A plurality of filler balls and carriers are filled in the reaction kettle. The filler balls are equipped with a plurality of carriers. The main volume of the reaction kettle 5 is 32 L, and the maximum can simultaneously treat 24 L of water inside. The reaction kettle 41 is provided with a water bath insulation layer with a thickness of 7.0 cm, and the whole reaction kettle is wrapped with insulation cotton with a thickness of 2.5 cm. The filling rate of the filler balls in the reaction kettle is 55%, and the carriers are filled in the filler balls, and the carriers occupy 70% of the space inside the filler balls. Example 5

[0036] The preparation method of the anaerobic ammonia oxidation reactor carrier includes the following steps: A, configure the mass ratio of polyvinylpyrrolidone aqueous solution is 120:1, carbon nanotubes into the polyvinylpyrrolidone aqueous solution, dispersed uniformly, get carbon nanotube dispersion; carbon nanotube dispersion, carbon nanotube concentration is 0.04wt%; The preparation method of the carbon nanotube dispersion includes the following steps: To the above obtained mixed solution, add carbon nanotubes, stirring at 400r / min for 3 hours, and then add to the high speed homogenizer for homogenization treatment for 40min, wherein the homogenization speed is 000r / min, to obtain the carbon nanotube dispersion; B, the modified lithium mica slag is added to the carbon nanotube dispersion, and is dispersed by ultrasonic to obtain a composite dispersion; in the composite dispersion, the mass ratio of modified lithium mica slag and carbon nanotube dispersion is 1: 160; C, add methoxytrimethylsilane to ethanol solution to obtain a treatment liquid; in the treatment liquid, the mass ratio of methoxytrimethylsilane and ethanol solution is 1:50; the mass fraction of ethanol solution is 55% D, the polyurethane sponge is cleaned with anhydrous ethanol, dried at 60℃ for 5 hours, then the polyurethane sponge and the composite dispersion are mixed uniformly at a mass ratio of 1:60, the temperature is adjusted to 90℃, and stirring is carried out for 3 hours, then the treatment liquid is added, the mass ratio of the treatment liquid and the composite dispersion is 1:16, and stirring is continued for 5 hours, then filtration is carried out, and the carrier is placed in a drying box at 130℃ and dried for 3 hours.

[0037] The preparation method of the modified lithium mica slag includes the following steps: The lithium mica slag is ultra-finely pulverized to obtain lithium mica slag powder with an average particle size of 20μm; the lithium mica slag powder and nano-silicon dioxide are added to an ethanol solution with a mass fraction of 92%, stirred uniformly, and then ultrasonically dispersed for 10min to obtain a lithium mica slag powder and nano-silicon dioxide dispersion; wherein the mass ratio of lithium mica slag powder, nano-silicon dioxide and ethanol solution is 33; 3: 320; KH550 is added to an ethanol solution with a mass fraction of 90%, mixed uniformly, and configured into a KH550 dispersion with a mass fraction of 10%; The KH550 dispersion is added to the lithium mica slag powder and nano-silicon dioxide dispersion at a volume ratio of 1:6, stirred at 600r / min for 6 hours under water bath at 70℃, then vacuum impregnation treatment is carried out at 60℃ and a vacuum degree of 0.12Pa for 40min, filtered, washed with water, and dried at 100℃ for 3 hours to obtain the modified lithium mica slag. The vacuum impregnation temperature is.

[0038] The anaerobic ammonia oxidation reactor 5 of the embodiment comprises a reaction kettle, a kettle cover arranged at the top of the reaction kettle, a stirrer arranged in the reaction kettle, and a water inlet pipe arranged at the bottom of the reaction kettle. The reaction kettle is provided with a water bath heat preservation layer. A round opening for conveniently observing the internal condition is arranged on the kettle cover. A plurality of filler balls and carriers are filled in the reaction kettle. The filler balls are assembled with a plurality of carriers. The main volume of the reaction kettle 5 is 32L, and the highest can simultaneously process 24L of water inside. The reaction kettle 41 is provided with a 7.0cm thick water bath heat preservation layer, and the whole reaction kettle is wrapped with 2.5cm of heat preservation cotton. The filling rate of the filler balls in the reaction kettle is 55%, and the carriers are filled in the filler balls, and the carriers occupy 70% of the space inside the filler balls. Embodiment 6

