CN109650536A - The device and method of ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving - Google Patents
The device and method of ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving Download PDFInfo
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- CN109650536A CN109650536A CN201910004302.9A CN201910004302A CN109650536A CN 109650536 A CN109650536 A CN 109650536A CN 201910004302 A CN201910004302 A CN 201910004302A CN 109650536 A CN109650536 A CN 109650536A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The present invention provides a kind of device and method of ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving, it is characterized by: adding nitrate into the Feammox system containing iron, cause nitric acid salt-dependent iron oxidation (NDFO), the Fe (III) of generation continues to participate in Feammox and carries out denitrogenation.Steps are as follows: one, the provenance sludge containing Feammox microorganism being mixed to get mud mixture with culture solution.Two, mud mixture is accessed in anaerobic reactor, exposes N2DO < 0.02mg/L into mud mixture.Supernatant, the new above-mentioned culture solution of addition equivalent are discharged after five days, so circulation completes 5~7 periods.Three, the mixture of nitrogenous effluent or nitrogenous solid and water is added, exposes N2DO < 0.02mg/L into mud mixture, and nitrate solution is periodically added, stirring is opened, the running temperature of reactor is 25~35 DEG C, and pH control is run 90~100 days 5.0~6.0.
Description
Technical field
The invention belongs to waste water/solid waste denitrogenation fields.
Technical background
A large amount of ammonia nitrogen waste water discharge is had in life and industry, traditional denitrogenation mode is nitrification-denitrification, i.e., first leads to
It is NO that aeration, which is crossed, by ammonium oxidationx -(most of is NO3 -), NOx -N is generated using the denitrification under anaerobic condition2.However nitre
Change-denitrification needs aerobic and anaerobism alternately, and energy consumption is big, is only applicable to middle low concentration nitrogen containing waste water, and cannot handle
Low C/N waste water.Anammox (anammox) can handle high-concentration ammonia nitrogenous wastewater (NH under anaerobic conditions4 ++NO2 -→N2+
2H2O), but anammox is there is also some problems, and such as anammox bacterium generation cycle is long (≈ 11 days), sensitive to environmental factor,
Such as pH, salinity and content of organics, and NO2 -It must be present in system in advance, and short distance nitration effect is to generate at present
NO2 -Main mode, but NO2 -It is easily further oxided as NO3 -, it means that NO necessary to anammox2 -It is not allow
It is facile.And the NO being easy to get by nitrification3 -But it cannot function as the final electron acceptor during anammox, even if
Thermodynamically NO3 -It is that can aoxidize NH4 +(5NH4 ++3NO3 -→4N2+9H2O+2H+△G0'=- 3297Kj/mol).
It has recently been demonstrated that dissimilatory iron reduction coupling Anammox (Feammox) is widely present in nature, such as
Paddy soils, wetland, ocean, Feammox play important role in Fe/N circulation.Feammox process is in anaerobic condition
Under, electron acceptor of the Fe (III) as ammoxidation, product is mainly N2(67%-78%), some NO2 -And NO3 -(equation
Formula 1-3).It is worth noting that, the product NO of Feammoxx -It can be reacted with Fe (II) and regenerate Fe (III), which is claimed
(NDFO) is aoxidized for (Asia) nitric acid salt-dependent iron, equation 4-5).Since Feammox process only has seldom NOx -It generates, and
And 6 or 8mol Fe (III) can be only generated 1mol NO2 -Or NO3 -(equation 2-3), even if all NO generated2 -Or NO3 -It participates in
NDFO process, also only 2 or 5mol Fe (III) generates (equation 4-5).So even if there are the ferrikinetics of itself, Fe (III)
Production quantity also can be less and less.This means that only constantly addition Fe (III) just can guarantee holding for Feammox and denitrogenation
Continuous property, but be worthless in reality.
3Fe(OH)3+5H++NH4 +→3Fe2++9H2O+0.5N2 (1)
6Fe(OH)3+10H++NH4 +→6Fe2++16H2O+NO2 - (2)
8Fe(OH)3+14H++NH4 +→8Fe2++21H2O+NO3 - (3)
4Fe(II)+2NO2 -+8H+→4Fe(III)+N2+4H2O (4)
10Fe(II)+2NO3 -+12H+→10Fe(III)+N2+6H2O (5)
If additional ' nitrification is easy to get ' NO3 -Make up the NO originated from Feammoxx -Deficiency then produces more Fe
(III), it participates in Feammox.The present invention is based on this theories, periodically add NO into Feammox system3 -, Oxidation of Fe (II)
The Fe (III) of generation continues to participate in Feammox, and the Fe (II) of generation is again by additional new NO3 -Oxidation, in this way by periodically adding
Add NO3 -It will make limited iron that more N be brought to remove.In this course, NO3 -It is considered as the final of Anammox
Electron acceptor, and Fe (II)/Fe (III) is considered as NH4 +And NO3 -Between electronics wear lock body, be also considered as this class
The catalyst of anammox reaction.
