CN108479379A - The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO - Google Patents
The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO Download PDFInfo
- Publication number
- CN108479379A CN108479379A CN201810606156.2A CN201810606156A CN108479379A CN 108479379 A CN108479379 A CN 108479379A CN 201810606156 A CN201810606156 A CN 201810606156A CN 108479379 A CN108479379 A CN 108479379A
- Authority
- CN
- China
- Prior art keywords
- edta
- reactor
- concentration
- solution
- anammox
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/95—Specific microorganisms
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a kind of methods that the up-flow iron bed Anammox absorbed based on Fe (II) EDTA handles NO, include the following steps：Sponge iron filler is placed on anaerobic ammonia oxidation reactor bottom, sludge seeding containing anaerobic ammonia oxidizing bacteria strain is entered in the middle part of reactor, and substrate reaction liquid is added, a part of solution enters reactor from bottom again after being come out from reactor upper return mouth, sludge is set to be in suspension growth state by reflux, gas containing NO is passed through from reactor bottom, keep reactor longtime running, Fe (II) EDTA solution, ternary mixed liquor is periodically added, the water outlet of respective volume is discharged after mixing of intaking every time from reactor top.The method of the present invention is very high to NO removal efficiency, and in the case of air inlet NO a concentration of 5% or even 10%, tail gas NO concentration can be reduced to 1ppm or so, and removal efficiency is close to 100%.
Description
Technical field
The invention belongs to nitrogen oxides treatment technical fields, and in particular to the up-flow that one kind is absorbed based on Fe (II) EDTA
The method of iron bed-Anammox processing NO.
Background technology
Nitrogen oxides is to cause one of important arch-criminal of the atmosphere polluting problems such as acid rain, gray haze, photochemical fog, is directly arranged
Being put into air can bring the very big harm, main harm to include to environment：To the toxic effect of human body；Harm to plant；
It is one of the main reason for forming acid rain and acid mist；Photochemical fog is caused with hydrocarbon reaction；Destroy ozone layer etc..It passes
The selective catalysis reduction of nitrogen oxides treatment technology of system, selective non-catalytic reduction, charcoal reduction method, absorption method, absorption process,
Direct biological treatment etc..Wherein selective catalytic reduction and selective non-catalytic reduction are industrially applied more, but this
There are some defects for two methods：For example investment operating cost is high, catalyst is easy inactivation, generates N2O and NH3Equal secondary pollutions
Object etc..
Biotechnology has many advantages, such as that investment operating cost is low, environmental pollution is small, it is considered to be a kind of promising replacement
The method that SCR removes denitrification, but nitrogen oxides 95% exists all in the form of the NO for being difficult to handle in coal-fired flue-gas, NO exists
Solubility in water is very low to cause its gas-liquid mass transfer efficiency low, cannot well be utilized by microorganism so that at direct bioanalysis
It is very low to manage the practical nitric efficiencies of NO.Many scholars have studied the nitrogen in chemical absorbing combination biological reducing method removal flue gas in recent years
Oxide.The method is that the NO absorbed using complexing agents such as Fe (II) EDTA in flue gas forms complex compound, to considerably increase NO
Solubility in water enhances the bioavailability of NO.Then it is complexed to the effect of NO in liquid phase microorganism in water
Under be reduced to nitrogen and removed.Common is that Fe (II) EDTA complexings combine NO in denitrification removal flue gas, but anti-nitre
It is mostly heterotrophic microorganism to change bacterium, needs outer plus organic carbon source as electron donor in biological treatment process, increases and actually answer
Operating cost in, while also will produce greenhouse gases N2O.Many Fe (II) EDTA complexings have also been emerged in large numbers in recent years and have been combined has detested
The denitrating technique of anaerobic ammonium oxidation.
Anammox refers to that under anaerobic, anaerobic ammonia oxidizing bacteria is with NO2 -As electron acceptor, by NH4 +Direct oxygen
It turns to as N2Microbiological process.NO is the intermediate product of Anammox reaction, can be with ammonia nitrogen in anaerobic ammonia oxidizing bacteria
Hydrazine synthesis enzyme effect under generate hydrazine, hydrazine is converted into nitrogen under the action of hydrazine dehydrogenase, and reaction mechanism is：
NO+NH4 ++2H++3e-=N2H4+H2O
N2H4=N2+4H++4e-
Compared to traditional biological method denitrating technique, Fe (II) EDTA complexings combine Anammox removal NO to have many good qualities：
1. not needing additional organic electron donors.Using factory ammonia-containing water provide ammonium ion, and with the nitric oxide in flue gas
Reaction, achievees the purpose that " treatment of wastes with processes of wastes against one another ".2. sludge output is low, greenhouse gases N is not generated in reaction process2O.But it reacted
Journey complexing agent Fe (II) EDTA easily by oxidation cause its complexing power decline, be influence NOx removal efficiency an important factor for,
So seeking suitable reducing agent regeneration Fe (II) EDTA also becomes research hotspot.
