CN109876641A - A kind of processing method and processing device of the flue gas containing NOx - Google Patents
A kind of processing method and processing device of the flue gas containing NOx Download PDFInfo
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- CN109876641A CN109876641A CN201711277175.7A CN201711277175A CN109876641A CN 109876641 A CN109876641 A CN 109876641A CN 201711277175 A CN201711277175 A CN 201711277175A CN 109876641 A CN109876641 A CN 109876641A
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- gas
- nox
- flue gas
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- microalgae
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- 239000003546 flue gas Substances 0.000 title claims abstract description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000012545 processing Methods 0.000 title claims abstract description 33
- 238000003672 processing method Methods 0.000 title claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 69
- 239000000706 filtrate Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 15
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000003306 harvesting Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 39
- 241000195493 Cryptophyta Species 0.000 claims description 26
- 238000005286 illumination Methods 0.000 claims description 19
- 239000001963 growth medium Substances 0.000 claims description 18
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000010802 sludge Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000003519 ventilatory effect Effects 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- 241000589565 Flavobacterium Species 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 241000607142 Salmonella Species 0.000 claims description 3
- 241000191940 Staphylococcus Species 0.000 claims description 3
- 230000003698 anagen phase Effects 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- 235000015097 nutrients Nutrition 0.000 claims description 3
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000012010 growth Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000000258 photobiological effect Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011953 bioanalysis Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- 244000046052 Phaseolus vulgaris Species 0.000 description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002054 inoculum Substances 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 235000012149 noodles Nutrition 0.000 description 4
- 238000009777 vacuum freeze-drying Methods 0.000 description 4
- 241000195651 Chlorella sp. Species 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 241000352081 Glutamicibacter creatinolyticus Species 0.000 description 2
- 241001237849 Kocuria palustris Species 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 241001147698 Staphylococcus cohnii Species 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 241000196169 Ankistrodesmus Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 208000027109 Headache disease Diseases 0.000 description 1
- VCZKTIKPEDMZNW-UHFFFAOYSA-N O=S(=O)=S Chemical class O=S(=O)=S VCZKTIKPEDMZNW-UHFFFAOYSA-N 0.000 description 1
- 241000190872 Sphingobacterium mizutaii Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical class S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Treating Waste Gases (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to a kind of processing methods of flue gas containing NOx, including (1), and flue gas to be passed through in bioreactor and is used for microdisk electrode, collects discharge gas, and the microalgae is to be resistant to the microalgae of NOx；(2) step (1) cultivating system is separated by solid-liquid separation, respectively harvesting microalgae cell and filtrate；(3) sodium peroxide is added in step (2) filtrate, and step (1) discharge gas is passed through in filtrate and is handled, is purified gas；(4) step (3) Filtrate carries out denitrification processing.The present invention also provides a kind of processing units for the flue gas containing NOx.The present invention mainly uses the CO in bioanalysis removing flue gas2、NOX, without using catalyst and a large amount of chemical reagent, have many advantages, such as that removal effect is good, processing cost is low, economic and environment-friendly.
Description
Technical field
The invention belongs to smoke gas treatment technical fields, and in particular to a kind of processing method and processing device of the flue gas containing NOx.
Background technique
Nitrogen oxides (NOx) has N2O、NO、NO2、N2O3、N2O4And N2O5Etc. diversified forms, and a variety of harm can be caused, such as
Photochemical fog can be generated with the volatile organic matter (VOC) in atmosphere, to cause strong impulse to make in eyes, throat
With, and cause headache and respiratory disease etc., serious person will cause death.China's NOx discharge is for years more than 2000
Ten thousand tons, 2010 are 21,940,000 tons, and 2011 are 2404.3 ten thousand tons, and 2012 are 2337.8 ten thousand tons, and 2013 are 2227.3 ten thousand
Ton, 2014 are 20,780,000 tons, although continuous decreasing trend has been presented since 2012, its pollution situation is still severe.
