CN110902828B - Comprehensive treatment process for high ammonia nitrogen wastewater - Google Patents

Comprehensive treatment process for high ammonia nitrogen wastewater Download PDF

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CN110902828B
CN110902828B CN201911248108.1A CN201911248108A CN110902828B CN 110902828 B CN110902828 B CN 110902828B CN 201911248108 A CN201911248108 A CN 201911248108A CN 110902828 B CN110902828 B CN 110902828B
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thiourea
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CN110902828A (en
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赵选英
程夫苓
杨峰
田帅慧
周腾腾
刘君君
单昊
唐为清
戴建军
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Jiangsu Nanda Huaxing Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2209/14—NH3-N
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Abstract

The invention discloses a comprehensive treatment process of high ammonia nitrogen wastewater, belonging to the technical field of chemical wastewater treatment. It comprises the following steps: (1) pretreating the high ammonia nitrogen wastewater, and carrying out nitration reaction on the pretreated effluent; (2) carrying out denitrification reaction on the effluent after the nitrification reaction, and using the wastewater containing thiourea as the water quality regulation; (3) and carrying out aerobic reaction on the effluent after the denitrification reaction. The invention can effectively reduce the ammonia nitrogen concentration in the wastewater, simultaneously can synchronously purify the thiourea-containing organic wastewater, and the effluent reaches the general garden take-over standard, namely COD is less than or equal to 500mg/L and the ammonia nitrogen is less than or equal to 50 mg/L.

Description

Comprehensive treatment process for high ammonia nitrogen wastewater
Technical Field
The invention belongs to the technical field of chemical wastewater treatment, and particularly relates to a comprehensive treatment process of high ammonia nitrogen wastewater.
Background
With the development of modern industry, the discharge amount of high-concentration ammonia nitrogen (hereinafter referred to as high ammonia nitrogen) wastewater is gradually increased, the source of the high-concentration ammonia nitrogen wastewater is extremely wide, and the high-concentration ammonia nitrogen wastewater relates to various industries, and a series of ecological environment problems are caused by excessive discharge of the high-concentration ammonia nitrogen wastewater. For the reasons, the national discharge standard of the ammonia nitrogen wastewater is further improved, so that the treatment of the high ammonia nitrogen wastewater is concerned for various industries.
The purpose of qualified discharge can be achieved by selecting a proper wastewater treatment method according to the self properties of the ammonia nitrogen wastewater. The existing treatment method aiming at the high ammonia nitrogen wastewater is not limited to three types of physical method, chemical method and biological method and combination thereof. However, physical methods and chemical methods alone have the disadvantages that the range of the water quality of the wastewater which can be treated is wide, but the treatment efficiency of the wastewater is relatively low, the treatment cost is high, the management is complex, and even secondary pollution to the environment is caused, so that the wastewater cannot be applied and popularized on a large scale; regarding the biological method, common biological treatment means mainly include an activated sludge method, a biofilm method and an anaerobic biological treatment method, and the treatment of sewage does not cause secondary pollution to the environment, but has great requirements on the quality of inlet water of the wastewater. For example, anaerobic treatment has the disadvantages of high process sensitivity, weak denitrification function, unpleasant odor, long start-up period, and the like.
Besides containing ammonia nitrogen, a large amount of ammonia nitrogen wastewater containing thiourea can be generated in a plurality of industrial productions, and the method is widely applied to the fields of industry, medicine, agriculture and the like, the thiourea has high toxicity, genetic harm exists on human bodies and animals, the dosage is large, even death can occur, and the thiourea wastewater also has an inhibiting effect on microorganisms, so the thiourea wastewater has the practical problems of poor biodegradability (B/C ratio of 0.0151) and large treatment difficulty. At present, the commonly used treatment method of the ammonia nitrogen wastewater containing thiourea is limited to a physical method and a chemical method. For example, the Chinese patent application with publication number CN110104861A and publication number 2019.08.09 discloses a process for treating thiourea-containing wastewater, which comprises the steps of firstly carrying out deep oxidation on the wastewater by adopting electro-Fenton to achieve the purpose of fully removing thiourea, then adjusting pH to carry out reduced pressure stripping, absorbing the generated ammonia gas by using acid, and fully removing ammonia nitrogen substances. However, the treatment method of the thiourea-containing wastewater is mainly a chemical and/or physical method, and has the conventional defects of the chemical/physical method.
