CN109876641B - Method and device for treating NOx-containing flue gas - Google Patents
Method and device for treating NOx-containing flue gas Download PDFInfo
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- CN109876641B CN109876641B CN201711277175.7A CN201711277175A CN109876641B CN 109876641 B CN109876641 B CN 109876641B CN 201711277175 A CN201711277175 A CN 201711277175A CN 109876641 B CN109876641 B CN 109876641B
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/59—Biological synthesis; Biological purification
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Abstract
The invention relates to a method for treating NOx-containing flue gas, which comprises the steps of (1) introducing the flue gas into a photobioreactor for microalgae culture, and collecting exhaust gas, wherein the microalgae is tolerant to NOx; (2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate; (3) adding sodium peroxide into the filtrate obtained in the step (2), and introducing the exhaust gas obtained in the step (1) into the filtrate for treatment to obtain purified gas; (4) and (4) carrying out denitrification treatment on the filtrate treated in the step (3). The invention also provides a treatment device for the NOx-containing flue gas. 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.
Description
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to a method and a device for treating NOx-containing flue gas.
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. In China, the NOx emission amount exceeds 2000 ten thousand tons continuously for many years, 2194 ten thousand tons in 2010, 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, and although the NOx emission amount has a continuous reduction trend since 2012, the pollution condition is still severe. 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 are respectively reachedTo 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 a vanadium-tungsten catalyst, and ammonium metavanadate is converted into V after being calcined2O5，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 NOx-containing flue gas. The invention mainly adopts a biological method to remove CO in the flue gas2、NOXWithout using catalyst and great amount of chemical reagent, and has high eliminating effectLow cost, economy, environmental protection and the like.
The treatment method of the NOx-containing flue gas comprises the following steps:
(1) introducing the flue gas into a photobioreactor for microalgae culture, and collecting exhaust gas, wherein the microalgae is tolerant to NOx;
(2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate;
(3) adding sodium peroxide into the filtrate obtained in the step (2), and introducing the exhaust gas obtained in the step (1) into the filtrate for treatment to obtain purified gas;
(4) and (4) carrying out denitrification treatment on the filtrate treated in the step (3).
In the invention, the flue gas containing NOx in the step (1) contains NOx and CO2Of flue gas, NOx being mainly NO and/or NO2For example, the sulfur recovery device can be at least one of incineration tail gas of a sulfur recovery device, catalytic cracking regeneration tail gas, coal-fired flue gas, sintering flue gas and the like. 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 gas2The content of CO in each stage of photobioreactor can be controlled by arranging a plurality of stages of photobioreactors2The content is less than 45v%, preferably 5v% to 35 v%; NOx content below 0.1v%, preferably below 0.06 v%; the ventilation volume is 0.1-1.0 vvm.
In the invention, a microalgae culture medium and microalgae seed liquid are inoculated into the photobioreactor in the step (1), and the microalgae culture medium adopts a liquid culture medium for culturing microalgae, such as BG11, SE, BBM and the like which are well known to persons in the art, and is determined according to the species of the microalgae. The preparation of the microalgae culture medium and the microalgae seed liquid is the same as the conventional technical means in the field, and the inoculation amount of the microalgae seed liquid is 1-50 percent of the volume of the culture medium, preferably 5-30 percent.
In the present invention, the NOx-tolerant microalgae in step (1) is any one of the disclosed microalgae capable of tolerating NOx, preferably fibrophyta (A), (B), (C)Ankistrodesmus sp.) SS-B7, which has been preserved in China general microbiological culture Collection center (CGMCC) on 4 and 15 months in 2013, the preservation number is CGMCC No. 7478, and the preservation address isThe institute of microbiology, national academy of sciences No.3, Xilu No. 1, Beijing, Chaoyang, Beijing. This strain has been published in CN 105713836a and submitted for preservation and proof of survival.
Further, it is preferable to simultaneously administer a certain amount of chlorella (chlorella)Chlorella sp.) SF-B1, the genus Chlorella (A)Chlorella 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. Under microscope, the chlorella SF-B1 is green, unicellular algae, single-grown, spherical and elliptical in cell shape, contains pigment bodies, and has a diameter of 5-6 μm.
In the invention, the preparation method of the microalgae seed liquid comprises the following steps: adjusting the pH value of a microalgae culture medium to 6-9, carrying out shaking culture at the temperature of 20-30 ℃, the illumination period of 24 hours, the light-dark time ratio of 14: 10-10: 14 and the illumination intensity of 2000-10000 Lux until the microalgae culture medium reaches the logarithmic phase. The volume ratio of the fibroalgae SS-B7 seed liquid to the microalgae culture medium is 1: 20-1: 5. When Chlorella vulgaris SF-B1 is further inoculated, the volume ratio of the Chlorella vulgaris SS-B7 seed liquid to the Chlorella vulgaris SF-B1 seed liquid is 1:1-50: 1.