Sponge iron is a kind of cheap reducing agent, is a kind of common trade waste, and zeroth order iron content is more than 88%,
Our research indicate that sponge iron there is good reducing property, reduction efficiency can reach 90% or more Fe (III) EDTA,
And studies have reported that sponge iron can improve adaptability of the anaerobic ammonia oxidizing bacteria under low temperature and impact load, reinforced anaerobic
Ammoxidation performance.In addition, nitrate electronation can be NH by Zero-valent Iron4 +, can also be NH by NO electronations4 +, and NH4 +It is the matrix of Anammox reaction, nitrogen can be converted by anaerobic ammonia oxidizing bacteria together with NO.
Invention content
In view of the above technical problems, the present invention is intended to provide a kind of up-flow iron bed-absorbed based on Fe (II) EDTA is detested
The method that anaerobic ammonium oxidation handles NO.
For this purpose, the technical solution adopted in the present invention is：
A method of the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO, including walks as follows
Suddenly：Sponge iron filler is placed on anaerobic ammonia oxidation reactor bottom, the sludge seeding containing anaerobic ammonia oxidizing bacteria strain is entered
In the middle part of reactor, and substrate reaction liquid is added, a part of solution enters from bottom anti-again after being come out from reactor upper return mouth
Device is answered, makes sludge be in suspension growth state by reflux, the gas containing NO is passed through from reactor bottom, keeps reactor long-term
Operation, is periodically added Fe (II) EDTA solution, ternary mixed liquor, and corresponding body is discharged from reactor top after mixing of intaking every time
Long-pending water outlet；The substrate reaction liquid includes the component of following concentration：1.4~1.5mM of Fe (II) EDTA, NH4 +20~
30mgN/L、NaHCO31~1.5g/L, CaCl2·2H20.2~0.4g/L of O, MgSO4·7H20.2~0.4g/L of O, KH2PO4
0.04~0.06g/L, FeSO40.0060~0.0065g/L, 0.0060~0.0065g/L of EDTA, trace element solution 1~
1.5ml/L。
Fe (II) EDTA solution is added in the periodicity, ternary mixed liquor refers to：Reactor volume 6 is added within every 5~7 days
The ternary mixed liquor of reactor volume 6~8% is added in~8% Fe (II) EDTA solution daily；Fe (II) EDTA solution concentrations
For 15~25mmol/L, NH in ternary mixed liquor4 +Solution concentration is 110~140mgN/L, and the component and content of nutrient are such as
Under：NaHCO31~1.5g/L, CaCl2·2H20.2~0.4g/L of O, MgSO4·7H20.2~0.4g/L of O, KH2PO4 0.04
~0.06g/L, FeSO40.0060~0.0065g/L, 0.0060~0.0065g/L of EDTA are added in every liter of mixed liquor micro
1~1.5ml of Element Solution.
Fe (II) the EDTA solution FeSO4·7H2O and Na2EDTA presses 1:1 molar ratio.
The ammonia nitrogen solution is prepared with ammonium sulfate.
The trace element solution includes the component of following concentration：13~17g/L of EDTA, H3BO40.012~0.016g/
L、MnCl2·4H20.90~1.10g/L of O, CuSO4·5H20.20~0.30g/L of O, ZnSO4·7H20.35~0.50g/ of O
L、NiCl2·6H20.15~0.25g/L of O, Na2SeO4·10H20.15~0.26g/L of O, Na2MoO4·2H2O 0.17~
0.27g/L、Na2WO4·2H20.03~0.07g/L of O.
The each component of the nutrient is a concentration of：NaHCO3 1.25g/L、CaCl2·2H2O 0.3g/L、MgSO4·
7H2O 0.3g/L、KH2PO4 0.05g/L、FeSO40.00625g/L、EDTA 0.00625g/L；The trace element additive amount
For 1.25ml/L, each component is a concentration of in trace element solution：EDTA 15g/L、H3BO4 0.014g/L、MnCl2·4H2O
0.99g/L、CuSO4·5H2O 0.25g/L、ZnSO4·7H2O 0.43g/L、NiCl2·6H2O 0.19g/L、Na2SeO4·
10H2O 0.21g/L、Na2MoO4·2H2O 0.22g/L、Na2WO4·2H2O 0.05g/L。
The anaerobic ammonia oxidation reactor uses UASB reactors or EGSB reactors.