Based on this, the best selection for the thiourea-containing wastewater/high ammonia nitrogen wastewater is to perform classified collection and separate treatment, but from the current research and application situation and development of domestic and foreign wastewater biological treatment, or from the economic perspective, any single treatment method in three treatment methods of physical method, chemical method and biological method cannot achieve the purpose of considering both the water treatment effect and controlling the economic cost, and the future wastewater treatment needs to be taken out, especially the thiourea-containing wastewater/high ammonia nitrogen wastewater needs to be applied by combining the above multiple processes, so how to develop an advanced, efficient and energy-saving comprehensive wastewater treatment process on the basis of the existing process is still the development of the future water treatment process.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the existing single treatment method of the thiourea-containing wastewater or the high ammonia nitrogen wastewater cannot achieve the purposes of considering both the water treatment effect and controlling the economic cost, the invention provides a comprehensive treatment process of the high ammonia nitrogen wastewater, which can effectively reduce the ammonia nitrogen concentration in the wastewater and simultaneously can synchronously achieve the purification purpose of the thiourea-containing organic wastewater, and the effluent reaches the general campus takeover standard, namely COD is less than or equal to 500mg/L and ammonia nitrogen is less than or equal to 50 mg/L.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a comprehensive treatment process of high ammonia nitrogen wastewater, which comprises the following steps:
(1) pretreating the high ammonia nitrogen wastewater, and carrying out nitration reaction on the pretreated effluent;
(2) carrying out denitrification reaction on the effluent after the nitrification reaction, and using the wastewater containing thiourea as the water quality regulation;
(3) and carrying out aerobic reaction on the effluent after the denitrification reaction.
Preferably, in the step (1), Fenton oxidation, neutralization and precipitation, anaerobic treatment and aerobic reaction are carried out on the high ammonia nitrogen wastewater to complete pretreatment; the aerobic reaction is mainly used for removing organic matters, the pH of inlet water is controlled to be 7-8, and the hydraulic retention time is 1-2 d.
Preferably, the high ammonia nitrogen wastewater is neutralized and precipitated and then separated to obtain supernatant and metal mud, and low-concentration wastewater is introduced into the supernatant to be used as water quality regulation for homogenizing and homogenizing.
Preferably, the COD of the low-concentration wastewater is 2000-4000mg/L, and the ammonia nitrogen concentration is 80-150 mg/L; the source is low-concentration waste water, initial rainwater and domestic sewage generated in the production process;
preferably, the effluent quality COD after the pretreatment of the high ammonia nitrogen wastewater in the step (1) is 4000-6000mg/L, and the ammonia nitrogen concentration is 200-250 mg/L.
Preferably, the COD of the effluent after the nitration reaction in the step (1) is 500-800mg/L, and the ammonia nitrogen concentration is 5-20 mg/L; the nitration reaction is mainly used for removing ammonia nitrogen, the pH of inlet water is controlled to be 7-9, and the hydraulic retention time is 2-4 d.
Preferably, in the step (2), the thiourea content of the thiourea wastewater is 2-5mg/L, and the volume ratio of the introduced quantity of the thiourea wastewater to the water inflow of the denitrification reaction is 1: 40.
Preferably, the thiourea wastewater is wastewater subjected to complexing precipitation, catalytic oxidation and neutralization precipitation treatment; the metal ion solution used for the complex precipitation can be derived from a solution containing metal ions obtained by carrying out acid dissolution on the separated metal mud, wherein the metal ions comprise one or more of alkaline earth metal, scandium, yttrium, lanthanide, iron, ferrous and copper; the catalytic oxidation is electrocatalytic oxidation, electro-Fenton or ozone catalytic oxidation and the like.
Preferably, in the step (2), the effluent COD after the denitrification reaction is 200-500mg/L, and the ammonia nitrogen concentration is 10-40 mg/L; the denitrification reaction is mainly used for removing nitrate nitrogen, the pH of inlet water is controlled to be 7-8, and the hydraulic retention time is 1-2 d.
Preferably, the method is characterized in that: the COD of the high ammonia nitrogen wastewater is 8000mg/L of 5000-.
