CN108191050B - Low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater - Google Patents

Low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater Download PDF

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CN108191050B
CN108191050B CN201810093468.8A CN201810093468A CN108191050B CN 108191050 B CN108191050 B CN 108191050B CN 201810093468 A CN201810093468 A CN 201810093468A CN 108191050 B CN108191050 B CN 108191050B
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wastewater
ammonia nitrogen
sulfate
flue gas
gas desulfurization
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CN108191050A (en
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张肖静
陈召
马云霞
马永鹏
周月
母佰龙
袁东丽
张楠
周佳暖
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Zhengzhou University of Light Industry
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2101/101—Sulfur compounds
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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Abstract

A low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater comprises the following steps: (1) converging the flue gas desulfurization wastewater containing sulfate and ammonia nitrogen wastewater into a mixing tank for mixing; (2) adjusting the pH value and the temperature of the mixed wastewater in a mixing tank; (3) inoculating the cultured activated sludge into a biological reaction tank, introducing mixed wastewater from the mixing tank, and in the biological reaction tank, reducing sulfate into elemental sulfur and oxidizing ammonia nitrogen into nitrogen by using ammonia nitrogen as an electron donor by microorganisms in the activated sludge, thereby realizing synchronous removal of sulfur and nitrogen. The invention solves the problems that the water quality of the flue gas desulfurization wastewater treated by the conventional physicochemical method is difficult to reach the standard and the biodegradability of the flue gas desulfurization wastewater is poor and difficult to treat by a biological method, and realizes the cooperative treatment of the two types of wastewater.