A concentration of 1.5mM of Fe (II) EDTA in the substrate reaction liquid.
At 30~35 DEG C, pH is controlled 7.0~8.0 for reactor temperature control
Sponge iron filler is placed on reactor bottom by the present invention, and the sludge seeding containing anaerobic ammonia oxidizing bacteria strain is entered
In the middle part of reactor, and substrate reaction liquid is added, the refluxing opening on a part of reacted device top of solution flows through peristaltic pump again from bottom
Into reactor, sludge is set to be in suspension growth state by reflux.NO gases are passed through from reactor bottom, by sponge iron filler
While react and be complexed as Fe (II) EDTA-NO with Fe in reactor (II) EDTA, the work of anaerobic ammonium oxidation sludge at middle part
Under, NO synthesizes hydrazine with ammonia nitrogen and is eventually converted to nitrogen and removed, the reacted device top discharge of outlet.Anaerobism ammonia oxygen
Change process will produce a part of nitrate, and nitrate reduction can be NH by sponge iron4 +, NO can also be reduced to NH4 +, and
NH4 +It is the matrix of Anammox, and can be utilized together by anaerobic ammonia oxidizing bacteria with NO, is converted into nitrogen.This not only can be with
The accumulation of nitrate is reduced, and the usage amount of ammonia nitrogen matrix can be reduced.Sponge iron can also be by the Fe (III) in system also
Originally it was Fe (II), and realized the regeneration of Fe (II) EDTA.In order to realize that the reduction of system cost, reactor keep not arranging as possible
Water periodically supplements ammonia nitrogen matrix and other nutrients.
The beneficial effects of the invention are as follows：
1) Fe (II) EDTA complexed absorption NO are utilized, NO is solved solubility is low in water and denitrification is gone to bioanalysis
Limitation.
2) sponge iron filler is added in reactor to play the role of regenerating Fe (II) EDTA, reduces Fe (II) and EDTA
The consumption of drug.And the nitrate reduction that can generate Anammox is NH4 +, NO is reduced to NH4 +, not only can be with
The accumulation for reducing nitrate, can also reduce the usage amount of ammonia nitrogen matrix, reduce operating cost.
3) it compares other biological method and handles nitrogen oxides technology, the final product of the method for the present invention is N2, no NO2, N2O,
N2O3Equal by-products, not will produce secondary pollution.And it is very high to NO removal efficiency, the case where air inlet NO a concentration of 5% or even 10%
Under, tail gas NO concentration can be reduced to 1ppm or so, and removal efficiency is close to 100%.This technology can effectively remove flue gas and give up
NO gases in gas have good prospects for commercial application.
4) one of matrix of the technique is NH4 +, it is that a kind of common important pollutant, this method can be by waste water in sewage
Denitrogenation combines with denitrating flue gas, realizes " treatment of wastes with processes of wastes against one another ", is that one kind is economic and environment-friendly, investment operating cost is few, secondary pollution
Small technique.
Description of the drawings
Fig. 1 is the UASB structure of reactor schematic diagrames that the present invention uses, wherein 1 main body, 1a air inlets, 1b water inlets, 1c
Water-bath import, 1d mud discharging mouths, 1e water outlets, 1f water-baths outlet, 1g water-baths interlayer, 1h refluxing openings, 2 liquid tanks, 3 lids, 3a are seen
Examine hole, the gas outlets 3b, 4 anaerobic ammonium oxidation sludges, 5 sponge iron fillers.
Fig. 2 is the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox removal NO reactions that the present invention uses
System schematic.
Fig. 3 is various concentration SO3 2-To Fe (III) EDTA reduction efficiency results.
Fig. 4 be under various concentration azanol to Fe (III) EDTA reduction efficiency results.
Fig. 5 be under different quality sponge iron to the reduction efficiency result of Fe (III) EDTA.
Fig. 6 is reduction efficiency and reaction ratio result of the different quality sponge iron to nitrate.
Fig. 7 is reduction efficiency and reaction ratio result of the different quality sponge iron to Fe (II) EDTA-NO.
Fig. 8 is up-flow iron bed-anaerobic ammonia oxidation reactor longtime running result, wherein a is NO concentration result of variations
Figure, b are NO removal rate figures.