Preferably, in the step (3), the aerobic reaction is mainly used for removing organic matters, the pH value of inlet water is controlled to be 7-9, and the hydraulic retention time is 1-2 d.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the comprehensive treatment process of the high-ammonia-nitrogen wastewater reasonably allocates the nitrification and carbon oxidation functions, avoids the possibility that inhibitory substances or heterotrophic bacteria influence nitrifying bacteria in a combined system, reduces the nitrification performance, further degrades and mineralizes organic matters in anaerobic effluent through an aerobic reaction system, mostly degrades organic inhibitory substances before influencing the nitrifying bacteria, can generate a synergistic effect with the nitrifying bacteria when entering a same-level nitrification reactor, and degrades CO generated by the organic matters by the heterotrophic bacteria2Can be used as an inorganic carbon source of nitrifying bacteria to ensure the normal operation of the nitrification function.
(2) The comprehensive treatment process of the high-ammonia-nitrogen wastewater provided by the invention effectively avoids the inhibition effect of thiourea substances in the wastewater on a biological nitrification system, the thiourea wastewater enters the denitrification system in a cross-stage manner after complex precipitation-catalytic oxidation, the inhibition effect of the thiourea substances on the nitrification system is avoided, meanwhile, the thiourea wastewater can be used as the denitrification system to provide a carbon source and an electron donor, the denitrification efficiency of the denitrification system is improved, and the thiourea wastewater is further biodegraded.
Drawings
FIG. 1 is a schematic view of a process flow of comprehensive treatment of high ammonia nitrogen wastewater provided by the present invention;
FIG. 2 is a schematic view of the process flow for treating high ammonia nitrogen wastewater in comparative example 1;
FIG. 3 is a schematic view of the process flow for treating high ammonia nitrogen wastewater in comparative example 2;
FIG. 4 is a schematic view of the process flow for treating high ammonia nitrogen wastewater in comparative example 3.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
In this embodiment, the steps for treating the high ammonia nitrogen wastewater are as follows:
(1) pretreating high ammonia nitrogen wastewater, sending pretreated effluent into a nitration reaction device added with activated sludge for nitration reaction, wherein the used microorganism is mainly used for removing ammonia nitrogen, controlling the pH of the influent to 9, and the hydraulic retention time is 4 d;
(2) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the inlet water to 7, controlling the hydraulic retention time to be 2d, and using thiourea-containing wastewater (the quality of the wastewater is shown in Table 2) as the water quality regulation;
(3) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction;
(4) and (4) precipitating the effluent obtained in the step (3) and discharging supernatant.
The effluent quality is shown in table 1.
TABLE 1 wastewater treatment Water quality index
Figure BDA0002308255490000041
TABLE 2 Water quality index of thiourea-containing wastewater
Figure BDA0002308255490000042
Example 2
As shown in fig. 1, in this embodiment, the steps of treating the high ammonia-nitrogen wastewater are as follows:
(1) pretreating high ammonia nitrogen wastewater, sending pretreated effluent into a nitration reaction device added with activated sludge for nitration reaction, controlling the pH of the influent by using sodium carbonate to 9, and keeping the hydraulic retention time to 2 d;
firstly, performing Fenton oxidation, neutralization and precipitation treatment, and then separating to obtain supernatant and metal mud; the Fenton oxidation comprises the steps of adjusting the pH value of high ammonia nitrogen wastewater to be 3 by adding calcium hydroxide, adding 1% of hydrogen peroxide (the mass concentration of hydrogen peroxide is 30%) by taking the volume of the high ammonia nitrogen wastewater as a reference, adding 1 ‰ of ferrous sulfate, reacting for 3 hours, and obtaining a Fenton oxidation treatment solution after the reaction is finished; the neutralization precipitation is to add calcium hydroxide into the Fenton oxidation treatment liquid, adjust the pH to 9 and react for 30 min;
then, taking the supernatant into a regulating reservoir, and introducing low-concentration wastewater into the regulating reservoir, wherein the low-concentration wastewater is derived from domestic sewage (the water quality of the wastewater is shown in table 4), and the volume ratio of the low-concentration wastewater to the supernatant introduced into the regulating reservoir is 1:3, so as to obtain a mixed water body;
then, carrying out anaerobic treatment on the mixed water body, and controlling the pH of inlet water to be 8 by using calcium hydroxide and the hydraulic retention time to be 3 d;
finally, carrying out aerobic reaction treatment on the effluent after the anaerobic reaction treatment, and controlling the pH of the inlet water to be 7 by using dilute sulfuric acid and the hydraulic retention time to be 1 d;
(2) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the inlet water to 7, controlling the hydraulic retention time to be 1d, and using thiourea-containing wastewater (the water quality of the wastewater is shown in Table 4) as the water quality regulation, wherein the volume ratio of the introduction amount of the thiourea wastewater to the inlet water of the denitrification device is 1: 40;
the steps for pretreating the thiourea wastewater are as follows:
firstly, taking the iron mud separated in the step (1), and carrying out acid dissolution by using sulfuric acid to obtain a solution containing iron ions;
then, adding the obtained metal ion solution into thiourea-containing wastewater for complexing precipitation, and adding a solution containing iron ions with the molar ratio of thiourea in the thiourea-containing wastewater to the iron ions being 1:2 based on the thiourea in the thiourea-containing wastewater;
then, the supernatant fluid of the complex precipitation enters an electrocatalytic oxidation device for electrocatalytic oxidation treatment, wherein the anode plate adopts IrO2Controlling electrocatalytic oxidation for 30min by using a titanium-based coating electrode; neutralizing the effluent of the electrocatalytic oxidation, and separating out supernatant to serve as water quality adjustment;
(3) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction, controlling the pH of the influent water to 8 by using calcium hydroxide, and keeping the hydraulic retention time to be 1 d;
(4) and (4) precipitating the effluent obtained in the step (3) and discharging supernatant.
