CN109876642B - Method and device for treating flue gas containing nitrogen oxides - Google Patents

Method and device for treating flue gas containing nitrogen oxides Download PDF

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CN109876642B
CN109876642B CN201711278514.3A CN201711278514A CN109876642B CN 109876642 B CN109876642 B CN 109876642B CN 201711278514 A CN201711278514 A CN 201711278514A CN 109876642 B CN109876642 B CN 109876642B
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flue gas
chlorella
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CN109876642A (en
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赵磊
师文静
刘洋
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Abstract

The invention relates to a method for treating flue gas containing nitrogen oxides, which comprises the following steps of (1) introducing the flue gas into a photobioreactor for microalgae culture, wherein the pH of a microalgae culture medium is not lower than 9, then inoculating microalgae with high pH tolerance, and collecting exhaust gas; (2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate; (3) denitrifying bacteria are inoculated into the filtrate, and the exhaust gas in the step (1) is introduced for denitrification treatment to obtain purified gas2、NOXAnd the method does not need to use a catalyst and a large amount of chemical reagents, and has the advantages of good removal effect, low treatment cost, economy, environmental protection and the like.

Description

Method and device for treating flue gas containing nitrogen oxides
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to a method and a device for treating flue gas containing nitric oxide.
Background
Nitrogen oxides (NOx) having N2O、NO、NO2、N2O3、N2O4And N2O5And the like, and can cause various hazards, such as photochemical smog generated by Volatile Organic Compounds (VOC) in the atmosphere, strong stimulation to eyes and throat, headache, respiratory diseases and the like, and death of serious patients. The NOx emission amount of China continuously exceeds 2000 ten thousand tons for years, 2194 ten thousand tons in 2010 and 2404.3 ten thousand tons in 2011,2337.8 ten thousand tons in 2012, 2227.3 ten thousand tons in 2013 and 2078 ten thousand tons in 2014, although the pollution condition is still severe although the trend of continuous reduction is shown since 2012. 9/12/2014, United release about printing<Coal-electricity energy-saving emission-reducing upgrade and transformation action plan (2014-2020)>Notification of (correction energy [ 2014)]2093), the ultra-clean emission of the flue gas of the coal burning boiler is required, namely, the smoke dust and SO2And NOx emission concentration index respectively reaches 10mg/Nm3、35mg/Nm3And 50mg/Nm3。
The existing flue gas denitration technology mainly comprises the following steps: SCR (selective catalytic reduction) and SNCR (selective non-catalytic reduction) for gas phase reaction, liquid absorption, solid adsorption, high-energy electron activation oxidation (EBA electron beam irradiation and PPCP pulsed corona plasma), and the like. Among various flue gas denitration treatment technologies, a liquid absorption method has low denitration efficiency; the adsorption method has high denitration efficiency, but has small adsorption quantity, frequent regeneration and not wide application; the high-energy electronic activation oxidation method can realize desulfurization and denitrification at the same time, but has high energy consumption and short service life; the SNCR method has a high escape rate of ammonia, and causes a safety problem. Compared with other technologies, the SCR technology has the advantages of high denitration efficiency, mature technology and the like, and is the most applied technology in the flue gas denitration engineering at home and abroad at present. The SCR method is to use NH at the reaction temperature of 200 ℃ and 400 DEG C3Catalytic reduction of NOx to N as a reducing agent2Oxygen in the exhaust gas rarely participates in the reaction, and the heat release is small. However, this reaction still needs to be carried out at a relatively high temperature in the presence of a catalyst, and there are problems such as ammonia slip.
The flue gas denitration process disclosed by Chinese patents CN103768903A, CN103768932A, CN103768934A and the like needs a flue gas temperature of 300-400 ℃, large-scale transformation is implemented on a boiler, and the investment cost is high. CN102716752A discloses a low-temperature SCR denitration catalyst, which is used for preparing a denitration catalyst with SO content of 300ppm2And under the condition of 10 percent of water vapor content, the removal rate of NOx under the condition of 150-250 ℃ is 38-72 percent, and the good removal rate of nitrogen oxide can be kept between 150-250 ℃. However, the catalyst prepared by the invention belongs to vanadium tungstenCatalyst system, ammonium metavanadate is converted into V after calcination2O5，V2O5Is a highly toxic substance and can cause serious pollution in the production and use processes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating flue gas containing nitrogen oxides. The invention mainly adopts a biological method to remove CO in the flue gas2、NOXAnd a catalyst and a large amount of chemical reagents are not needed, so that the method has the advantages of good removal effect, low treatment cost, economy, environmental protection and the like.