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 6-9, 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 10g/L, and the oil content can reach more than 40 percent of the dry weight of the cells.
In the invention, a certain amount of sodium peroxide is added into the filtrate obtained in the step (3), and is specifically determined according to the content of residual NOx in the exhaust gas, so that the residual NOx is converted into nitrite, and the preferable addition amount is 1-30 g/L. In the obtained purified gas, CO2And NOx removal rate is more than 70%. If the NOx removal rate is lower than 80%, the purification gas obtained in the step (3) is introducedAnd (5) entering the denitrification treatment system in the step (4) for further treatment.
In the invention, the filtrate in the step (4) is mainly nitrite and nitrate, denitrifying bacteria are inoculated for denitrification treatment, and the concentration of the inoculated sludge is 2000-10000 mg/L. 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 denitrogenation bacteria such as Coccocus palustris: (Kocuria palustris) FSDN-A, Staphylococcus cohnii (Staphylococcus cohnii) FSDN-C, Arthrobacter (A)Arthrobacter creatinolyticus) FDN-1, Flavobacterium aquatile: (Flavobacterium mizutaii) The total nitrogen removal rate of at least one of FDN-2 can reach more than 95 percent. Wherein the preservation numbers of the Coicoccus palustris FSDN-A, the Staphylococcus cohnii FSDN-C, the Arthrobacter FDN-1 and the Flavobacterium aquatile FDN-2 are CGMCC NO.5061, CGMCC NO.5062, CGMCC NO.3657 and CGMCC NO.3659 which are disclosed in CN103103141A, CN103014128A, CN102465106A and CN102465105A respectively, and the preservation and survival evidence is submitted.
The invention also provides a device for treating the NOx flue gas, which comprises a photo-biological reaction system, an exhaust gas collecting system, a solid-liquid separation system, an oxidation system and a denitrification system, wherein the photo-biological reaction system mainly comprises a plurality of stages of photo-biological reactors, and the introduced NOx-containing flue gas is used for culturing microalgae; 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; the oxidation system is used for adding sodium peroxide to obtain purified gas; the denitrification system is used for carrying out denitrification treatment on the obtained 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) By tolerant NOXThe microalgae in the method can be used for treating flue gas and CO in the flue gas2Can be used by microalgae to generate O2Oxidation of NO in flue gas to NO2Formation of NO in water3 -And NO2 -And then converted to N in the course of denitrification2The above processes act synergistically to achieve CO2And NOXThe removal is efficient.
(3) Tolerance to NO with Cellulosia SS-B7XGood performance and high carbon fixation efficiency, and can obtain high-yield algae cells. Further adding chlorella (A)Chlorella sp.）SF-B1，NOXThe removal effect is better.
(4) The invention can not only treat the smoke in an environment-friendly and economic way, but also obtain the microalgae cells with high oil content, and obviously improves the economic benefit and the environment-friendly benefit.
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 separation system, 104-an oxidation system and 105-a denitrification system; 201-culture medium and seed liquid, 202-filtrate, 203-microalgae cells, 204-sodium peroxide, 205-filtrate after reaction, 206-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, an oxidation 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, 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 an oxidation system 104, sodium peroxide 204 is added, then exhaust gas 302 is introduced for reaction, and purified gas 303 is discharged; and after the reaction, the filtrate 205 enters the denitrification system 105 for treatment, and water 206 is obtained after the 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
Table 2 composition of a5+ Co solution in table 1
Preparing BG11 liquid culture medium according to tables 1 and 2, adjusting pH to 8.0, inoculating fibroalgae SS-B7 and chlorella SF-B1 into microalgae culture medium, culturing in a constant temperature light shaking table at 25 deg.C with light period of 24h, light-dark time ratio of 14:10 and light intensity of 5000Lux at 120rpm, and performing shaking culture to logarithmic phase to obtain fibroalgae SS-B7 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) And adding the prepared fibroalgae SS-B7 seed liquid and a microalgae culture medium into a 10L photobioreactor, wherein the addition amount of the microalgae culture medium is 6L, and the addition amount of the seed liquid is 0.9L. 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 40%.
(2) After 7 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 11.7g/L, and the oil content is 43.5% of the dry cell weight.
(3) And (3) adding sodium peroxide into the filtrate obtained in the step (2), wherein the adding amount is 2.8g/L, and introducing the exhaust gas collected in the step (1) into the filtrate for treatment to obtain purified gas. Purifying the gas of CO2The removal rate was 92% and the NO removal rate was 91%.