Summary of the invention:
The purpose of the present invention: it proposes a kind of novel with NO3 -The class of final electron acceptor as ammonia nitrogen anaerobic oxidation
Anammox Approach of Removal of Nitrogen.In fact, periodically adding NO into Feammox system3 -, first pass through NDFO effect and aoxidize Fe (II)
Fe (III) for Fe (III), generation continues to participate in Feammox, achievees the purpose that denitrogenation.
The present invention is a kind of technical solution of the device and method of ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving, dress
Be set to be equipped with and be fixedly arranged above the sample inlet pool 1 of blender i-2, connect equipped with valve i-3 with one end pipeline i-6 of peristaltic pump 5 into
The feed inlet 7 of the lower section side in sample pond 1 and the top of other end connection fermentor 8.The upper cover of fermentor 8 is equipped with escape pipe upwards
11 are fixed with downwards blender ii-9.The bottom of fermentor 8 is fixed with aerator 10.The downside of fermentor 8 is equipped with mud valve
16 and middle downside be equipped with drain valve 12.Equipped with the nitrate solution pond 13 for being fixedly arranged above blender iii-14.Equipped with valve
Connecting pin and other end connection nitrate solution pond 13 between the one end the pipeline ii-15 connecting valve i-3 and peristaltic pump 5 of ii-4
Downside.
Method is periodically to add NO into Feammox system3 -, it first passes through NDFO effect and generates Fe (III), the Fe of generation
(III) Feammox is participated in, achievees the purpose that denitrogenation.Key step is as follows:
1), prepared by Feammox microorganism provenance mud mixture.(100 revs/min of i-2 of stirring is opened in sample inlet pool 1
Clock), the provenance sludge containing Feammox microorganism is mixed to get mud mixture with culture solution, the culture solution is by nutrition
Liquid and trace element solution are mixed and are obtained, composition and ratio MgCl2·6H2O (0.4g/L), CaCl2·H2O (0.1g/L),
NH4Cl (0.027g/L), KH2PO4(0.6g/L), vitamin 1ml/L, microelement 1ml/L and bicarbonate buffer
30mmol/L.The solid content of this mud mixture controls between 5%~6%；
2) Feammox microorganism adapts to and is enriched with.Open valve i-3 closes valve ii-4, starts peristaltic pump 5 for sample introduction
I-6 from injection port 7 is pumped into progress microorganism enrichment in anaerobic reaction-pot 8 by the road for mud mixture in pond 1.Start reactor
Agitating device ii-9 (100 revs/min) opens aerator 10 and exposes N2DO < 0.02mg/L into mud mixture.Wherein, N2Stream
Amount is 5L/min, and the oxygen etc. in reactor is discharged through exhaust valve 11, and at 25~35 DEG C, pH is controlled the temperature control in reactor
Supernatant, the new above-mentioned culture solution of addition equivalent is discharged through drain valve 12 after 5.0~6.0, five days, so circulation completes 5~7
A period.
3) reactor runs (denitrogenation) stage.Open valve i-3 closes valve ii-4, starts peristaltic pump 5, passes through pipeline
High concentration nitrogen-containing waste water in sample inlet pool 1 is added to anaerobic reactor 8 by i-6, and ensures that the mud mixture in reactor 8 is total
Volume is between the 1/2~2/3 of total measurement (volume).In nitrate solution pond 13, open agitating device iii-14 (100 revs/min),
Prepare the sodium nitrate solution of 2mol/L.Valve i-3, Open valve ii-4 are closed, starts peristaltic pump 5, by pipeline ii-15 every 4
A certain amount of nitrate solution is added within~6 days into reactor, the ultimate density of nitrate is 3.5~4.5mmol/ in reactor
L, total iron content are controlled in 700~900mg/L, solid content 1.5%~2.5%.DO < 0.02mg/L in reactor, operation
Temperature is 25~35 DEG C, and pH is controlled 5.0~6.0.Stirring ii-9 (100 revs/min) is opened, reactor 8,90~100 is run
Terminate a cycle after it.Supernatant is discharged by drain valve 12 after standing 2 days, nitrogenous effluent is rejoined later, under
One denitrogenation period.If not using the reactor, sludge can be discharged by mud valve 16.