The method for treating the flue gas containing the nitrogen oxides comprises the following steps:
(1) introducing the flue gas into a photobioreactor for microalgae culture, wherein the pH of a microalgae culture medium is not lower than 9, then inoculating microalgae tolerant to high pH, and collecting exhaust gas;
(2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate;
(3) introducing denitrifying bacteria into the filtrate, and introducing the exhaust gas in the step (1) for denitrification treatment to obtain purified gas.
In the invention, the flue gas containing nitrogen oxides in the step (1) contains NOx and CO2Of flue gas, NOx being mainly NO and/or NO2For example, the sulfur recovery device can be derived from at least one of flue gas such as incineration tail gas of a sulfur recovery device, catalytic cracking regeneration tail gas, S-zorb regeneration tail gas, coal-fired flue gas and sintering flue gas. When the flue gas contains sulfur compounds such as sulfur dioxide, the flue gas is firstly subjected to desulfurization pretreatment. According to NOx and CO in the flue gas2Content, setting multiple stages of photobioreactor, controlling CO in each stage of photobioreactor2The content is less than 45v%, preferably 5v% to 35 v%; NOx content below 0.1v%, preferably below 0.05 v%; the ventilation volume is 0.1-1.0 vvm.
In the invention, the microalgae culture medium in the step (1) is a liquid culture medium for culturing microalgae by using BG11, SE, BBM and the like which are well known to those skilled in the art, and is specifically determined according to the species of the microalgae. And (3) adjusting the pH value of the microalgae culture medium to be not less than 9, preferably 10-12 by using strong alkali such as NaOH and KOH, and then inoculating microalgae seed liquid to perform microalgae culture. The inoculation amount of the microalgae seed liquid is 1-50%, preferably 5-30% of the volume of the microalgae culture medium.
In the present invention, the microalgae tolerant to high pH in step (1) is disclosed as microalgae tolerant to high pH, such as Chlorella Kelvin: (A)Parachlorella kessleri) FSH-Y3 or/and Scenedesmus obliquus (Scenedesmus obliquus)Scenedesmus obliqnus) FSH-Y2. The Chlorella chekiangensis (A) and (B)Parachlorella kessleri) FSH-Y3 has been deposited at 26.5.2014 in the China general microbiological culture Collection center (CGMCC) with the collection number of CGMCC 9238. (ii) Scenedesmus obliquusScenedesmus obliqnus) FSH-Y2 has been deposited at the China general microbiological culture Collection center (CGMCC) on 11/9 of 2012 with the collection number of CGMCC 6551. The above microalgae have been disclosed in CN106467896A, CN104611227A, respectively, and submitted for preservation and proof of survival.
In the invention, the preparation method of the seed liquid of the Chlorella Kelvin FSH-Y3 and Scenedesmus obliquus FSH-Y2 comprises the following steps: adjusting the pH value of the culture medium to 10-12, performing shaking culture at the temperature of 20-30 ℃, the illumination period of 24 hours, the light-dark time ratio of 10: 14-14: 10 and the illumination intensity of 2000-10000 Lux until the logarithmic phase. When two kinds of microalgae are contained simultaneously, the volume ratio of the seed liquid of the Chlorella Kelvin FSH-Y3 to the Scenedesmus obliquus FSH-Y2 is 5:1-1: 5.