The effluent quality is shown in table 3.
TABLE 3 wastewater treatment Water quality index
Figure BDA0002308255490000051
TABLE 4 wastewater quality index
Figure BDA0002308255490000052
Example 3
As shown in fig. 1, in this embodiment, the steps of treating the high ammonia-nitrogen wastewater are as follows:
(1) pretreating high ammonia nitrogen wastewater, sending pretreated effluent into a nitration reaction device added with activated sludge, controlling the pH of the influent by using sodium carbonate to 7, and controlling the hydraulic retention time to be 4 d;
the pretreatment steps of the high ammonia nitrogen wastewater are as follows:
firstly, after Fenton oxidation, neutralization and precipitation treatment, supernatant and metal mud are obtained by separation. The Fenton oxidation is to add calcium hydroxide to adjust the pH value of the high ammonia-nitrogen wastewater to 3, add 1% hydrogen peroxide (the mass concentration of hydrogen peroxide is 30%) based on the volume of the high ammonia-nitrogen wastewater, add 1 ‰ ferrous sulfate, react for 3 hours, and obtain a Fenton oxidation treatment solution after the reaction is finished; and the neutralization precipitation is to add calcium hydroxide into the Fenton oxidation treatment solution, adjust the pH to 9 and react for 30 min. Then, taking the supernatant into a regulating reservoir, and introducing low-concentration wastewater into the regulating reservoir, wherein the wastewater is derived from domestic sewage (the quality of the wastewater is shown in table 6), and the volume ratio of the low-concentration wastewater to the supernatant introduced into the regulating reservoir is 1:3, so as to obtain a mixed water body;
then, carrying out anaerobic treatment on the mixed water body, controlling the pH of the inlet water to be 7 by using calcium hydroxide, and controlling the hydraulic retention time to be 3 d;
finally, performing aerobic reaction treatment on the effluent after the anaerobic reaction treatment, and controlling the pH of the inlet water to be 8 by using calcium hydroxide and the hydraulic retention time to be 2 d;
(2) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the inlet water to 8 by using sodium carbonate/calcium hydroxide, controlling the hydraulic retention time to be 2d, and using thiourea-containing wastewater (the quality of the wastewater is shown in table 6) as the water quality regulation, wherein the volume ratio of the introduction amount of the thiourea wastewater to the inlet water of the denitrification device is 1: 40;
the steps for pretreating the thiourea wastewater are as follows:
firstly, taking the metal mud separated in the step (1), and carrying out acid dissolution by using sulfuric acid to obtain a copper ion-containing solution;
then, adding the obtained metal ion solution into thiourea-containing wastewater for complexing precipitation, and adding a copper ion-containing solution with the molar ratio of thiourea in the thiourea-containing wastewater to copper ions being 1:1 based on thiourea in the thiourea-containing wastewater;
then, the supernatant fluid of the complex precipitation is treated by ozone catalytic oxidation, the supernatant fluid of the complex precipitation is pumped into a catalytic oxidation tower, and 1 percent of H is added by taking the volume of the supernatant fluid as the reference2O2Introducing ozone into the solution (the mass fraction is 30 percent) at the concentration of 4.0-6.0 mg/min for O3/H2O2Performing catalytic oxidation, controlling the reaction time to be 30min, and separating out supernate after the reaction is finished to be used for adjusting the water quality; neutralizing the effluent of the catalytic oxidation of ozone, and separating supernatant to serve as water quality regulation;
(3) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction, controlling the pH of the influent water to 7 by using calcium hydroxide, and controlling the hydraulic retention time to be 2 d;
(4) and (4) precipitating the effluent obtained in the step (3) and discharging supernatant.