Description

Low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater
Technical Field
The invention belongs to the field of industrial water pollutant control, relates to a method for the cooperative treatment of two types of wastewater, and particularly relates to a low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater.
Background
In recent years, with the implementation of a series of relevant environmental protection regulation standards such as "air pollution prevention and control action plan" (abbreviated as "ten atmosphere"), new "emission standard of air pollutants for thermal power plants" (GB 13223-2011), special emission limit value, "environmental air quality standard" (GB 3095-2012), and the like, the development of the industrial flue gas desulfurization industry is comprehensively promoted. Wet flue gas desulfurization is the most flue gas desulfurization technique that adopts at present, and has the advantage such as efficient, the handling capacity is big, but the operation in-process can produce a large amount of waste water that contains the sulphate, and its inorganic salt content is high, and the biodegradability is poor, be difficult to handle with the biological method, with the industrial enterprise waste water with the current situation that the biochemical method was handled mismatch, and the waste water that contains a large amount of sulphate diffuses into the sedimentary deposit after discharging into the water, sulphate reduction can produce a large amount of hydrogen sulphide foul smell, sulphide and simultaneously, the reaction such as iron salt, manganese salt generates black colloidal substances such as FeS, MnS, leads to the water to present black foul state. Therefore, the treatment of flue gas desulfurization wastewater is a complicated and urgent problem to be solved.
The flue gas desulfurization wastewater has the characteristics of high salinity and low biochemical property. At present, the wastewater is treated by a conventional physical method and a chemical method, but the process only has a good removal effect on suspended matters and heavy metal ions, but is difficult to remove a large amount of sulfate contained in the wastewater, the effluent quality is difficult to meet the requirements, and the process has the defects of large medicament consumption, high energy consumption, high cost and the like. Therefore, in order to further remove contaminants such as sulfate from water, it is necessary to perform treatment by a biological method. The existing method for treating sulfur-containing wastewater by using microorganisms mainly comprises sulfate reduction, sulfide oxidation, desulfurization denitrification and the like, and has the advantages of advanced technology, economy, reasonability, higher sustainability and the like compared with the conventional physical chemical method. Wherein, the desulfurization denitrification can also realize the synchronous removal of nitrogen and sulfur. However, sulfate-reducing bacteria (SRB), which play a major role in the sulfate-reduction process, belong to heterotrophic bacteria, and require the use of organic matter as an electron donor to reduce sulfate. Therefore, an external carbon source is needed when the flue gas desulfurization wastewater with poor biodegradability is treated, and although the external carbon source is not needed in the processes of sulfide oxidation and desulfurization denitrification, the method is not suitable for the desulfurization wastewater containing a large amount of sulfate.
Disclosure of Invention
The invention aims to provide a low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater.
Based on the above purposes, the invention adopts the following technical scheme:
a low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater comprises the following steps:
(1) converging the flue gas desulfurization wastewater containing sulfate and ammonia nitrogen wastewater into a mixing tank for mixing;
(2) adjusting the pH value and the temperature of the mixed wastewater in a mixing tank;
(3) inoculating activated sludge into a biological reaction tank, introducing mixed wastewater from the mixing tank, and in the biological reaction tank, reducing sulfate into elemental sulfur by using ammonia nitrogen as an electron donor by microorganisms in the activated sludge, and oxidizing the ammonia nitrogen into nitrogen to synchronously remove the sulfur and the nitrogen; the activated sludge contains 20 to 30 percent ofCandidatus Kuenenia20 to 30% ofAnammoxo-globus sulfateAnd 20 to 30% ofBacillus benzoevoransPopulation，The three microorganisms can work cooperatively under the condition of no molecular oxygen, and sulfate is taken as an electron acceptor to oxidize ammonia nitrogen, so that the sulfate and the ammonia nitrogen are synchronously removed.
The desulfurization waste water containing sulfate is obtained by treating flue gas containing sulfur dioxide by a wet desulfurization system.
The concentration of ammonia nitrogen in the ammonia nitrogen wastewater is 50-450 mg/L, the concentration of sulfate in the desulfurization wastewater is 130-2000 mg/L, the molar ratio of ammonia nitrogen to sulfate radical in a mixed solution of the two types of wastewater is 1.5-2.5: 1, the hydraulic retention time in the biological reaction tank is 8-10 h, and the concentration of activated sludge is 8-12 g/L.
In the step (2), the temperature is adjusted to be 28-32 ℃, and the pH is adjusted to be 7.5-8.5.
According to the invention, sulfate replaces nitrite as an electron acceptor to oxidize ammonia nitrogen into nitrogen, and sulfate is reduced into sulfur simple substance, so that low-energy consumption synchronous removal of nitrogen and sulfur can be realized, and the effect of treating waste with waste can be achieved. Industries such as nonferrous metal smelting and the like are often matched with a nitrogen fertilizer production line to generate ammonia nitrogen wastewater, and the nitrogen fertilizer industry generates desulfurization wastewater by coal-fired flue gas desulfurization, so that an industrial application place is provided for low-consumption cooperative treatment of the desulfurization wastewater and the ammonia nitrogen wastewater.
In the invention, 20-30% of activated sludge is selectedCandidatus Kuenenia20 to 30% ofAnammoxo-globus sulfateAnd 20 to 30% ofBacillus benzoevoransThe three microorganisms in the proportion can cooperatively work under the condition of no molecular oxygen, sulfate is used as an electron acceptor to oxidize ammonia nitrogen, synchronous removal of the sulfate and the ammonia nitrogen is realized, and the removal rate is high, wherein the removal rate of the sulfate is over 75 percent, and the removal rate of the ammonia nitrogen is over 87 percent. If it isCandidatus KueneniaThe population quantity accounts for less than 20 percent of the total quantity,Anammoxo-globus sulfateandBacillus benzoevoransmass propagation of the population will cause the reduction of the ammonia nitrogen removal rate; if it isAnammoxo- globus sulfateAndBacillus benzoevoransthe population content is low, and the method has the advantages of low population content,Candidatus Kueneniathe population is propagated in a large quantity, and the sulfate removal rate is reduced.
Compared with the prior art, the invention has the following advantages:
(1) the problems that the water quality of the flue gas desulfurization wastewater treated by the conventional physicochemical method is difficult to reach the standard and the biodegradability is poor and difficult to treat by a biological method are solved;
(2) reducing sulfate into elemental sulfur for recycling, and oxidizing ammonia nitrogen into nitrogen, thereby realizing complete harmless treatment of nitrogen and sulfur in the wastewater;