Further, after culturing for a period of time, preferably 1 to 5 days, chlorella (c) is inoculatedChlorella sp.) SF-B1, further improving the NOx removal effect. The chlorella (A) is preparedChlorella sp.) SF-B1 has been deposited in the general microbiological center of China Committee for culture Collection of microorganisms (CGMCC) No. 11005 at 7/6/2015 with the collection address of the institute for microbiology, China academy of sciences No.3, Siro 1, North Cheng, the sunward area, Beijing. The preparation method of the chlorella SF-B1 seed liquid comprises the following steps: adjusting the pH value of the culture medium to 6-9, and carrying out shaking culture to logarithmic growth phase at the temperature of 10-30 ℃, in an illumination period of 24 hours, in a light-dark time ratio of 10: 14-14: 10 and in an illumination intensity of 2000-20000 Lux. The inoculation amount of the chlorella SF-B1 is equal to that of the chlorella keiskei, (C)Parachlorella kessleri) FSH-Y3 or/and Scenedesmus obliquus (Scenedesmus obliquus)Scenedesmus obliqnus) The volume ratio of the FSH-Y2 seed liquid is 1:1-1: 50.
In the invention, after the flue gas is used for culturing microalgae, CO in the flue gas2Is utilized by microalgae to generate O2On the one hand, NOx is converted into nitrite in the presence of strong alkali, and on the other hand, a large amount of O is generated due to microalgae cultivation2NO is oxidized to NO2And further converted into nitrates, whereby the exhaust gas collected contains only a small amount of NOx, CO2The removal rate of nitrogen oxide can reach more than 70 percent, and CO2The utilization rate reaches more than 50 percent.
In the invention, the microalgae culture conditions in the step (1) are as follows: the temperature is 10-35 ℃, the illumination period is 24 hours, the light-dark time ratio is 10: 14-14: 10, the pH value is 9-12, the illumination intensity is 2000-20000 Lux, and the culture is carried out until the growth stabilization period is finished.
In the invention, the solid-liquid separation in the step (2) adopts the modes of centrifugation, filtration and the like to respectively harvest microalgae cells and filtrate, and the dry weight of the cells and the oil content are measured, wherein the dry weight of the cells can reach more than 5g/L, and the oil content can reach more than 40 percent of the dry weight of the cells.
In the invention, the filtrate in the step (3) is mainly nitrate and nitrite, denitrifying bacteria are inoculated for denitrification treatment, and the concentration of the inoculated sludge is 2000-10000 mg/L. Purification of CO from gas2The removal rate reaches more than 70 percent, and the NOx removal rate reaches more than 80 percent. The removal rate of the total nitrogen in the effluent reaches over 90 percent.
Further, it is preferable to add a certain amount of denitrifying bacteria such as Paracoccus denitrificans (B.) (Paracoccus denitrificans) DN-3, Methylobacterium (Methylobacterium: (M))Methylobacterium phyllosphaerae) The total nitrogen removal rate of at least one of SDN-3 can reach more than 95%. The preservation numbers of paracoccus denitrificans DN-3 and methylobacterium SDN-3 are CGMCC No.3658 and CGMCC No.3660 respectively, are disclosed in CN102465104A and CN102465103, and submit preservation and survival certificates.
The invention also provides a device for treating the flue gas containing the nitrogen oxides, which comprises a photo-biological reaction system, an exhaust gas collecting system, a solid-liquid separation system and a denitrification system, wherein the photo-biological reaction system mainly comprises a plurality of stages of photo-biological reactors, and microalgae culture is carried out by utilizing the introduced flue gas containing the nitrogen oxides; the exhaust gas collecting system is used for collecting exhaust gas; the solid-liquid separation system is used for carrying out solid-liquid separation on the culture system; and the denitrification system is used for carrying out denitrification treatment on the separated filtrate.
Compared with the prior art, the invention has the following advantages:
(1) biological method for removing CO in flue gas2、NOXAnd a catalyst and a large amount of chemical agents are not needed, so that the method has the advantages of good removal effect, low treatment cost, economy, environmental protection and the like.
(2) The adoption of microalgae which can tolerate high pH can increase CO in a culture system2The solubility of (A) is favorable for microalgae to react with CO2The absorption and utilization of the carbon are realized, and the carbon fixation efficiency is improved. Meanwhile, NO can be added when microalgae are cultured at a high pH valueXConversion to nitrite, increase of NOXAnd NO can be avoidedXPoisoning of microalgae.
(3) Introducing flue gas into microalgae culture, wherein CO is contained in the flue gas2Can be used by microalgae to generate O2Conversion of NO in flue gas to NO2Formation of NO in water3 -And NO2 -And then converted to N in denitrification2The above processes act synergistically to achieve CO2And NOXThe removal is efficient.