Specific implementation mode
By way of example and in conjunction with the accompanying drawings, the invention will be further described：
Embodiment 1 is based on up-flow iron bed-nitric oxide production method of Anammox processing that Fe (II) EDTA absorbs
NO processing is carried out using up-flow iron bed shown in FIG. 1-Anammox UASB reactors in laboratory, is used
UASB reactors be the prior art, be put into sponge iron filler for convenience, reactor head designs lid and liquid tank, is put into
Closed with covers is sealed with screwed flange using silicagel pad after sponge iron, and by liquid tank water seal, air is avoided to enter reaction
Device.Liquid tank is arranged on the outer wall at the top of reactor body, is circumferentially arranged, by liquid tank water seal to protect when reactor is run
Inside reactor anaerobic environment is held, peep hole and gas outlet are provided on lid.
The reactor is assembled with miscellaneous equipment, as shown in Figure 2：By the reactor and Fe (II) EDTA water inlets, ammonia
Nitrogen water inlet, NO aerations, thermostat water bath, outlet pipe, airbag connect.About 1.6kg sponge iron is weighed, is soaked with 1mol/L HCl
It after steeping 20min, is rinsed repeatedly with anaerobic deionized water, the ironing surface impurity of removal sponge and oxidation film are put into reactor bottom.
Then the anaerobic ammonium oxidation sludge of enrichment culture is accessed into reactor, anaerobism ammonia oxygen of the seed sludge from laboratory long-term cultivation
Change EGSB reactors.Substrate reaction liquid is added in UASB reactors, control inside reactor temperature is maintained at 30~32 DEG C, instead
It answers and is wrapped up with masking foil outside device, illumination is avoided to generate harmful effect to anaerobic ammonia oxidizing bacteria.Periodic measurement inside reactor pH
And it is controlled in 7.0-7.5 ranges using the hydrochloric acid of 1mol/L or sodium hydroxide.Component in substrate reaction liquid and its a concentration of：Fe
(II) 1.4~1.5mM of EDTA, NH4 +20~30mgN/L, NaHCO31~1.5g/L, CaCl2·2H20.2~0.4g/L of O,
MgSO4·7H20.2~0.4g/L of O, KH2PO40.04~0.06g/L, FeSO40.0060~0.0065g/L, EDTA
0.0060~0.0065g/L, 1~1.5ml/L of trace element solution.Following (the unit g of the component and content of trace element solution
L-1)：EDTA 15,H3BO4 0.014,MnCl2·4H2O 0.99,CuSO4·5H2O 0.25,ZnSO4·7H2O 0.43,
NiCl2·6H2O 0.19,Na2SeO4·10H2O 0.21,Na2MoO4·2H2O 0.22andNa2WO4·2H2O 0.050。
As shown in Fig. 2, removing NO reaction systems in the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox
In, Fe (II) EDTA solution and ammonia nitrogen solution enter reactor with reactor backflow mixed liquor from bottom, by lower part sponge iron
It after filler, middle part anaerobic ammonium oxidation sludge, is discharged from reactor top, refluxing opening of a part of solution through side flows through peristaltic pump
Enter reactor from bottom again.NO gases are passed through from reactor bottom, by while sponge iron filler with reactor in Fe
(II) EDTA reactions are complexed as Fe (II) EDTA-NO, and at middle part under the action of anaerobic ammonium oxidation sludge, NO synthesizes connection with ammonia nitrogen
Ammonia is simultaneously eventually converted to nitrogen and is removed, and the reacted device top of outlet, which is discharged, is simultaneously collected with airbag, dense for measuring tail gas
Degree.Reaction system keeps not draining as possible after starting, but will produce consumption with carry out ammonia nitrogen and Fe (II) EDTA of reaction,
In order to supplement ammonia nitrogen and Fe (II) EDTA, periodically intakes and drain to reactor.Use FeSO4·7H2O and Na2EDTA presses 1:1
Molar ratio Fe (II) EDTA solution, concentration 20mmol/L, supplement is primary within about 5 days or so, supplements about 400ml (this hair every time
The volume of the bright UASB reactors used is 5.37L).Daily into a ternary mixed liquor, ternary mixed liquor is NH4 +, nutrition member
The mixed liquor of element and trace element solution, each liquid inlet volume about 400ml, NH in mixed liquor4 +A concentration of 124mgN/L, uses ammonium sulfate
It prepares, the component and content of the nutrient in mixed liquor are as follows：KH2PO4 0.05g/L、CaCl2·2H2O 0.3g/L、
MgSO4·7H2O 0.3g/L、NaHCO3 1.25g/L、FeSO40.00625g/L、EDTA 0.00625g/L；Every liter of mixed liquor
Middle addition 1.25mL trace element solutions.The reactor that ammonia nitrogen solution and the water inlet of Fe (II) EDTA solution can be measured according to experiment
Interior real-time matrix residue situation slightly adjusts, and the water outlet of respective volume is discharged after mixing of intaking every time from reactor top, makes anti-
Liquor capacity in device is answered to keep certain.Refluxing opening is arranged in reactor top, and anaerobism ammonia oxygen in reactor is made by way of reflux
Change sludge suspension growth.