(3) the desulfurization high-salinity wastewater and the ammonia nitrogen wastewater are mixed in the same industry, so that the nitrogen and the sulfur can be synchronously removed in the same bioreactor, the wastewater treatment cost is reduced, and the energy consumption is saved.
Drawings
FIG. 1 is a process flow diagram of the present invention; wherein, the wastewater 1 is the wastewater generated by flue gas desulfurization, and the wastewater 2 is the ammonia nitrogen wastewater discharged in the industrial production process.
Detailed Description
The present invention is further illustrated by the following specific examples.
The invention relates to rawThe reaction of the materials is as follows: 2NH4 ++SO4 2-→ N2↑+S+4H2And O. The flue gas containing sulfur dioxide is purified by wet desulphurization to generate desulphurization waste water mainly containing sulfate. Mixing the desulfurization wastewater with ammonia nitrogen wastewater according to a certain proportion, adjusting the pH and the temperature, then discharging the mixture into a biological reaction tank, reducing sulfate into elemental sulfur by using ammonia nitrogen as an electron donor by microorganisms under the action of sulfate type anaerobic ammonium oxidation bacteria, and oxidizing the ammonia nitrogen into nitrogen gas at the same time, thereby realizing synchronous removal of sulfur and nitrogen. Emphasis was placed on achieving simultaneous removal of N, S from both wastewaters.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
It should be noted that the percentage content of various microorganisms in the activated sludge in the present invention is analyzed by high throughput sequencing technology, and the percentage content of the microorganisms is 20-30%Candidatus Kuenenia"," 20 to 30%Anammoxo-globus sulfateAnd 20 to 30%Bacillus benzoevorans"percent" refers to the percentage of the microbial population in the total microbial population in the system.
Example 1
A certain chemical fertilizer plant in Henan uses a coal-fired boiler to provide steam in the production process, and correspondingly produces SO-containing2Flue gas is desulfurized by wet sodium method to produce a large amount of Na2SO4The concentration of the desulfurized wastewater of (1) is about 645 mg/L. The ammonia nitrogen concentration of the ammonia nitrogen wastewater generated in the production process of the nitrogen fertilizer is 160 mg/L. Converging the two kinds of waste water to a mixing tank through a sewage pump, stirring, fully homogenizing, mixing the waste water and then adding NH4 +-N: SO4 2-1.7:1 (molar ratio). The main process conditions controlled by the mixing tank are as follows: the pH was 7.5 and the temperature was 30 ℃. Inoculating the activated sludge into a biological reaction tank, wherein the activated sludge contains 27 percent ofCandidatus Kuenenia24% ofAnammoxo-globus sulfateAnd 23% ofBacillus benzoevoransPopulation，Introducing homogeneous waste water from the mixing tank, starting the bioreactorThe hydraulic retention time is controlled to be 9h, and the concentration of the activated sludge is 10 g/L. Through water quality monitoring and analysis, the ammonia nitrogen concentration in the effluent is 19mg/L, the sulfate concentration is 140mg/L, and the removal rates of the ammonia nitrogen and the sulfate are respectively 88.1 percent and 78.3 percent.
Example 2
In the process of production, a certain lead-zinc smelting enterprise produces a large amount of SO with medium-low concentration due to the smelting of non-ferrous metal ores2The waste gas is desulfurized by wet sodium method to produce Na containing main component2SO4The sulfate radical concentration of the desulfurization waste water is 445 mg/L; in the process of producing ammonium sulfate in a matched nitrogen fertilizer plant, a large amount of high ammonia nitrogen wastewater is produced, and the ammonia nitrogen concentration is about 130 mg/L. Converging the two kinds of waste water to a mixing tank through a sewage pump, stirring, fully homogenizing, mixing the waste water and then adding NH4 +:SO4 2-2:1 (molar ratio). The main process conditions controlled by the mixing tank are as follows: the pH was 8.5 and the temperature 28 ℃. Inoculating activated sludge into a biological reaction tank, wherein the activated sludge contains 26 percent of active sludgeCandidatus Kuenenia24% ofAnammoxo- globus sulfateAnd 23% ofBacillus benzoevoransPopulation，Introducing homogeneous wastewater from the mixing tank, starting the bioreactor, controlling the hydraulic retention time to be 9h and the concentration of the activated sludge to be 9 g/L. Through water quality monitoring and analysis, the ammonia nitrogen concentration in the effluent is 17mg/L, the sulfate concentration is 86mg/L, and the removal rates of the ammonia nitrogen and the sulfate are 87.1 percent and 80.5 percent respectively.
Example 3
In a sewage treatment plant for receiving sulfur-containing wastewater, the concentration of sulfate radical in wastewater entering the plant is about 130mg/L, the concentration of ammonia nitrogen is 50mg/L, and NH is added4 +: SO4 2-2.5:1 (molar ratio). The main process conditions controlled by the reactor are as follows: the pH was 7.5 and the temperature was 30 ℃. Inoculating activated sludge into a biological reaction tank, wherein the activated sludge contains 24 percent of activated sludgeCandidatus Kuenenia21% ofAnammoxo-globus sulfateAnd 20% ofBacillus benzoevoransPopulation，Introducing the simulated wastewater into a reactor, starting the bioreactor, and controlling the hydraulic retention time to be 8h and the concentration of the activated sludge to be 8 g/L. Menstrual water qualityMonitoring and analyzing, wherein the ammonia nitrogen concentration in the effluent is 5mg/L, the sulfate concentration is 30mg/L, and the removal rates of ammonia nitrogen and sulfate are 90% and 77% respectively.
Example 4
Some thermal power plant uses coal and garbage incineration to generate electricity at the same time, and sulfur contained in the coal can generate SO in the combustion process2The waste gas is desulfurized by wet sodium method to produce Na containing main component2SO4The sulfate radical concentration of the desulfurization waste water is 2000 mg/L; the landfill leachate contains a large amount of high ammonia nitrogen wastewater, and the ammonia nitrogen concentration is about 450 mg/L. The landfill leachate is subjected to anaerobic digestion and then converged into a mixing tank through a sewage pump and desulfurization wastewater to be fully stirred and homogenized, and NH is formed after the wastewater is mixed4 +: SO4 2-1.5:1 (molar ratio). The main process conditions controlled by the mixing tank are as follows: the pH was 7.8 and the temperature was 30 ℃. Inoculating activated sludge into a biological reaction tank, wherein the activated sludge contains 28 percent of activated sludgeCandidatus Kuenenia24% ofAnammoxo-globus sulfateAnd 23% ofBacillus benzoevoransPopulation，Introducing homogeneous wastewater from the mixing tank, starting the bioreactor, controlling the hydraulic retention time to be 10h and the concentration of the activated sludge to be 12 g/L. Through water quality monitoring and analysis, the ammonia nitrogen concentration in the effluent is 50mg/L, the sulfate concentration is 490mg/L, and the removal rates of the ammonia nitrogen and the sulfate are 88.9 percent and 75.2 percent respectively.
In other embodiments, the activated sludge is 20-30%Candidatus Kuenenia20 to 30% ofAnammoxo-globus sulfateAnd 20 to 30% ofBacillus benzoevoransThe purpose of the invention can be achieved.