(4) Adopts chlorella (A) and (B)Chlorella sp.）SF-B1，NOXThe removal effect is better.
(5) The invention can not only treat NO-containing gas in an environment-friendly and economical wayXThe smoke can also obtain the microalgae cells with high oil content, and the economic benefit and the environmental protection benefit are obviously improved.
Drawings
FIG. 1 is a flue gas treatment plant according to the invention;
101-a photo-biological reaction system, 102-a discharge gas collecting system, 103-a solid-liquid separating system and 104-a denitrification system; 201-culture medium and seed liquid, 202-filtrate, 203-microalgae cells, and 204-effluent; 301-flue gas, 302-exhaust gas, 303-purge gas.
Detailed Description
The present invention will be described in further detail by way of examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, v% is a volume fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The flue gas treatment device disclosed by the invention is shown in a figure 1 and comprises a photo-biological reaction system, an exhaust gas collection system, a solid-liquid separation system and a denitrification system, wherein the photo-biological reaction system 101 is a photo-biological reactor or a plurality of photo-biological reactors are connected in series or in parallel, after a microalgae culture medium and seed liquid 201 are added, flue gas 301 is introduced for microalgae culture, and exhaust gas 302 is collected through the exhaust gas collection system 102; the microalgae culture system enters a solid-liquid separation system 103 for separation, and microalgae cells 203 and filtrate 202 are respectively harvested; the filtrate 202 enters the denitrification system 104 for treatment, and the exhaust gas 302 is introduced in the treatment process to obtain purified gas 303 and effluent 204 after treatment.
The removal rate of the invention is (gas content-vent gas content)/gas content.
The culture of the microalgae adopts BG11 culture medium, and the formula is shown in tables 1 and 2.
TABLE 1 BG11 culture Medium
Figure DEST_PATH_IMAGE002
Table 2 composition of a5+ Co solution in table 1
Figure DEST_PATH_IMAGE004
BG11 liquid medium was prepared according to tables 1 and 2, and the medium for culturing Chlorella Kelvin FSH-Y3 and Scenedesmus obliquus FSH-Y2 was adjusted to pH 10, and the medium for culturing Chlorella sp-B1 was adjusted to pH 8, and then inoculated into each of the above media. Culturing in constant temperature light shaking table at 25 deg.C for 24h with light-dark time ratio of 14:10 and light intensity of 5000Lux at 120rpm until logarithmic phase to obtain Chlorella Kelly FSH-Y3 seed solution, Scenedesmus obliquus FSH-Y2 seed solution, and Chlorella SF-B1 seed solution.
The denitrification sludge used in the embodiment of the invention is taken from a denitrification treatment tank of a certain sewage treatment plant, and the removal rate of the total nitrogen in the effluent reaches more than 90 percent.
The flue gas adopted by the invention contains NOx and CO2Of flue gas, NOx being mainly NO and/or NO2. When the flue gas contains sulfur compounds such as sulfur dioxide, the flue gas is firstly subjected to desulfurization pretreatment.
Example 1
(1) Adding 6L of prepared microalgae culture medium into a 10L photobioreactor, adjusting the pH of the microalgae culture medium to 10 by using NaOH, and inoculating 0.9L of Chlorella Kelly FSH-Y3 seed solution for culturing. Introducing flue gas containing CO2The content of (A) was 5v%, the NO content was 0.03v%, and the ventilation amount was 0.5 vvm. The illumination intensity of the culture is 5000Lux, the culture temperature is 25 ℃, the illumination period is 24h, and the light-dark time ratio is 14: 10. In the collected exhaust gas, CO2The removal rate is 85%, and the removal rate of NO is 80%.
(2) After 5 days of culture, microalgae cells and filtrate were harvested by centrifugation. And (4) measuring the dry weight and the oil content of the cells. And (3) carrying out vacuum freeze drying at the temperature of-60 ℃ to constant weight, measuring the dry weight of the algae powder, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 5.5g/L, and the oil content is 44.1 percent of the dry cell weight.