On September 12nd, 2014, three ministries and commissions such as National Development and Reform Commission, Environmental Protection Department and National Energy Board joint publication " about print and distribute <
Coal electricity energy-saving and emission-reduction upgrading with transformation action plan (2014-2020) > notice " (hair changes the energy [2014] 2093),
It asks and " ultra-clean discharge " is carried out to fire coal boiler fume, is i.e. flue dust, SO210mg/ is respectively reached with NOx emission concentration index
Nm3、35mg/Nm3And 50mg/Nm3。
Gas denitrifying technology mainly has at present: the SCR(selective catalytic reduction of gas phase reaction)) and SNCR(selectivity
Noncatalytic reduction), liquid absorption method, solid absorption method, high energy electron active oxidation method (EBA electron beam irradiation method and PPCP
Impulse electric corona plasma method) etc..In numerous denitrating flue gas processing techniques, liquid absorption method denitration efficiency is low；Absorption method is de-
Nitre is high-efficient, but adsorbance is small, and frequently, application is not extensive for regeneration；High energy electron active oxidation method can with simultaneous SO_2 and NO removal, but
Energy consumption is high, and the service life is short；The escapement ratio of SNCR method ammonia is high, can generate safety problem.SCR technology has de- compared with other technologies
The advantages that nitre is high-efficient, technology maturation is that Flue Gas Denitrification Engineering applies most technologies both at home and abroad at present.SCR method refers to anti-
200-400 DEG C of temperature is answered, NH is used3Make reducing agent and NOx catalysis is reduced to N2, the oxygen in exhaust gas seldom participates in reaction, thermal discharge
It is small.But the reaction is in the presence of a catalyst, still needs to carry out in higher temperature, and the problems such as there are the escaping of ammonia.
Flue-gas denitration process disclosed in Chinese patent CN103768903A, CN103768932A, CN103768934A etc. needs
The flue-gas temperature for wanting 300~400 DEG C implements large-scale redevelopment to boiler, and investment cost is higher.CN102716752A discloses one
Kind low temperature SCR denitration catalyst, the catalyst is in 300ppm SO2Under the conditions of 10% water vapour content, under the conditions of 150-250 DEG C
The removal rate of NOx can keep good removal of nitrogen oxide rate in 38-72% between 150-250 DEG C.But the invention system
Standby catalyst belongs to vanadium W-Sn deposits, and ammonium metavanadate becomes V after calcining2O5, V2O5It is a kind of extremely toxic substance,
Serious pollution can be generated in production, use process.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of processing method and processing devices of flue gas containing NOx.Master of the present invention
It will be using the CO in bioanalysis removing flue gas2、NOX, without using catalyst and a large amount of chemical reagent, place good with removal effect
Manage the advantages that at low cost, economic and environment-friendly.
The processing method of present invention flue gas containing NOx, including following content:
(1) flue gas is passed through in bioreactor and is used for microdisk electrode, collect discharge gas, the microalgae is the micro- of tolerance NOx
Algae；
(2) step (1) cultivating system is separated by solid-liquid separation, respectively harvesting microalgae cell and filtrate；
(3) sodium peroxide is added in step (2) filtrate, and step (1) discharge gas is passed through in filtrate and is handled, obtains net
Change gas；
(4) step (3) Filtrate carries out denitrification processing.
In the present invention, flue gas containing NOx described in step (1) is containing NOx, CO2Flue gas, NOx is mainly NO and/or NO2, such as
It can be in the flue gases such as sulfur recovery facility incineration tail gas, catalytic cracked regenerated tail gas, coal-fired flue-gas, sintering flue gas extremely
Few one kind.When containing sulfur dioxide sulfides in flue gas, flue gas carries out desulfurization pretreatment first.According to NOx in flue gas,
CO2Multistage bioreactor can be set in content, controls CO in every grade of bioreactor2Content is lower than 45v%, preferably
5v%~35v%；NOx content is lower than 0.1v%, preferably shorter than 0.06v%；Ventilatory capacity is 0.1-1.0vvm.
In the present invention, step (1) accesses micro-algae culture medium and microalgae seed liquor, micro-algae culture medium in bioreactor
Using the fluid nutrient medium of the culture microalgae such as BG11, SE, BBM well known in the art, determined with specific reference to the type of microalgae.
The preparation of micro-algae culture medium and microalgae seed liquor is culture volume with ability conventional technical means, the inoculum concentration of microalgae seed liquor
1%~50%, preferably 5%~30%.
In the present invention, the microalgae of step (1) the tolerance NOx is the published any microalgae for being resistant to NOx, preferably
Using algae fibre (Ankistrodesmus sp.) SS-B7, the algae strain be preserved in China Microbiological on April 15th, 2013
Culture presevation administration committee common micro-organisms center, deposit number are CGMCC No. 7478, and preservation address is court, Beijing
No. 3 Institute of Microorganism, Academia Sinica, institute of positive area's North Star West Road 1.Algae strain discloses in CN 105713836A, and
Having submitted preservation and survival proves.