[0039] The high ammonia-nitrogen coal gasification wastewater is treated by using a system, which is a short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system commonly used in the prior art, comprising a water inlet bucket 1, a PN reactor 2, a lye bucket 3, a regulating tank 4, an anaerobic ammonia oxidation reactor 5, a water outlet bucket, and a regulating system in sequence. The PN reactor domesticates short-cut nitrification bacteria, ensures the stable supply of nitrite in the anaerobic ammonia oxidation reactor, and creates the best environment for the stable growth of ammonia oxygen ammonia oxidation bacteria. The regulating system comprises: a pH automatic regulating device, which adjusts the pH of the PN reactor to the range of 7.5-8.5; an aeration device, which ensures that the DO concentration of the PN reactor is maintained at 1.1-1.4mg / L; a heating device, which ensures that the anaerobic ammonia oxidation reaction temperature is maintained at 30-35℃; and a stirring device, which makes the water inlet more uniform and the denitrification treatment effect better.

[0040] The water inlet bucket 1 is a 100L plastic bucket. The PN reactor 2 comprises a sewage water inlet arranged at the bottom of the side wall of the reactor, a water outlet arranged at the upper part of the side wall of the reactor, an alkali water inlet arranged at the middle part of the side wall of the reactor, an aeration pipe 6 arranged at the bottom of the reactor, and a pH automatic regulating device. An aeration pump and a gas flow meter connected with the aeration pipe are arranged outside the reactor. The pH automatic regulating device of the reactor comprises a pH online monitor placed in the reactor, and a peristaltic pump controlled by the pH online monitor. When the pH is lower than 7.5, the peristaltic pump controlled by the pH online monitor pumps the alkali in the lye bucket 3 into the PN reactor through the alkali water inlet arranged at the middle part of the side wall of the reactor.

[0041] The main function of the PN reactor 2 is to provide a short-cut nitrification area and to occur a short-cut nitrification reaction. The short-cut nitrification reaction refers to that the nitrification bacteria partially oxidize ammonia nitrogen (NH4 ⁺ ) in the wastewater into nitrite (NO2 ⁻ ) under aerobic conditions.

[0042] In addition, the PN reactor in which the short-cut nitrification process occurs can provide the nitrite (NO2 ⁻ ].

[0043] The adjusting tank 4 draws the wastewater in the water inlet bucket 1 into the adjusting tank and mixes it with the effluent of the PN reactor 2 through the water inlet peristaltic pump, and then draws it into the Anammox reactor through the water inlet peristaltic pump 2.

[0044] The method for treating high-ammonia-nitrogen coal-gas wastewater by using the short-cut nitrification-Anammox combined denitrification process system comprises the following steps: Step one, start the system, the wastewater in the water inlet bucket is the high-ammonia-nitrogen coal-gas wastewater and tap water, the ammonia-nitrogen concentration of the inlet water is 120±5 mg / L, the pH of the inlet water is between 7.30 and 7.80, and the water inlet is 24 L per day; Step two, draw the wastewater in the water inlet bucket through the PN water inlet pump, and inlet the wastewater from the bottom of the sidewall of the PN reactor; the working flow of the water inlet pump is 24 L / h, and the working time is 30 min per day; Step three, the short-cut nitrification reaction occurs in the PN reactor, the reaction time is 23 h, the wastewater is drawn into the adjusting tank through the PN water outlet pump after 30 min of precipitation, the PN reactor is inoculated with 1 / 3 of the volume of nitrification sludge, and the wastewater is drawn into the adjusting tank through the water inlet peristaltic pump. Step four, draw the wastewater from the water inlet bucket to the bottom of the adjusting tank through the adjusting tank water inlet pump, the working flow of the adjusting tank water inlet pump is 0.5 L / h, and the working time is 24 h per day; Step five, draw the mixed wastewater from the middle of the adjusting tank through the Anammox water inlet pump, and pump it into the bottom of the Anammox reactor, the working flow of the Anammox water inlet pump is 0.5 L / h, and the working time is 24 h per day; Step six, Anammox denitrification occurs in the Anammox reactor; the agitator in the Anammox reactor is always on to keep the reactor in a mixed state; the Anammox reactor is inoculated with 1 / 4 of the volume of Anammox sludge; the filler balls and carriers are added to the Anammox reactor, the filling rate is 52%, and a plurality of carriers are arranged in each filler ball. Step seven, after the denitrification reaction of the Anammox reactor, the wastewater flows into the water outlet bucket by gravity.