(3) And (3) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the exhaust gas in the step (1) into a reaction system for treatment to obtain purified gas. Purifying the gas of CO2The removal rate is 90%, and the removal rate of NO is 85%. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 2
(1) 6L of the prepared microalgae culture medium is added into a 10L photobioreactor, the pH value of the microalgae culture medium is adjusted to 11 by adopting NaOH, and 1.0L of the Chlorella Kelvin FSH-Y3 seed liquid is inoculated for culture. Introducing flue gas containing CO2The content of (A) was 10v%, the NO content was 0.05v%, and the ventilation amount was 0.5 vvm. The illumination intensity of the culture is 5000Lux, the culture temperature is 25 ℃, the illumination period is 24h, and the light-dark time ratio is 14: 10. CO in the collected exhaust gas2The removal rate was 80% and the NO removal rate was 75%.
(2) After 6 days of culture, microalgae cells and filtrate were harvested by centrifugation. And (4) measuring the dry weight and the oil content of the cells. And (3) carrying out vacuum freeze drying at the temperature of-60 ℃ to constant weight, measuring the dry weight of the algae powder, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 5.2g/L, and the oil content is 42.7% of the dry cell weight.
(3) And (3) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the gas discharged in the step (1) into a reactor for treatment to obtain purified gas. Purifying the gas of CO2The removal rate is 85%, and the removal rate of NO is 80%. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 3
(1) 6L of the prepared microalgae culture medium is added into a 10L photobioreactor, the pH of the microalgae culture medium is adjusted to 12 by NaOH, and 1.2L of the Chlorella Kelvin FSH-Y3 seed liquid is inoculated for culture. Introducing flue gas containing CO2Has a content of 40v%, a NO content of 0.05v%, and a ventilation amount of 0.3 vvm. The illumination intensity of the culture is 5000Lux, the culture temperature is 25 ℃, the illumination period is 24h, and the light-dark time ratio is 14: 10. CO in the collected exhaust gas2The removal rate was 60% and the NO removal rate was 75%.
(2) After 6 days of culture, microalgae cells and filtrate were harvested by centrifugation. And (4) measuring the dry weight and the oil content of the cells. And (3) carrying out vacuum freeze drying at the temperature of-60 ℃ to constant weight, measuring the dry weight of the algae powder, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 5.1g/L, and the oil content is 41.5 percent of the dry cell weight.
(3) And (3) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the gas discharged in the step (1) into a reactor for treatment to obtain purified gas. Purifying the gas of CO2The removal rate was 70% and the NO removal rate was 80%. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 4
(1) 6L of prepared microalgae culture medium is added into a 10L photobioreactor, the pH value of the microalgae culture medium is adjusted to 10 by NaOH, and 1.2L of Chlorella Kelly FSH-Y3 seed liquid is inoculated for culture. Introducing flue gas containing CO2The content of (A) was 10v%, the NO content was 0.7v%, and the ventilation amount was 0.2 vvm. The illumination intensity of the culture is 5000Lux, the culture temperature is 25 ℃, the illumination period is 24h, and the light-dark time ratio is 14: 10. CO in the collected exhaust gas2The removal rate was 80% and the NO removal rate was 70%.
(2) After 6 days of culture, microalgae cells and filtrate were harvested by centrifugation. And (4) measuring the dry weight and the oil content of the cells. And (3) carrying out vacuum freeze drying at the temperature of-60 ℃ to constant weight, measuring the dry weight of the algae powder, calculating the biomass yield, and measuring the total lipid content by adopting a normal hexane-ethyl acetate method. After detection, the dry cell weight can reach 5.2g/L, and the oil content is 42.5% of the dry cell weight.
(3) And (3) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the gas discharged in the step (1) into a reactor for treatment to obtain purified gas. Purifying the gas of CO2The removal rate is 85%, and the removal rate of NO is 80%. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 5
The same culture procedure and culture conditions as in example 1 were used, except that: the microalgae is Scenedesmus obliquus FSH-Y2. CO in the exhaust gas collected after the culture in the step (1)2The removal rate was 86% and the NO removal rate was 81%. After the detection in the step (2), the dry cell weight can reach 5.7g/L, and the oil content is 44.8% of the dry cell weight. CO in the purified gas after the treatment in the step (3)2The removal rate is 90%, and the removal rate of NO is 85%.