The effluent quality is shown in table 5.
TABLE 5 wastewater treatment Water quality index
Figure BDA0002308255490000061
TABLE 6 wastewater quality index
Figure BDA0002308255490000071
Comparative example 1
The comparative example is basically the same as example 2, and only differs from the comparative example in that the steps of the treatment process for the high ammonia nitrogen wastewater are shown in figure 2:
(1) pretreatment of high ammonia nitrogen wastewater, namely, pretreatment of the high ammonia nitrogen wastewater, and inlet and outlet water quality and low-concentration wastewater quality before and after the treatment are the same as those in example 2, and the effluent after the pretreatment is sent to a regulating reservoir;
introducing low-concentration wastewater into the regulating reservoir, wherein the wastewater is derived from domestic sewage (the quality of the wastewater is shown in table 6), mixing the domestic sewage and the wastewater, homogenizing and homogenizing to obtain a mixed water body;
meanwhile, thiourea wastewater is pretreated, supernatant is separated and is used as the regulated water quality to be sent into a regulating reservoir, and the pretreatment step and the water quality of inlet and outlet water before and after pretreatment are the same as those in the embodiment 2; the volume ratio of the introduction amount of the thiourea wastewater to the inlet water of the regulating tank is 1: 40;
carrying out anaerobic treatment and aerobic reaction on the mixed water body (same as the example 2);
(2) sending the effluent after the aerobic reaction into a nitration reaction device added with activated sludge for nitration reaction, controlling the pH of the influent water to 9 by using sodium carbonate, and keeping the hydraulic retention time to be 2 d;
(3) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the influent water to 7, and controlling the hydraulic retention time to be 1 d;
(4) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction, controlling the pH of the influent water to 8 by using calcium hydroxide, and keeping the hydraulic retention time to be 1 d;
(5) and (4) precipitating the effluent obtained in the step (4), and discharging the supernatant.
The effluent quality is shown in table 7.
TABLE 7 wastewater treatment quality index
Figure BDA0002308255490000072
The mixed high-concentration wastewater of thiourea wastewater treatment effluent enters a regulating reservoir, the concentration of final effluent pollutants is higher, and especially the removal effect of pollutants in the nitration reaction process is poor, because the thiourea in the wastewater inhibits the nitration reaction of the wastewater, so that the activity of the nitrated sludge is reduced and even dies, and the concentration of the final effluent pollutants is increased.
Comparative example 2
The comparative example is basically the same as example 2, and only differs from the comparative example in that the treatment process of the high ammonia nitrogen wastewater is shown in figure 3:
(1) pretreatment of high ammonia nitrogen wastewater, pretreatment steps, and inlet and outlet water quality and low-concentration wastewater quality before and after treatment are the same as those in example 2;
sending the effluent after pretreatment of the high ammonia nitrogen wastewater into a nitration reaction device added with activated sludge for nitration reaction, controlling the pH of the inlet water to 9 by using sodium carbonate, controlling the hydraulic retention time to be 2d, using the supernatant of the pretreated thiourea wastewater as the water quality regulation, and carrying out the pretreatment step on the thiourea wastewater and the inlet and outlet water quality before and after the pretreatment as in example 2, wherein the volume ratio of the inlet amount of the thiourea wastewater to the inlet water of the nitration device is 1: 40;
(2) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the influent water to 7, and controlling the hydraulic retention time to be 1 d;
(3) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction, controlling the pH of the influent water to 8 by using calcium hydroxide, and keeping the hydraulic retention time to be 1 d;
(4) and (4) precipitating the effluent obtained in the step (3) and discharging supernatant.
The effluent quality is shown in table 8.
TABLE 8 wastewater treatment quality index
Figure BDA0002308255490000081
The thiourea wastewater treatment effluent is added in the same stage nitration reaction step, the final effluent pollutant concentration is higher, and the final effluent pollutant concentration is similar to that in comparative example 1, because thiourea in the wastewater inhibits the nitration reaction of the wastewater, but has no obvious influence on anaerobic biochemical reaction, so that the activity of the nitrified sludge is reduced and even dies, and the final effluent pollutant concentration is increased.