NO gases are continuously passed through reactor, NO a concentration of 10% (Ar is carrier gas), charge flow rate from bottom in reaction process
For 2ml/min.Reactor continuous operation 80 days, detects that NO concentration is lower and lower in tail gas, and the later stage stablizes in 1ppm or so,
NO is averaged removal efficiency and average removal rate is respectively 99.99% and 7.61mM d-1, NO, which is substantially achieved, to be completely removed, reaction
Device can be with stable operation.NO is not detected in reactor During Process of Long-term Operation2 -And NO3 -, N2O concentration be constantly in detection limit with
Under.
Sponge iron filler is added in reactor, plays the role of regenerating Fe (II) EDTA, former researcher is in sbr reactor
The research of Fe (II) EDTA absorbing coupling Anammoxs removal NO has been carried out in device, Fe (II) EDTA oxidative phenomenas are serious,
It is 0.5636mmol/L/h that Fe (II), which loses rate, and up-flow iron bed-Anammox removes Fe (II) EDTA in NO new processes
Oxidation obtains very big alleviation, and it is only 0.0079mmol/L/h that Fe (II), which loses rate,.But there are still Fe (II) concentration to reduce
The phenomenon that, it needs periodically to supplement Fe (II) into reactor.Reason includes：1) it is dense to dilute Fe (II) EDTA for periodical Inlet and outlet water
Degree；2) there may be Fe in operational process3O4Precipitation causes a part of Fe (II) to lose；3) microorganism panning and utilize iron,
A part of Fe (II) is caused to lose.
Based on the present invention to the good removal capacity of higher concentration NO and sponge iron to the good reproducibilities of Fe (II) EDTA
Can, and NO concentration is far below 10% in practical flue gas, can apply the inventive method to nitrogen oxidation in industrial waste gas or flue gas
In object processing.
2 up-flow iron bed of embodiment-anaerobic ammonia oxidation reactor removes NO long-term experiments
According to the method for embodiment 1, the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox removal NO operations
The results detailed in Fig. 8, reactor has been run 80 days, the preceding NO being passed through for 17 days a concentration of 5%, flow 5ml/min, using interval into
Gas mode, aeration period 2h detect that NO concentration is very low in tail gas, and 34ppm or so is gradually lowered to from 200ppm.NO is average
Removal efficiency and average removal rate are respectively 99.89% and 4.75mM d-1.It observes that NO removal effects are fine, opens within the 18th day
Begin continuous 24 hours to be passed through NO, a concentration of 5%, flow 3ml/min, monitors that tail gas NO concentration is still very low, be reduced to
20ppm or so.18th~30 day NO is averaged removal efficiency and average removal rate is respectively 99.94% and 5.70mM d-1.By
In NO removal effects very well and a high level can be maintained at, start within the 31st day increase NO concentration, be continuously passed through within 24 hours
A concentration of 10% NO gases, flow 2ml/min detect that outlet NO concentration is lower and lower, and the later stage stablizes in 1ppm or so, NO
Average removal efficiency and average removal rate are respectively 99.99% and 7.61mM d-1, NO, which is substantially achieved, to be completely removed.Based on Fe
(II) the up-flow iron bed that EDTA absorbs-Anammox removal NO systems can be run steadily in the long term.
3 reducing agent contrast experiment of embodiment
One, Fe (III) EDTA reduction experiments
Experimental design：
Ammonium sulfite is the intermediate by-products of the ammonia process of desulfurization, have reproducibility, can with the Fe (III) in reduction system, and
The matrix NH of Anammox can be provided4 +, theoretically for be a kind of good reducing agent, Fe (III) EDTA can be restored.
Azanol is the intermediate product of Anammox reaction, and is reducing substances, and adding azanol in right amount in reactor contributes to anaerobism
Ammonia oxidation bacteria is grown.Sponge iron is a kind of cheap reducing agent, is a kind of common trade waste, some researches show that sponge iron
Adaptability of the anaerobic ammonia oxidizing bacteria under low temperature and impact load can be improved.Therefore selection ammonium sulfite, azanol, sponge iron
These three reducing agents have studied it under the UASB reactor service conditions for implementing 1 to the reproducibility of Fe (III) EDTA respectively
Energy.30 DEG C of temperature, under the conditions of pH6.5, the ammonium sulfite, azanol and the sponge iron that add various concentration respectively have carried out Fe (III)
EDTA reduction experiments.