Example 6
The same culture procedure and culture conditions as in example 1 were used, except that: the microalgae simultaneously adopt Scenedesmus obliquus FSH-Y2 and Chlorella Kelvin FSH-Y3, and the volume ratio of seed liquid of the Scenedesmus obliquus FSH-Y2 to seed liquid of the Chlorella Kelvin FSH-Y3 is 1: 1. CO in the exhaust gas collected after the culture in the step (1)2The removal rate was 87% and the NO removal rate was 82%. After the detection in the step (2), the dry cell weight can reach 5.8g/L, and the oil content is 45.2% of the dry cell weight. CO in the purified gas after the treatment in the step (3)2The removal rate was 92% and the NO removal rate was 88%.
Example 7
The same culture procedure and culture conditions as in example 2 were used, except that: after culturing the Chlorella Kelly in FSH-Y3 for 4 days, inoculating Chlorella SF-B1, wherein the volume ratio of the Chlorella SF-B1 seed liquid to the Chlorella Kelly FSH-Y3 seed liquid is 1: 1.
CO in the exhaust gas collected after the culture in the step (1)2The removal rate is 85%, and the removal rate of NO is 85%. In the purified gas finally obtained, CO2The removal rate is 90%, and the removal rate of NO is 90%.
Example 8
The same culture procedure and culture conditions as in example 2 were used, except that: after culturing the Chlorella Kelly in FSH-Y3 for 2 days, inoculating Chlorella SF-B1, wherein the volume ratio of the Chlorella SF-B1 seed liquid to the Chlorella Kelly FSH-Y3 seed liquid is 1: 5. CO in the exhaust gas collected after the culture in the step (1)2The removal rate is 80%, and the removal rate of NO is 80%. In the purified gas finally obtained, CO2The removal rate is 90%, and the removal rate of NO is 85%.
Example 9
The same culture procedure and culture conditions as in example 2 were used, except that: any one of paracoccus denitrificans DN-3 and methylobacterium SDN-3 is added in the step (3), the preparation method of the inoculation liquid is the same as that in CN102465104A and CN102465103, and the inoculation amount is 1 percent of the volume of the sewage treatment system. Obtaining CO in the purified gas2The removal rate is 90 percent, the removal rate of NO is 85 percent, and the removal rate of the total nitrogen in the treated effluent reaches more than 95 percent.
Example 10
The same culture procedure and culture conditions as in example 2 were used, except that: CO in flue gas2In an amount of 10v%, NO2The content was 0.05 v%. The treatment effect was substantially the same as in example 2.
Comparative example 1
The same culture procedure and culture conditions as in example 1 were used, except that: with the chlorella strain FY1# described in CN102311921A, since microalgae are neither tolerant to high pH nor to NOXTherefore, after a period of growth, a large number of the plants die, and subsequent processes cannot be performed.
Comparative example 2
The same culture procedure and culture conditions as in example 1 were used, except that: with the fibrophyta SS-B7 described in CN105713836A, microalgae are not tolerant to high pH, and therefore die after a period of growth, and subsequent processes cannot be performed.
In conclusion, the method provided by the invention can be used for treating the flue gas containing the nitrogen oxides in the microalgae culture process, so that the high-efficiency treatment of the flue gas is realized, the microalgae grease can be obtained, and the economic benefit and the environmental benefit are obviously improved.

Claims (15)

1. A method for treating flue gas containing nitrogen oxides is characterized by comprising the following steps:
(1) introducing the flue gas into a photobioreactor for microalgae culture, wherein the pH of a microalgae culture medium is not lower than 9, then inoculating microalgae tolerant to high pH, and collecting exhaust gas; the microalgae which can tolerate high pH is Chlorella chevalieri FSH-Y3 or/and Scenedesmus obliquus FSH-Y2; after being cultured for a period of time, the chlorella is inoculated with SF-B1 with the preservation number of CGMCC number 11005; according to NOx and CO in the flue gas2Content, setting multiple stages of photobioreactor, controlling CO in each stage of photobioreactor2The content is lower than 45v%, the NOx content is lower than 0.1v%, and the ventilation volume is 0.1-1.0 vvm; wherein v% is volume fraction;
(2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate;
(3) and (3) inoculating denitrifying bacteria into the filtrate, and introducing the exhaust gas in the step (1) for denitrification treatment to obtain purified gas.