Further, it is preferable to access simultaneously a certain amount of chlorella (Chlorella sp.) SF-B1, the chlorella
(Chlorella sp.) to be preserved in China Committee for Culture Collection of Microorganisms on July 6th, 2015 common by SF-B1
Microorganism center, deposit number are CGMCC No. 11005, and preservation address is in Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3
Institute of microbiology, the academy of sciences, state.Frustule is green to the chlorella SF-B1 under the microscope, single-cell algae, Dan Sheng, carefully
Born of the same parents' shape is spherical and ellipse, inside there is chromatoplast, and diameter is 5-6 μm.
In the present invention, the microalgae seed liquor the preparation method is as follows: the pH of micro-algae culture medium is adjusted to 6~9, in temperature
Degree is 20~30 DEG C, and periodicity of illumination is that for 24 hours, brightness time ratio is 14:10~10:14, and intensity of illumination is 2000~10000Lux,
Shaken cultivation is to logarithmic growth phase.The volume ratio of incoming fiber algae SS-B7 seed liquor and micro-algae culture medium in bioreactor
For 1:20~1:5.As further access chlorella SF-B1, algae fibre SS-B7 seed liquor and chlorella SF-B1 seed liquor
Volume ratio is 1:1-50:1.
In the present invention, the condition of step (1) described microdisk electrode are as follows: 10~35 DEG C of temperature, periodicity of illumination for 24 hours, when brightness
Between than 10:14~14:10, pH value 6~9,2000~20000Lux of intensity of illumination, culture to growth stationary phase terminates.
In the present invention, step (2) is separated by solid-liquid separation using modes such as centrifugation, filterings, and harvesting microalgae cell and filtrate, survey respectively
Determine dry cell weight and fat content, dry cell weight can reach 10g/L or more, and fat content can reach 40% of dry cell weight or more.
In the present invention, a certain amount of sodium peroxide is added in step (3) filtrate, with specific reference to the remaining NOx in discharge gas
Content determines, it is made to be converted into nitrite, and the amount of being preferably added to is 1~30g/L.In obtained purified gas, CO2And NOx removal
Rate is up to 70% or more.If NOx removal rate is lower than 80%, step (3) purified gas is passed through step (4) denitrification processing system
In, it is further processed.
It is mainly nitrite, nitrate in step (4) filtrate in the present invention, access denitrifying bacterium carries out at denitrification
Reason, the sludge concentration after inoculation are 2000-10000mg/L.The removal efficiency of total nitrogen reaches 90% or more in water outlet.Further, excellent
A certain amount of denitrification denitrogenation bacterium is added in choosing, as marsh cock Salmonella (Kocuria palustris) FSDN-A, Coriolis grape ball
Bacterium (Staphylococcus cohnii) FSDN-C, arthrobacterium (Arthrobacter creatinolyticus) FDN-1, water
Family name's Flavobacterium (Flavobacterium mizutaiiAt least one of) FDN-2, nitrogen removal rate can achieve 95% or more.
Wherein the preservation of marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2 are compiled
Number be respectively CGMCC NO.5061, CGMCC NO.5062, CGMCC No.3657, CGMCC No.3659, in
It is disclosed in CN103103141A, CN103014128A, CN102465106A, CN102465105A, and has submitted preservation and survival
It proves.
The present invention also provides a kind of devices for NOx fume treatment, including optical-biological reaction system, discharge gas to collect system
System, solid-liquid separation system, oxidative system and denilrification system, optical-biological reaction system mainly include several grades of optical-biological reactions
Device carries out microdisk electrode using the flue gas containing NOx being passed through；Gas collection system is discharged for collecting discharge gas；Solid-liquid separation system
For cultivating system to be separated by solid-liquid separation；Oxidative system is purified gas for sodium peroxide to be added；Denilrification system be used for
The filtrate arrived carries out denitrification processing.
Compared with prior art, the invention has the following advantages that
(1) using the CO in bioanalysis removing flue gas2、NOX, without using catalyst and a large amount of chemical agents, there is removing effect
The advantages that fruit is good, processing cost is low, economic and environment-friendly.