[0045] The temperature of the PN reactor changes with the natural temperature, and the temperature is 25.5±1.9℃; the temperature of the Anammox reactor is controlled, and the temperature is 30℃.

[0046] Based on the system and the test method, a carrier comparison experiment is carried out, and the specific experimental conditions are as follows: I. Preparation of a comparison case: The carrier of the comparative example 1 is prepared by using the method of the example 1, and the difference from the example 1 is that the carrier is replaced by untreated polyurethane sponge.

[0047] Comparative Example 2 carrier: prepared by the method of Example 1, distinguished from Example 1 in that the lithium mica residue was not modified during the carrier preparation process.

[0048] The main chemical components of the lithium mica residue in the examples and comparative examples are as follows in Table 1: Table 1 mass percentage silicon dioxide 47.63 alumina 25.25 iron oxide 5.32 calcium oxide 18.63 potassium oxide 7.15 sodium oxide 5.57 magnesium oxide 3.02 titanium oxide 0.05 other balance II. Experimental process: 1. The coal gasification wastewater from a certain thermal power plant in Pingguo City was used as raw water in the influent tank of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system, and the NH4 + -N concentration was maintained at 918.3±28.1 mg / L; the carrier used in the anaerobic ammonia oxidation reactor was the carrier prepared in Example 1; Table 2: Effluent quality of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system: running days unit (mg / L) effluent ammonia nitrogen effluent nitrite total nitrogen removal rate 59 12.54 7.93 79.53858 60 11.36 6.58 79.93809 61 8.27 3.58 81.84378 62 7.25 0.98 83.41957 63 15.87 4.61 80.43371 64 14.84 1.97 80.90262 65 10.79 3.72 81.97974 66 16.23 2.18 80.47028 67 26.64 15.57 77.77333 68 11.29 3.32 83.23984 69 14.12 4.21 82.53214 70 13.58 3.81 82.70651 71 9.24 21.76 79.7049 72 67.54 63.42 68.53472 73 66.84 65.4 68.34102 74 49.64 59.32 71.40679 75 49.17 60.44 71.30668 76 33.25 43.16 75.81028 77 32.68 42.12 76.21058 78 34.21 40.95 76.18313 79 12.22 20.11 81.94733 80 7.57 6.29 84.65496 81 7.22 4.32 83.94144 82 38.99 37.9 77.78356 83 19.99 12.22 81.94729 84 14.82 6.99 83.08585 85 14.99 5.26 84.10018 86 8.24 2.25 84.73427 87 32.78 13.19 81.64382 88 18.21 3.21 83.61533 89 19.19 4.1 83.55789 After a long period of stable operation of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system for treating high-ammonia-nitrogen coal gasification wastewater, the total nitrogen removal rate was stably above 68%, effectively proving the denitrification stability and excellent denitrification performance of the system.

[0049] 2. The experiment was divided into five groups, and the coal gasification wastewater from a certain thermal power plant in Pingguo City was used as raw water in the influent tank of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system in the five groups, and the NH4 + -N concentration was maintained at 918.3±28.1 mg / L; the carriers used in the anaerobic ammonia oxidation reactors in the five groups were the carriers prepared in Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 2, respectively; total nitrogen removal rate Example 1 84.65496 Example 2 84.02671 Example 3 84.33263 Comparative Example 1 70.32146 Comparative Example 2 78.55932 As can be seen from Table 3, the processes of Examples 1-3 of the present application have excellent denitrification performance.

[0050] 3. Based on the sample of Example 1, the influence of the filling rate of different filler balls on the total nitrogen removal rate was compared by counting after 70 days of operation: The coal gasification wastewater from a certain thermal power plant in Pingguo City was used as raw water in the influent tank of the short-cut nitrification-anaerobic ammonia oxidation combined denitrification process system, and the NH4 + -N concentration was maintained at 918.3±28.1 mg / L; filling rate total nitrogen removal rate 40 75.34189 45 79.21546 50 81.02769 55 82.70651 60 82.13423 As can be seen from Table 4, with the increase of the filling rate of the filler balls, the total nitrogen removal rate first increases and then decreases slightly, indicating that when the filling rate exceeds 55%, further increasing the filling rate cannot increase the total nitrogen removal rate. Considering the economic benefits and costs, the optimal filling rate is 55%.

[0051] The preferred embodiments of the application disclosed above are only to help explain the present application. The preferred embodiments are not intended to be exhaustive or to limit the application to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the application be limited not with this detailed description, but rather by the claims and the full range of equivalents to which such claims are entitled.