Comparative example 3
The comparative example is basically the same as example 2, and only differs from the comparative example in that the steps of the treatment process of the high ammonia nitrogen wastewater are shown in figure 4:
(1) high ammonia nitrogen wastewater pretreatment (pretreatment step of high ammonia nitrogen wastewater, water quality of inlet and outlet water before and after treatment, and water quality of low concentration wastewater are the same as those in example 2); sending the pretreated effluent into a nitration reaction device added with activated sludge for nitration reaction, controlling the pH of the influent by using sodium carbonate 9, and keeping the hydraulic retention time at 2 d;
(2) sending the effluent after the nitration reaction into a denitrification device added with activated sludge for denitrification reaction, controlling the pH of the influent water to 7, and controlling the hydraulic retention time to be 1 d;
(3) feeding the effluent after the denitrification reaction into an aerobic reaction device for aerobic reaction, controlling the pH of the influent water to 8 by using calcium hydroxide, and keeping the hydraulic retention time to be 1 d; introducing the supernatant of the pretreated thiourea wastewater (the pretreatment step of the thiourea wastewater and the water quality of inlet and outlet water before and after the pretreatment are the same as those in example 2) to regulate the water quality, wherein the volume ratio of the introduction amount of the thiourea wastewater to the inlet water of the aerobic reaction device is 1: 40;
(4) and (4) precipitating the effluent obtained in the step (3) and discharging supernatant.
The effluent quality is shown in table 9.
TABLE 9 wastewater treatment quality index
Figure BDA0002308255490000091
The thiourea wastewater treatment effluent is added in the aerobic reaction step before effluent, the concentration of final effluent pollutants is lower, and the concentration of final effluent pollutants is similar to that in comparative example 1, because the thiourea wastewater only inhibits the nitrification reaction from influencing the denitrification and biological denitrification reaction, but because the thiourea is not easily biodegraded, the COD, ammonia nitrogen and total nitrogen of the final effluent are slightly increased.

Claims (5)

1. A comprehensive treatment process of high ammonia nitrogen wastewater is characterized in that:
the COD of the high ammonia nitrogen wastewater is 8000mg/L of 5000-;
the method comprises the following steps:
(1) performing Fenton oxidation, neutralization and precipitation, anaerobic treatment and aerobic reaction on the high ammonia-nitrogen wastewater to finish pretreatment, and performing nitration reaction on pretreated effluent;
(2) carrying out denitrification reaction on the effluent after the nitrification reaction, and using the wastewater containing thiourea as the water quality regulation; the COD of the effluent after the nitration reaction is 500-800mg/L, and the ammonia nitrogen concentration is 5-20 mg/L;
the thiourea wastewater is treated by complexing precipitation, catalytic oxidation and neutralization precipitation, the thiourea content is 2-5mg/L, and the volume ratio of the introduced quantity of the thiourea wastewater to the water inflow of the denitrification reaction is 1: 40; the metal ion solution used for the complex precipitation is a metal mud separated from the neutralization precipitation in the step (1), and is subjected to acid dissolution to obtain a solution containing metal ions;
(3) and carrying out aerobic reaction on the effluent after the denitrification reaction.
2. The comprehensive treatment process of high ammonia nitrogen wastewater according to claim 1, characterized in that: neutralizing and precipitating the high ammonia-nitrogen wastewater, separating to obtain supernatant, and introducing low-concentration wastewater to adjust water quality for homogenizing.
3. The comprehensive treatment process of high ammonia nitrogen wastewater according to claim 2, characterized in that: the COD of the low-concentration wastewater is 2000-4000mg/L, and the ammonia nitrogen concentration is 80-150 mg/L.
4. The comprehensive treatment process of high ammonia nitrogen wastewater according to claim 3, characterized in that: in the step (1), the effluent COD of the high ammonia nitrogen wastewater after pretreatment is 4000-6000mg/L, and the ammonia nitrogen concentration is 200-250 mg/L.
5. The comprehensive treatment process of high ammonia nitrogen wastewater according to claim 1, characterized in that: in the step (2), the effluent COD after the denitrification reaction is 200-500mg/L, and the ammonia nitrogen concentration is 10-40 mg/L.
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