(2) using tolerance NOXMicroalgae handle flue gas, CO in flue gas2It is utilized for microalgae and generates O2, NO oxygen in flue gas
It is melted into NO2, NO is formed in water3 -And NO2 -, N is then converted in denitrification process2, above process synergistic effect, realization
CO2And NOXEfficient removal.
(3) algae fibre SS-B7 is used, NO is resistant toXPerformance is good, and carbon sequestration is high-efficient, the frustule of available high yield.Into
One step addition chlorella (Chlorella sp.) SF-B1, NOXRemoval effect it is more preferable.
(4) present invention not only can be with the processing flue gas of environmental protection and economy, but also the microalgae cell of available high fat content,
Economic benefit and environmental benefit are obviously improved.
Detailed description of the invention
Fig. 1 is the device of fume treatment of the invention；
Wherein 101- optical-biological reaction system, 102- discharge gas collection system, 103- solid-liquid separation system, 104- oxidative system,
105- denilrification system；201- culture medium and seed liquor, 202- filtrate, 203- microalgae cell, 204- sodium peroxide, 205- reaction
Filtrate afterwards, 206- water outlet；301- flue gas, 302- discharge gas, 303- purified gas.
Specific embodiment
Below by embodiment, invention is further described in detail.Embodiment is based on the technical solution of the present invention
Under implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following
Embodiment.In the present invention, v% is volume fraction.
Experimental method in following embodiment is unless otherwise specified conventional method in that art.Institute in following embodiments
Experimental material is commercially available from routine biochemistry reagent shop unless otherwise specified.
Flue gas processing device of the invention is as shown in Fig. 1, including optical-biological reaction system, discharge gas collection system, solid
Liquid separation system, oxidative system and denilrification system, wherein optical-biological reaction system 101 is a bioreactor or more
A bioreactor serial or parallel connection after micro-algae culture medium and seed liquor 201 is added, is passed through flue gas 301 and carries out microdisk electrode,
Discharge gas 302 is collected by discharge gas collection system 102；Microdisk electrode system enters solid-liquid separation system 103 and is separated, point
Other harvesting microalgae cell 203 and filtrate 202；Filtrate 202 enters oxidative system 104, and sodium peroxide 204, the row of then passing to is added
Deflation 302 is reacted, and purified gas 303 is discharged；Filtrate 205 enters denilrification system 105 and handles after reaction, must be discharged after processing
206。
Removal efficiency of the present invention is (be passed through Gas content-discharge Gas content)/it is passed through Gas content.
Microdisk electrode of the present invention uses BG11 culture medium, is formulated as shown in table 1, table 2.
1 BG11 culture medium of table
* in 2 table 1 of table A5+Co solution composition
BG11 fluid nutrient medium is prepared first, in accordance with Tables 1 and 2, pH is adjusted to 8.0, then by algae fibre SS-B7, chlorella
SF-B1 is inoculated in micro-algae culture medium, cultivates in constant temperature illumination shaking table, and cultivation temperature is 25 DEG C, and periodicity of illumination is brightness for 24 hours
Time ratio is 14:10, and intensity of illumination 5000Lux, 120rpm shaken cultivation to logarithmic growth phase obtains algae fibre SS-B7, small
Ball algae SF-B1 seed liquor.
The denitrification sludge that the embodiment of the present invention uses is derived from the denitrification processing pond in certain sewage farm, is discharged total nitrogen
Removal efficiency is up to 90% or more.
The flue gas that the present invention uses is containing NOx, CO2Flue gas, NOx is mainly NO and/or NO2.When containing dioxy in flue gas
When changing sulphur sulfides, desulfurization pretreatment is carried out first.
Embodiment 1
(1) in 10L bioreactor, the algae fibre SS-B7 seed liquor prepared and micro-algae culture medium, microdisk electrode is added
The additional amount of base is 6L, and the additional amount of seed liquor is 0.9L.It is passed through flue gas, CO in flue gas2Content be 5v%, NO content is
0.03v%, ventilatory capacity 0.5vvm.The intensity of illumination of culture is 5000Lux, and cultivation temperature is 25 DEG C, and periodicity of illumination is light for 24 hours
Dark time ratio is 14:10.In the discharge gas of collection, CO2Removal efficiency is that 85%, NO removal efficiency is 40%.