(4) Denitrifying sludge is inoculated into the filtrate for denitrification treatment, and the sludge concentration is 5000 mg/L. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 2
(1) And adding the prepared fibroalgae SS-B7 seed liquid and a microalgae culture medium into a 10L photobioreactor, wherein the addition amount of the microalgae culture medium is 6L, and the addition amount of the seed liquid is 1.0L. 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. In the collected exhaust gas, CO2The removal rate was 75%, and the NO removal rate was 30%.
(2) After 8 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 11.1g/L, and the oil content is 42.2% of the dry cell weight.
(3) Adding sodium peroxide into the filtrate obtained in the step (2) in an amount of 6.2g/L, and performing the step (a)1) And introducing the collected exhaust gas into the filtrate for treatment to obtain purified gas. Purifying the gas of CO2The removal rate was 88% and the NO removal rate was 75%.
(4) And (4) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the purified gas obtained in the step (3) into a reaction system for treatment to obtain secondary purified gas. Secondary purification of CO in gas2The 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 3
(1) And adding the prepared fibroalgae SS-B7 seed liquid and a microalgae culture medium into a 10L photobioreactor, wherein the addition amount of the microalgae culture medium is 6L, and the addition amount of the seed liquid is 1.2L. Introducing flue gas containing CO2The content of (A) is 40v%, the NO content is 0.05 v%; the ventilation was 0.25 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 was 55% and the NO removal rate was 20%.
(2) After 8 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 10.7g/L, and the oil content is 41.8% of the dry cell weight.
(3) And (3) adding sodium peroxide into the filtrate obtained in the step (2), wherein the adding amount is 3.6g/L, and introducing the exhaust gas collected in the step (1) into the filtrate for treatment to obtain purified gas. Purifying the gas of CO2The removal rate was 70% and the NO removal rate was 75%.
(4) And (4) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the purified gas obtained in the step (3) into a reaction system for treatment to obtain secondary purified gas. Secondary purification of CO in gas2The removal rate is 75%, and the removal rate of NO is 85%. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 4
(1) CO in the flue gas adopted2Is 10v% and NO containsThe amount was 1.0v%, and the ventilation amount was 0.3 vvm. The prepared fibrophyta SS-B7 seed liquid and a microalgae culture medium are respectively added into a two-stage photobioreactor with the volume of 10L, the addition amount of the microalgae culture medium is 6L, and the addition amount of the seed liquid is 1.2L. 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. The exhaust gas of the first-stage reactor enters a second-stage reactor. CO in the exhaust gas of the secondary reactor2The removal rate is 80%, and the removal rate of NO is 35%.
(2) After 8 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 10.6g/L, and the oil content is 42.5% of the dry cell weight.
(3) And (3) adding sodium peroxide into the filtrate obtained in the step (2), wherein the adding amount is 3.6g/L, and introducing the exhaust gas collected in the step (1) into the filtrate for treatment to obtain purified gas. Purifying the gas of CO2The removal rate is 85%, and the removal rate of NO is 70%.
(4) And (4) introducing denitrification sludge into the filtrate, wherein the sludge concentration is 5000mg/L, and introducing the purified gas obtained in the step (3) into a reactor for treatment to obtain secondary purified gas. Secondary purification of CO in gas2The removal rate is 90%, 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 2 were used, except that: simultaneously adding chlorella SF-B1 in the step (1), wherein the inoculation amount is unchanged, and the volume ratio of the chlorella SF-B1 seed liquid to the chlorella SS-B7 seed liquid is 1: 1. After the treatment in the step (1), collecting CO in the exhaust gas2The removal rate was 75%, and the NO removal rate was 70%. The addition amount of the sodium peroxide in the step (3) is reduced by nearly half, and CO in the obtained purified gas2The removal rate was 91% and the NO removal rate was 88%. The treatment of step (4) is not required. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 6
The same culture procedure and culture conditions as in example 2 were used, except that: simultaneously adding chlorella SF-B1 in the step (1), wherein the inoculation amount is unchanged, and the volume ratio of the chlorella SF-B1 seed liquid to the chlorella SS-B7 seed liquid is 1: 5. After the treatment in the step (1), collecting CO in the exhaust gas2The removal rate was 75%, and the NO removal rate was 60%. In the obtained purified gas, CO2The removal rate was 90% and the NO removal rate was 82%. The treatment of step (4) is not required. The total nitrogen removal rate in the treated effluent reaches over 90 percent.