2. The method of claim 1, wherein: the flue gas containing the nitrogen oxides in the step (1) contains NOx and CO2Of flue gas, NOx being mainly NO and/or NO2When the flue gas contains SO2When in use, the flue gas is firstly subjected to desulfurization pretreatment.
3. The method according to claim 1 or 2, characterized in that: the nitrogen oxide-containing flue gas in the step (1) is derived from at least one of incineration tail gas of a sulfur recovery device, catalytic cracking regeneration tail gas, S-zorb regeneration tail gas, coal-fired flue gas and sintering flue gas.
4. The method of claim 1, wherein: controlling CO in each stage of photobioreactor2The content is 5-35 v%, and the NOx content is lower than 0.05 v%.
5. The method of claim 1, wherein: the microalgae culture medium in the step (1) adopts liquid culture medium for culturing microalgae by BG11, SE and BBM, the pH value of the microalgae culture medium is adjusted to be not less than 9, then microalgae seed liquid is inoculated for microalgae culture, and the inoculation amount of the microalgae seed liquid is 1-50% of the volume of the microalgae culture medium.
6. The method of claim 5, wherein: adjusting the pH value of a microalgae culture medium to 10-12; the inoculation amount of the microalgae seed liquid is 5-30% of the volume of the microalgae culture medium.
7. The method of claim 1, wherein: the preparation method of the seed liquid of the Chlorella Kelvin FSH-Y3 and Scenedesmus obliquus FSH-Y2 comprises the following steps: adjusting the pH value of the culture medium to 10-12, performing shaking culture at the temperature of 20-30 ℃, the illumination period of 24 hours, the light-dark time ratio of 10: 14-14: 10 and the illumination intensity of 2000-10000 Lux until the logarithmic phase.
8. The method according to claim 1 or 7, characterized in that: when two kinds of microalgae are contained simultaneously, the volume ratio of the seed liquid of the Chlorella Kelvin FSH-Y3 to the Scenedesmus obliquus FSH-Y2 is 5:1-1: 5.
9. The method of claim 1, wherein: and inoculating chlorella SF-B1 after culturing for 1-5 days.
10. The method according to claim 1 or 9, characterized in that: the preparation method of the chlorella SF-B1 seed liquid comprises the following steps: adjusting the pH value of the culture medium to 6-9, and carrying out shaking culture to logarithmic growth phase at the temperature of 10-30 ℃, in an illumination period of 24 hours, in a light-dark time ratio of 10: 14-14: 10 and in an illumination intensity of 2000-20000 Lux.
11. The method according to claim 1 or 9, characterized in that: the inoculation amount of the chlorella SF-B1 is 1:1-1:50, and the volume ratio of the chlorella F-B1 to the seed liquid of the Chlorella vulgaris FSH-Y3 or/and Scenedesmus obliquus FSH-Y2 is 1:1-1: 50.
12. The method of claim 1, wherein: the microalgae culture conditions in the step (1) are as follows: the temperature is 10-35 ℃, the illumination period is 24 hours, the light-dark time ratio is 10: 14-14: 10, the pH value is 9-12, the illumination intensity is 2000-20000 Lux, and the culture is carried out until the growth stabilization period is finished.
13. The method of claim 1, wherein: the filtrate in the step (3) mainly contains nitrate and nitrite, denitrifying bacteria are inoculated for denitrification treatment, and the concentration of the inoculated sludge is 2000-10000 mg/L.
14. The method of claim 13, wherein: a certain amount of at least one of paracoccus denitrificans DN-3 and methylobacterium SDN-3 is added in the denitrification treatment, and the total nitrogen removal rate reaches more than 95 percent.
15. Apparatus for use in a method according to any one of claims 1 to 14 for treating flue gas containing nitrogen oxides, characterized in that: comprises a photo-biological reaction system, an exhaust gas collecting system, a solid-liquid separation system and a denitrification system.
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