(2) after cultivating 7 days, microalgae cell and filtrate is harvested by centrifugation.Measure dry cell weight and fat content.In -60 DEG C of items
Measure algae dried bean noodles weight under part after vacuum freeze drying to constant weight, calculate yield of biomass, and use n-hexane: ethyl acetate method is surveyed
Obtain total lipid content.Dry cell weight can reach 11.7g/L after detecting, and fat content is the 43.5% of dry cell weight.
(3) sodium peroxide, additional amount 2.8g/L are added in step (2) filtrate, the discharge gas that step (1) is collected leads to
Enter in filtrate and handled, is purified gas.In purified gas, CO2Removal efficiency is that 92%, NO removal efficiency is 91%.
(4) denitrification sludge is accessed in filtrate carry out denitrification processing, sludge concentration 5000mg/L.It is discharged after processing
Middle nitrogen removal rate is up to 90% or more.
Embodiment 2
(1) in 10L bioreactor, the algae fibre SS-B7 seed liquor prepared and micro-algae culture medium, microdisk electrode is added
The additional amount of base is 6L, and the additional amount of seed liquor is 1.0L.It is passed through flue gas, CO in flue gas2Content be 10v%, NO content is
0.05v%, ventilatory capacity 0.5vvm.The intensity of illumination of culture is 5000Lux, and cultivation temperature is 25 DEG C, and periodicity of illumination is light for 24 hours
Dark time ratio is 14:10.In the discharge gas of collection, CO2Removal efficiency is that 75%, NO removal efficiency is 30%.
(2) after cultivating 8 days, microalgae cell and filtrate is harvested by centrifugation.Measure dry cell weight and fat content.In -60 DEG C of items
Measure algae dried bean noodles weight under part after vacuum freeze drying to constant weight, calculate yield of biomass, and use n-hexane: ethyl acetate method is surveyed
Obtain total lipid content.Dry cell weight can reach 11.1g/L after detecting, and fat content is the 42.2% of dry cell weight.
(3) sodium peroxide, additional amount 6.2g/L are added in step (2) filtrate, the discharge gas that step (1) is collected leads to
Enter in filtrate and handled, is purified gas.In purified gas, CO2Removal efficiency is that 88%, NO removal efficiency is 75%.
(4) denitrification sludge, sludge concentration 5000mg/L are accessed in filtrate, and step (3) purified gas is passed through instead
It answers in system and handles, obtain secondary purification gas.In secondary purification gas, CO2Removal efficiency is that 90%, NO removal efficiency is 85%.After processing
Nitrogen removal rate is up to 90% or more in water outlet.
Embodiment 3
(1) in 10L bioreactor, the algae fibre SS-B7 seed liquor prepared and micro-algae culture medium, microdisk electrode is added
The additional amount of base is 6L, and the additional amount of seed liquor is 1.2L.It is passed through flue gas, CO in flue gas2Content be 40v%, NO content is
0.05v%；Ventilatory capacity is 0.25vvm.The intensity of illumination of culture be 5000Lux, cultivation temperature be 25 DEG C, periodicity of illumination be for 24 hours,
Brightness time ratio is 14:10.In the discharge gas of collection, CO2Removal efficiency is that 55%, NO removal efficiency is 20%.
(2) after cultivating 8 days, microalgae cell and filtrate is harvested by centrifugation.Measure dry cell weight and fat content.In -60 DEG C of items
Measure algae dried bean noodles weight under part after vacuum freeze drying to constant weight, calculate yield of biomass, and use n-hexane: ethyl acetate method is surveyed
Obtain total lipid content.Dry cell weight can reach 10.7g/L after detecting, and fat content is the 41.8% of dry cell weight.
(3) sodium peroxide, additional amount 3.6g/L are added in step (2) filtrate, the discharge gas that step (1) is collected leads to
Enter in filtrate and handled, is purified gas.In purified gas, CO2Removal efficiency is that 70%, NO removal efficiency is 75%.
(4) denitrification sludge, sludge concentration 5000mg/L are accessed in filtrate, and step (3) purified gas is passed through instead
It answers in system and is handled, obtain secondary purification gas.In secondary purification gas, CO2Removal efficiency is that 75%, NO removal efficiency is 85%.Place
After reason in water outlet nitrogen removal rate up to 90% or more.