Experimental result：
Fig. 3 is 30 DEG C, pH 6.5 when various concentration SO3 2-To Fe (III) EDTA reduction efficiencies, as can be seen from the figure SO3 2-
A concentration of 10,20,40mM when be respectively 8.68%, 8.81% and 8.85% to the reduction efficiency of Fe (III) EDTA, illustrate anti-
Answer SO under device service condition3 2-It is very low to Fe (III) EDTA reduction efficiencies.As shown in figure 4, the azanol of various concentration is to Fe at 30 DEG C
(III) EDTA reduction efficiencies are all very low, and smaller than 10%.The experimental results showed that ammonium sulfite and hydroxylamine reduction Fe (III) EDTA by
Temperature influences very big, and reduction efficiency is directly proportional to temperature, and reduction efficiency is below 10% at 30 DEG C, therefore is not suitable as Fe
(III) EDTA reducing agents.Fig. 5 is reduction efficiency of the sponge iron to Fe (III) EDTA for adding different quality, it can be seen that sponge
Iron is very high to the reduction efficiency of Fe (III), when adding 50g and 100g sponge iron, to Fe3+Reduction efficiency all close to 90%,
It can be considered to the later stages to add sponge iron into reactor.
Two, spongy iron reducing nitrate, spongy iron reducing Fe (II) EDTA-NO experiments
Fig. 6 is reduction efficiency and reaction ratio of the different quality sponge iron to nitrate, adds 50g, 100g, 200g sponge
NO when iron3 -Reduction efficiency respectively reach 100%, 99.53% and 92.38%, △ NO3 --N/△NH4 +N ratio is respectively
1.00,1.01 and 0.94.The removal amount of nitrate illustrates product master with ammonia nitrogen production quantity ratio close to 1: 1 in three groups of experiments
If NH4 +。
Generable chemical equation is as follows：
NO removal efficiency respectively reaches 92.69% and 97.31%, two kinds of feelings when Fig. 7 display addition 25g and 100g sponge iron
Δ NO-N/ Δs NH under condition4 +- N is close to 1: 1, therefore, is likely to be converted to NH with Fe (II) EDTA NO combined4 +.Zero-valent Iron
Reduction Fe (II) EDTA-NO chemical reaction equation be：
2Fe(II)EDTA-NO+5Fe+12H+→2Fe(II)EDTA+5Fe2++2NH4 +。
Claims (9)
1. the method for the up-flow iron bed that one kind is absorbed based on Fe (II) EDTA-Anammox processing NO, which is characterized in that packet
Include following steps：Sponge iron filler is placed on anaerobic ammonia oxidation reactor bottom, by the dirt containing anaerobic ammonia oxidizing bacteria strain
Mud is inoculated with into the middle part of reactor, and substrate reaction liquid is added, a part of solution from reactor upper return mouth come out after again the bottom of from
Portion enters reactor, makes sludge be in suspension growth state by reflux, and the gas containing NO is passed through from reactor bottom, keeps anti-
Device longtime running is answered, Fe (II) EDTA solution, ternary mixed liquor is periodically added, is arranged from reactor top after mixing of intaking every time
Go out the water outlet of respective volume；The substrate reaction liquid includes the component of following concentration：1.4~1.5mM of Fe (II) EDTA, NH4 +
20~30mgN/L, NaHCO31~1.5g/L, CaCl2·2H20.2~0.4g/L of O, MgSO4·7H20.2~0.4g/L of O,
KH2PO40.04~0.06g/L, FeSO40.0060~0.0065g/L, 0.0060~0.0065g/L of EDTA, trace element are molten
1~1.5ml/L of liquid.
2. the method as described in claim 1 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed,
It is characterized in that, periodical addition Fe (II) the EDTA solution, ternary mixed liquor refer to：Reactor is added within every 5~7 days to hold
The ternary mixed liquor of reactor volume 6~8% is added in Fe (II) EDTA solution of product 6~8% daily；Fe (II) EDTA solution
A concentration of 15~25mmol/L, NH in ternary mixed liquor4 +Solution concentration is 110~140mgN/L, the component of nutrient and is contained
Amount is as follows：NaHCO31~1.5g/L, CaCl2·2H20.2~0.4g/L of O, MgSO4·7H20.2~0.4g/L of O, KH2PO4
0.04~0.06g/L, FeSO40.0060~0.0065g/L, 0.0060~0.0065g/L of EDTA are added in every liter of mixed liquor
1~1.5ml of trace element solution.
3. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that Fe (II) the EDTA solution FeSO4·7H2O and Na2EDTA presses 1:1 molar ratio.
4. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that the ammonia nitrogen solution is prepared with ammonium sulfate.
5. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that the trace element solution includes the component of following concentration：13~17g/L of EDTA, H3BO40.012~
0.016g/L、MnCl2·4H20.90~1.10g/L of O, CuSO4·5H20.20~0.30g/L of O, ZnSO4·7H2O 0.35~
0.50g/L、NiCl2·6H20.15~0.25g/L of O, Na2SeO4·10H20.15~0.26g/L of O, Na2MoO4·2H2O
0.17~0.27g/L, Na2WO4·2H20.03~0.07g/L of O.
6. the method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox as described in right wants 5 handles NO,
It is characterized in that, each component of the nutrient is a concentration of：NaHCO3 1.25g/L、CaCl2·2H2O 0.3g/L、MgSO4·
7H2O 0.3g/L、KH2PO4 0.05g/L、FeSO40.00625g/L、EDTA 0.00625g/L；The trace element additive amount
For 1.25ml/L, each component is a concentration of in trace element solution：EDTA 15g/L、H3BO4 0.014g/L、MnCl2·4H2O
0.99g/L、CuSO4·5H2O 0.25g/L、ZnSO4·7H2O 0.43g/L、NiCl2·6H2O 0.19g/L、Na2SeO4·
10H2O 0.21g/L、Na2MoO4·2H2O 0.22g/L、Na2WO4·2H2O 0.05g/L。
7. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that the anaerobic ammonia oxidation reactor uses UASB reactors or EGSB reactors.
8. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that a concentration of 1.5mM of Fe (II) EDTA in the substrate reaction liquid.
9. the side as claimed in claim 1 or 2 based on Fe (II) EDTA up-flow iron bed-Anammox processing NO absorbed
Method, which is characterized in that at 30~35 DEG C, pH is controlled 7.0~8.0 for reactor temperature control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810606156.2A CN108479379A (en) | 2018-06-13 | 2018-06-13 | The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810606156.2A CN108479379A (en) | 2018-06-13 | 2018-06-13 | The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108479379A true CN108479379A (en) | 2018-09-04 |
Family
ID=63342856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810606156.2A Pending CN108479379A (en) | 2018-06-13 | 2018-06-13 | The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108479379A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099739A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for rapidly recovering activity of anaerobic ammonium oxidation bacteria |
| CN111117866A (en) * | 2019-12-03 | 2020-05-08 | 同济大学 | Denitrification equipment for enriching nitrous oxide and recovering energy |
| CN111389193A (en) * | 2020-01-14 | 2020-07-10 | 中国石油大学(华东) | Method for synchronously removing dissolved methane and NOx |
| CN114515501A (en) * | 2022-03-17 | 2022-05-20 | 哈尔滨工业大学 | Sulfur circulation and complexing agent regeneration-based complexing absorption NO synchronous denitrification method |
| CN115676850A (en) * | 2022-10-11 | 2023-02-03 | 电子科技大学 | Method for synthesizing ammonia by Fe (II) EDTA-assisted photocatalysis of NO |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100407204B1 (en) * | 1995-02-06 | 2004-05-07 | 바이오스타 디벨럽먼트 씨.브이. | Process for purifying flue gas containing nitrogen oxides |
| CN104084024A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for boiler flue gas denitration |
| CN104193002A (en) * | 2014-09-24 | 2014-12-10 | 山东大学 | Method for efficiently treating nitrogen-containing wastewater based on zero-valent iron coupled anaerobic ammonia oxidation |
| CN105152323A (en) * | 2015-09-08 | 2015-12-16 | 重庆大学 | Method for oxidation treatment of nitric oxide by combining complexing absorption with anaerobic ammonium and application of method |
| CN106865760A (en) * | 2017-03-15 | 2017-06-20 | 东北电力大学 | The technique of the filler-reinforced anaerobic ammonia oxidation reactor denitrification efficiency of sponge iron |
-
2018
- 2018-06-13 CN CN201810606156.2A patent/CN108479379A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100407204B1 (en) * | 1995-02-06 | 2004-05-07 | 바이오스타 디벨럽먼트 씨.브이. | Process for purifying flue gas containing nitrogen oxides |
| CN104084024A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for boiler flue gas denitration |
| CN104193002A (en) * | 2014-09-24 | 2014-12-10 | 山东大学 | Method for efficiently treating nitrogen-containing wastewater based on zero-valent iron coupled anaerobic ammonia oxidation |