Claims

1. An anaerobic ammonium oxidation reactor carrier, characterized in that: The preparation method comprises the following steps: A. Prepare a polyvinyl pyrrolidone aqueous solution with a mass ratio of 80-120:1, add carbon nanotubes into the polyvinyl pyrrolidone aqueous solution, and disperse them evenly to obtain a carbon nanotube dispersion; the carbon nanotube concentration in the carbon nanotube dispersion is 0.03-0.04 wt%; B. adding the modified lepidolite slag to the carbon nanotube dispersion, and performing ultrasonic dispersion to obtain a composite dispersion; in the composite dispersion, the mass ratio of the modified lepidolite slag to the carbon nanotube dispersion is 1:150-160; C. adding methoxytrimethylsilane to the ethanol solution to obtain a treatment solution; in the treatment solution, the mass ratio of methoxytrimethylsilane to the ethanol solution is 1:30-50; D. Mix the polyurethane sponge and the composite dispersion liquid in a mass ratio of 1:40-60, adjust the temperature to 70-90°C, keep stirring for 1-3 hours, then add the treatment liquid, the mass ratio of the treatment liquid to the composite dispersion liquid is 1:15-18, continue stirring for 3-5 hours, then filter, place in a drying oven at 110-130°C, and dry for 1-3 hours to obtain a carrier.

2. The anaerobic ammonium oxidation reactor carrier according to claim 1, characterized in that: In step A, the method for preparing the carbon nanotube dispersion comprises the following steps: Add carbon nanotubes to the mixed solution obtained above, stir at a speed of 300-400 r / min for 1-3 hours, then add to a high-speed homogenizer and homogenize for 15-40 minutes, wherein the homogenization speed is 4000-5000 r / min, to obtain a carbon nanotube dispersion.

3. The anaerobic ammonium oxidation reactor carrier according to claim 1, characterized in that: In the step D, the polyurethane sponge is cleaned with anhydrous ethanol, dried, and then evenly mixed with the composite dispersion according to a mass ratio.

4. The anaerobic ammonium oxidation reactor carrier according to claim 3, characterized in that: The polyurethane sponge is cleaned with anhydrous ethanol and then dried at 40-60° C. for 3-5 hours.

5. The anaerobic ammonium oxidation reactor carrier according to claim 1, characterized in that: In the step C, the mass fraction of the ethanol solution is 45-55%.

6. The anaerobic ammonium oxidation reactor carrier according to claim 1, characterized in that: The preparation method of the modified lepidolite slag comprises the following steps: The lepidolite slag is ultrafinely ground to obtain lepidolite slag powder with an average particle size of 20 μm; the lepidolite slag powder and nano-silica are added to an ethanol solution with a mass fraction of 85-92%, stirred evenly, and then ultrasonically dispersed for 10 minutes to obtain a lepidolite slag powder and nano-silica dispersion; wherein the mass ratio of the lepidolite slag powder to the nano-silica to the ethanol solution is 30-33; 3:230-320; KH550 was added to a 90% by mass ethanol solution and mixed evenly to prepare a 10% by mass KH550 dispersion. The KH550 dispersion is added to the lepidolite slag powder and the nano-silica dispersion in a volume ratio of 1:5-6, stirred at a speed of 400-600 r / min for 3-6 hours in a water bath at 50-70°C, then vacuum impregnated for 20-40 minutes, filtered, washed with water, and dried at 90-100°C for 1-3 hours to obtain modified lepidolite slag.

7. The anaerobic ammonium oxidation reactor carrier according to claim 6, characterized in that: The vacuum impregnation temperature is 50-60° C., and the vacuum degree is 0.08-0.12 Pa.

8. An anaerobic ammonium oxidation reactor, using the anaerobic ammonium oxidation reactor carrier according to any one of claims 1 to 7, characterized in that: The invention also comprises a reaction kettle, wherein the reaction kettle is filled with a plurality of filler balls, and a plurality of carriers are assembled in the filler balls.

9. The anaerobic ammonium oxidation reactor according to claim 8, characterized in that: The invention also includes a reactor cover arranged on the top of the reactor, a stirrer, and a water inlet pipe arranged at the bottom of the reactor.

10. The anaerobic ammonium oxidation reactor according to claim 8, characterized in that: The reactor is provided with a water bath insulation layer, and a transparent observation window is provided on the cover on the top of the reactor.

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