Embodiment 4
(1) CO in the flue gas used2Content be 10v%, NO content be 1.0v%, ventilatory capacity 0.3vvm.Using two-stage photoproduction
In object reactor, volume 10L is separately added into the algae fibre SS-B7 seed liquor prepared and micro-algae culture medium, micro-algae culture medium
Additional amount be 6L, the additional amount of seed liquor is 1.2L.The intensity of illumination of culture is 5000Lux, and cultivation temperature is 25 DEG C, illumination
Period is that for 24 hours, brightness time ratio is 14:10.First-stage reactor discharge gas enters second reactor.The second reactor of collection
It discharges in gas, CO2Removal efficiency is that 80%, NO removal efficiency is 35%.
(2) after cultivating 8 days, microalgae cell and filtrate is harvested by centrifugation.Measure dry cell weight and fat content.In -60 DEG C of items
Measure algae dried bean noodles weight under part after vacuum freeze drying to constant weight, calculate yield of biomass, and use n-hexane: ethyl acetate method is surveyed
Obtain total lipid content.Dry cell weight can reach 10.6g/L after detecting, and fat content is the 42.5% of dry cell weight.
(3) sodium peroxide, additional amount 3.6g/L are added in step (2) filtrate, the discharge gas that step (1) is collected leads to
Enter in filtrate and handled, is purified gas.In purified gas, CO2Removal efficiency is that 85%, NO removal efficiency is 70%.
(4) denitrification sludge, sludge concentration 5000mg/L are accessed in filtrate, and step (3) purified gas is passed through instead
It answers in device and is handled, obtain secondary purification gas.In secondary purification gas, CO2Removal efficiency is that 90%, NO removal efficiency is 80%.Processing
Afterwards in water outlet nitrogen removal rate up to 90% or more.
Embodiment 5
Using incubation and condition of culture same as Example 2, the difference is that: chlorella is added simultaneously in step (1)
SF-B1, inoculum concentration is constant, and the volume ratio of chlorella SF-B1 seed liquor and algae fibre SS-B7 seed liquor is 1:1.At step (1)
After reason, CO in the discharge gas of collection2Removal efficiency is that 75%, NO removal efficiency is 70%.The additional amount of step (3) sodium peroxide reduces close
Half, in obtained purified gas, CO2Removal efficiency is that 91%, NO removal efficiency is 88%.Without carrying out the processing of step (4).After processing
Nitrogen removal rate is up to 90% or more in water outlet.
Embodiment 6
Using incubation and condition of culture same as Example 2, the difference is that: chlorella is added simultaneously in step (1)
SF-B1, inoculum concentration is constant, and the volume ratio of chlorella SF-B1 seed liquor and algae fibre SS-B7 seed liquor is 1:5.At step (1)
After reason, CO in the discharge gas of collection2Removal efficiency is that 75%, NO removal efficiency is 60%.In obtained purified gas, CO2Removal efficiency is 90%,
NO removal efficiency is 82%.Without carrying out the processing of step (4).After processing in water outlet nitrogen removal rate up to 90% or more.
Embodiment 7
Using incubation and condition of culture same as Example 2, the difference is that: step (4) is added marsh simultaneously and examines
Kirschner bacterium (Kocuria palustris) FSDN-A, Staphylococcus cohnis (Staphylococcus cohnii) FSDN-C, section
Bacillus (Arthrobacter creatinolyticus) FDN-1, Shui Shi Flavobacterium (Flavobacterium mizutaii)
Any one in FDN-2, the same to CN103103141A, CN103014128A of the preparation method of inoculation liquid, CN102465106A,
CN102465105A, inoculum concentration are the 1% of sewage treatment system volume.In obtained purified gas, CO2Removal efficiency is 92%, NO de-
Except rate is 90%, after processing in water outlet nitrogen removal rate up to 95% or more.
Embodiment 8
Using incubation and condition of culture same as Example 2, the difference is that: CO in flue gas2Content be 10v%,
NO2Content is 0.05v%.The final effect of processing is substantially the same as embodiment 2.
Comparative example 1
Using incubation and condition of culture same as Example 1, the difference is that: using described in CN102311921A
Chlorella FY1#, due to not tolerating NOX, therefore mortality after a period of time is grown, subsequent process can not be carried out.
In summary, the present invention realizes the height of flue gas using the flue gas of microdisk electrode process processing nitrogen-containing oxide
Effect processing, while available microalgae grease, economic benefit and obvious environment benefit improve.