Example 7
The same culture procedure and culture conditions as in example 2 were used, except that: step (4) adding the Marsh Coicoccus simultaneouslyKocuria palustris) FSDN-A, Staphylococcus cohnii (Staphylococcus cohnii) FSDN-C, Arthrobacter (A)Arthrobacter creatinolyticus) FDN-1, Flavobacterium aquatile: (Flavobacterium mizutaii) Any one of FDN-2, the preparation method of the inoculation liquid is the same as CN103103141A, CN103014128A, CN102465106A and CN102465105A, and the inoculation amount is 1 percent of the volume of the sewage treatment system. In the obtained purified gas, CO2The removal rate is 92 percent, the NO removal rate is 90 percent, and the total nitrogen removal rate in the treated effluent reaches more than 95 percent.
Example 8
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 final effect of the treatment 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: the Chlorella vulgaris FY1# described in CN102311921A is used, because NO is not tolerantXTherefore, after a period of growth, a large number of the plants die, 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 NOx-containing flue gas is characterized by comprising the following steps:
(1) introducing the flue gas into a photobioreactor for microalgae culture, and collecting exhaust gas, wherein the microalgae is tolerant to NOx; 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; inoculating a microalgae culture medium and microalgae seed liquid into a photobioreactor, wherein the microalgae culture medium adopts BG11, SE and BBM to culture a liquid culture medium of microalgae; the inoculation amount of the microalgae seed liquid is 1-50% of the volume of the culture medium; the NOx-tolerant microalgae is fibroalgae SS-B7 with the preservation number of CGMCC number 7478;
(2) carrying out solid-liquid separation on the culture system in the step (1), and respectively harvesting microalgae cells and filtrate;
(3) adding sodium peroxide into the filtrate obtained in the step (2), and introducing the exhaust gas obtained in the step (1) into the filtrate for treatment to obtain purified gas;
(4) and (4) carrying out denitrification treatment on the filtrate treated in the step (3).
2. The method of claim 1, wherein: the flue gas containing NOx in the step (1) contains NOx and CO2Of flue gas, NOx being mainly NO and/or NO2(ii) a When 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 NOx-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 according to claim 1 or 2, characterized in that: step (1) controlling CO in each stage of photobioreactor2The content is 5v% -35 v%; the NOx content was below 0.06 v%.
5. The method of claim 1, wherein: the inoculation amount of the microalgae seed liquid in the step (1) is 5-30% of the volume of the culture medium.
6. The method of claim 1, wherein: the volume ratio of the fibroalgae SS-B7 seed liquid to the microalgae culture medium is 1: 20-1: 5.
7. The method according to claim 1 or 6, characterized in that: meanwhile, a certain amount of chlorella SF-B1 is inoculated, and the preservation number is CGMCC number 11005.
8. The method of claim 7, wherein: when the chlorella is inoculated with the strain SF-B1, the volume ratio of the chlorella SS-B7 seed liquid to the chlorella SF-B1 seed liquid is 1:1-50: 1.
9. The method according to claim 6 or 8, characterized in that: the preparation method of the seed liquid of the fibrophyta SS-B7 and the chlorella SF-B1 comprises the following steps: adjusting the pH value of a microalgae culture medium to 6-9, carrying out shaking culture at the temperature of 20-30 ℃, the illumination period of 24 hours, the light-dark time ratio of 14: 10-10: 14 and the illumination intensity of 2000-10000 Lux until the microalgae culture medium reaches the logarithmic phase.
10. 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 6-9, the illumination intensity is 2000-20000 Lux, and the culture is carried out until the growth stabilization period is finished.
11. The method of claim 1, wherein: and (4) adding sodium peroxide into the filtrate obtained in the step (3), and determining according to the content of the residual NOx in the exhaust gas to convert the residual NOx into nitrite, wherein the adding amount is 1-30 g/L.
12. The method according to claim 1 or 11, characterized in that: and (4) introducing the purified gas obtained in the step (3) into the denitrification treatment system obtained in the step (4) for further treatment if the removal rate of NOx in the purified gas obtained in the step (3) is lower than 80%.
13. The method of claim 1, wherein: the filtrate in the step (4) is mainly nitrite and nitrate, 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: and (4) adding at least one of the Coicoccus palustris FSDN-A, the Staphylococcus cohnii FSDN-C, the Arthrobacter FDN-1 and the Flavobacterium aquatile FDN-2 in the denitrification treatment.
15. A flue gas treatment plant containing NOx for use in a process according to any one of claims 1 to 14, characterized in that: comprises a photo-biological reaction system, a discharge gas collecting system, a solid-liquid separation system, an oxidation system and a denitrification system.
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| CN105713950A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Method for producing microalgal oil by using flue gas |
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| CN104190226A (en) * | 2014-07-23 | 2014-12-10 | 大连理工大学 | Complexing absorption and aerobic denitrification combined smoke denitration process |
| CN105713950A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Method for producing microalgal oil by using flue gas |
| CN106746158A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of coal water slurry gasification process produces the deepness denitrogenation method for treating of waste water |
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