| CN105152323A (en) * | 2015-09-08 | 2015-12-16 | 重庆大学 | Method for oxidation treatment of nitric oxide by combining complexing absorption with anaerobic ammonium and application of method |
| CN106865760A (en) * | 2017-03-15 | 2017-06-20 | 东北电力大学 | The technique of the filler-reinforced anaerobic ammonia oxidation reactor denitrification efficiency of sponge iron |
Non-Patent Citations (1)
| Title |
|---|
| 万新宇: "Fe(Ⅱ)EDTA络合吸收耦合厌氧氨氧化去除烟气中NO的工艺开发", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099739A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for rapidly recovering activity of anaerobic ammonium oxidation bacteria |
| CN111117866A (en) * | 2019-12-03 | 2020-05-08 | 同济大学 | Denitrification equipment for enriching nitrous oxide and recovering energy |
| CN111389193A (en) * | 2020-01-14 | 2020-07-10 | 中国石油大学(华东) | Method for synchronously removing dissolved methane and NOx |
| CN114515501A (en) * | 2022-03-17 | 2022-05-20 | 哈尔滨工业大学 | Sulfur circulation and complexing agent regeneration-based complexing absorption NO synchronous denitrification method |
| CN115676850A (en) * | 2022-10-11 | 2023-02-03 | 电子科技大学 | Method for synthesizing ammonia by Fe (II) EDTA-assisted photocatalysis of NO |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108479379A (en) | The method that the up-flow iron bed absorbed based on Fe (II) EDTA-Anammox handles NO | |
| CN101460412B (en) | System and methods for biological selenium removal from water | |
| CN100584777C (en) | Method and reactor for removing organic matter, sulfide, and nitrate in wastewater synchronously | |
| CN101280284B (en) | Microbial nutrient solution, simultaneous removing method and device for SO2 and NO2 in industrial waste gas | |
| CN110028155B (en) | Anaerobic ammonia oxidation coupling sulfur autotrophic denitrification device and wastewater treatment method | |
| CN104129851B (en) | A kind of method utilizing nitric nitrogen in burnt pyrite process underground water | |
| CN100506357C (en) | Apparatus and method for treating multi-component complex waste gas | |
| JP5355459B2 (en) | Organic wastewater treatment system | |
| WO2010016268A1 (en) | Water treatment system and water treatment method | |
| Morita et al. | Nitrogen-removal bioreactor capable of simultaneous nitrification and denitrification for application to industrial wastewater treatment | |
| CN103663842B (en) | A kind of deep treatment method of ethylene waste lye | |
| CN101234831A (en) | Waste water denitrogenation and marsh gas desulfurization coupling technique | |
| CN101302058A (en) | Method for removing sulphur and nitrogen in inorganic waste water synchronously | |
| JP2006037074A (en) | Method for removing sulfur compound from biogas | |
| CN113636640B (en) | Biological trickling filter pilot test device and short-cut nitrification domestication method using same | |
| CN105152323A (en) | Method for oxidation treatment of nitric oxide by combining complexing absorption with anaerobic ammonium and application of method | |
| CN108862623A (en) | A method of removing nitrate nitrogen in low organic carbon content water body | |
| Van der Maas et al. | NO removal in continuous BioDeNOx reactors: Fe (II) EDTA2− regeneration, biomass growth, and EDTA degradation | |
| Chen et al. | FeII (EDTA)–NO reduction by Mn powder in wet flue gas denitrification technology coupled with Mn2+ recycling: performance, kinetics, and mechanism | |
| CN103509719B (en) | A kind of co-culture method of efficient denitrification anaerobic methane oxidation and Anammox mixing microorganism system | |
| Yang et al. | A new approach for the effective removal of NOx from flue gas by using an integrated system of oxidation− absorption− biological reduction | |
| CN104190226A (en) | Complexing absorption and aerobic denitrification combined smoke denitration process | |
| Duangmanee | Micro-aeration for hydrogen sulfide removal from biogas | |
| CN210710928U (en) | Anaerobic ammonia oxidation coupling sulfur autotrophic denitrification device | |
| CN212127697U (en) | In-situ sewage and odor treatment device for sewage treatment plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180904 |
|
| RJ01 | Rejection of invention patent application after publication |