Claims (16)
1. a kind of processing method of flue gas containing NOx, it is characterised in that including following content:
(1) flue gas is passed through in bioreactor and is used for microdisk electrode, collect discharge gas, the microalgae is the micro- of tolerance NOx
Algae；
(2) step (1) cultivating system is separated by solid-liquid separation, respectively harvesting microalgae cell and filtrate；
(3) sodium peroxide is added in step (2) filtrate, and step (1) discharge gas is passed through in filtrate and is handled, obtains net
Change gas；
(4) step (3) Filtrate carries out denitrification processing.
2. according to the method described in claim 1, it is characterized by: flue gas containing NOx described in step (1) is containing NOx, CO2Cigarette
Gas, NOx are mainly NO and/or NO2；When containing SO in flue gas2When, flue gas carries out desulfurization pretreatment first.
3. method according to claim 1 or 2, it is characterised in that: flue gas containing NOx described in step (1) is returned from sulphur
In the flue gases such as receiving apparatus incineration tail gas, catalytic cracked regenerated tail gas, S-zorb regeneration tail gas, coal-fired flue-gas, sintering flue gas extremely
Few one kind.
4. method according to claim 1 or 2, it is characterised in that: step (1) is according to NOx, CO in flue gas2Content, can be with
Multistage bioreactor is set, CO in every grade of bioreactor is controlled2Content is lower than 45v%, preferably 5v%~35v%；
NOx content is lower than 0.1v%, preferably shorter than 0.06v%；Ventilatory capacity is 0.1-1.0vvm.
5. according to the method described in claim 1, it is characterized by: step (1) accesses microdisk electrode in bioreactor
Base and microalgae seed liquor, micro-algae culture medium cultivate the fluid nutrient medium of microalgae using BG11, SE, BBM；The inoculation of microalgae seed liquor
Amount is the 1%~50% of culture volume, preferably 5%~30%.
6. according to the method described in claim 1, it is characterized by: the microalgae of step (1) the tolerance NOx is to be resistant to
Any microalgae of NOx, it is preferred to use algae fibre SS-B7, deposit number are CGMCC No. 7478.
7. according to the method described in claim 6, it is characterized by: incoming fiber algae SS-B7 seed liquor in bioreactor
Volume ratio with micro-algae culture medium is 1:20~1:5.
8. method according to claim 6 or 7, it is characterised in that: while accessing a certain amount of chlorella SF-B1, preservation
Number is CGMCC No. 11005.
9. according to the method described in claim 8, it is characterized by: when accessing chlorella SF-B1, algae fibre SS-B7 seed liquor
Volume ratio with chlorella SF-B1 seed liquor is 1:1-50:1.
10. the method according to claim 7 or 9, it is characterised in that: the algae fibre SS-B7, chlorella SF-B1 seed
Liquid the preparation method is as follows: the pH of micro-algae culture medium is adjusted to 6~9, be 20~30 DEG C in temperature, periodicity of illumination is light for 24 hours
Dark time ratio is 14:10~10:14, and intensity of illumination is 2000~10000Lux, shaken cultivation to logarithmic growth phase.
11. according to the method described in claim 1, it is characterized by: the condition of step (1) described microdisk electrode are as follows: temperature 10
~35 DEG C, periodicity of illumination for 24 hours, brightness time ratio 10:14~14:10, pH value 6~9,2000~20000Lux of intensity of illumination, training
Supporting to growth stationary phase terminates.
12. according to the method described in claim 1, having it is characterized by: sodium peroxide is added in step (3) filtrate according to row
Remaining NOx content in deflation determines, it is made to be converted into nitrite, and the amount of being preferably added to is 1~30g/L.
13. according to claim 1 or method described in 12, it is characterised in that: in the purified gas that step (3) obtains, NOx removal rate
Lower than 80%, then step (3) purified gas is passed through in step (4) denitrification processing system, is further processed.
14. according to the method described in claim 1, it is characterized by: in step (4) filtrate be mainly nitrite, nitrate,
It accesses denitrifying bacterium and carries out denitrification processing, the sludge concentration after inoculation is 2000-10000mg/L.
15. according to the method for claim 14, it is characterised in that: marsh cock Salmonella in the processing of step (4) denitrification
At least one of FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2.
16. being used for the flue gas processing device containing NOx of any the method for claim 1-15, it is characterised in that: including photo-biological
Reaction system, discharge gas collection system, solid-liquid separation system, oxidative system and denilrification system.
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