Claims (3)

1. A low-consumption cooperative treatment method for flue gas desulfurization wastewater and ammonia nitrogen wastewater is characterized by comprising the following steps:
(1) converging the flue gas desulfurization wastewater containing sulfate and ammonia nitrogen wastewater into a mixing tank for mixing;
(2) adjusting the pH and the temperature of the mixed wastewater in a mixing tank, wherein the temperature is adjusted to be 28-32 ℃, and the pH is 7.5-8.5;
(3) inoculating activated sludge into a biological reaction tank, introducing mixed wastewater from the mixing tank, and in the biological reaction tank, reducing sulfate into elemental sulfur by using ammonia nitrogen as an electron donor by microorganisms in the activated sludge, and oxidizing the ammonia nitrogen into nitrogen to synchronously remove the sulfur and the nitrogen; the activated sludge contains 20 to 30 percent ofCandidatus Kuenenia20 to 30% ofAnammoxo-globus sulfateAnd 20 to 30% ofBacillus benzoevoransPopulationWherein, in the step (A),the percentage is the percentage of the microbial population in the total amount of the microbes in the activated sludge system, the three microbes can work cooperatively under the condition of no existence of molecular oxygen, sulfate is used as an electron acceptor to oxidize ammonia nitrogen, and the sulfate and the ammonia nitrogen are synchronously removed.
2. The low-consumption synergistic treatment method for the flue gas desulfurization wastewater and the ammonia nitrogen wastewater according to claim 1, characterized in that the sulfate-containing flue gas desulfurization wastewater is obtained by treating sulfur dioxide-containing flue gas with a wet desulfurization system.
3. The method for low-consumption synergistic treatment of flue gas desulfurization wastewater and ammonia nitrogen wastewater according to claim 1, characterized in that the concentration of ammonia nitrogen in the ammonia nitrogen wastewater is 50-450 mg/L, the concentration of sulfate in the desulfurization wastewater is 130-2000 mg/L, the molar ratio of ammonia nitrogen to sulfate in a mixed solution of the two types of wastewater is 1.5-2.5: 1, the hydraulic retention time in a biological reaction tank is 8-10 h, and the concentration of activated sludge is 8-12 g/L.
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CN110639349A (en) * 2018-06-27 2020-01-03 郑州大学 Chemical coupling biological synchronous waste gas desulfurization, deamination and sulfur combination recycling process
CN111099784A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Treatment method of desulfurization wastewater
CN110040848B (en) * 2019-03-13 2020-06-30 苏州科技大学 Method for realizing treatment of inorganic wastewater containing ammonia nitrogen and sulfate based on sulfur cycle
CN110052099A (en) * 2019-03-28 2019-07-26 昆明理工大学 A kind of method of sulfur-containing smoke gas biochemical de-sulfur and sulphur recovery
CN110316824B (en) * 2019-08-07 2022-03-25 大连海事大学 Cooperative treatment device and cooperative treatment method for ship waste gas washing waste liquid and ship domestic sewage

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