By adopting the above technical scheme, i.e., nitrate periodically is added into Feammox system, the Fe (III) generated by NDFO
Feammox is participated in again, continuously creates the environment of iron oxidation and reduction in this way, endlessly realizes N removal.The party
Method is convenient, easy to operate, investment is small.
Detailed description of the invention
Fig. 1 is the schematic device of invention.In figure: 1- sample inlet pool, 2- blender i, 3- valve i, 4- valve ii, 5- wriggling
Pump, 6- pipeline i, 7- injection port, 8- fermentor, 9- blender ii, 10- aerator, 11- escape pipe, 12- drain valve, 13- nitre
Acid salt solution pond, 14- blender iii, 15- pipeline ii, 16- mud valve.
Specific embodiment
The principle of the invention is periodically to add nitrate into Feammox system based on the principle of NDFO coupling Feammox,
Ammonia nitrogen in high density is removed using nitrate as the final electron acceptor of Anammox.
The experimental provision that the present invention uses is equipped with the sample inlet pool 1 for being fixedly arranged above blender i-2 as shown in Figure 1:.Equipped with valve
Door i-3 connect with one end pipeline i-6 of peristaltic pump 5 sample inlet pool 1 lower section side and the other end connect fermentor 8 top into
Material mouth 7.The upper cover of fermentor 8 is equipped with escape pipe 11 upwards and is fixed with blender ii-9 downwards.The bottom of fermentor 8 is fixed with
Aerator 10.The downside of fermentor 8 is equipped with mud valve 16 and is equipped with drain valve 12 in middle downside.It is stirred equipped with being fixedly arranged above
The nitrate solution pond 13 of device iii-14.The one end pipeline ii-15 connecting valve i-3 equipped with valve ii-4 and between peristaltic pump 5
Connecting pin and the other end connection nitrate solution pond 13 downside.
Ammonia nitrogen in high density is removed under anaerobic by the way of batch sampling (batch-type).Below with reference to schematic diagram pair
Each step further illustrates:
1) prepared by Feammox microorganism provenance mud mixture.Stirring i-2 (100 revs/min) is opened in sample inlet pool 1,
Provenance sludge containing Feammox microorganism is mixed to get mud mixture with culture solution, the culture solution by nutrient solution and
Trace element solution is mixed and is obtained, composition and ratio MgCl2·6H2O (0.4g/L), CaCl2·H2O (0.1g/L), NH4Cl
(0.027g/L), KH2PO4(0.6g/L), vitamin 1ml/L, microelement 1ml/L and bicarbonate buffer 30mmol/L.This
The solid content of mud mixture controls between 5%~6%.
2) Feammox microorganism adapts to and is enriched with.Open valve i-3 closes valve ii-4, starts peristaltic pump 5 for sample introduction
I-6 from injection port 7 is pumped into progress microorganism enrichment in anaerobic reaction-pot 8 by the road for mud mixture in pond 1.Start reactor
Blender ii-9 (100 revs/min) opens aerator 10 and exposes N2DO < 0.02mg/L into mud mixture.Wherein, N2Flow
For 5L/min, the oxygen etc. in reactor is discharged through exhaust valve 11, and at 25~35 DEG C, pH control exists the temperature control in reactor
Supernatant, the new above-mentioned culture solution of addition equivalent is discharged through drain valve 12 after 5.0~6.0, five days, so circulation completes 5~7
Period.
3) reactor runs (denitrogenation) stage.Open valve i-3 closes valve ii-4, starts peristaltic pump 5, passes through pipeline
High concentration nitrogen-containing waste water in sample inlet pool 1 is added to anaerobic reactor 8 by i-6, and ensures that the mud mixture in reactor 8 is total
Volume is between the 1/2~2/3 of total measurement (volume).In nitrate solution pond 13, turn on agitator iii-14 (100 revs/min) matches
The sodium nitrate solution of 2mol/L processed.Valve i-3, Open valve ii-4 are closed, starts peristaltic pump 5, by pipeline ii-15 every 4~6
A certain amount of nitrate solution is added into reactor for it, and the ultimate density of nitrate is 3.5~4.5mmol/L in reactor,
Total iron content is controlled in 700~900mg/L, solid content 1.5%~2.5%.DO < 0.02mg/L in reactor, operation temperature
Degree is 25~35 DEG C, and pH is controlled 5.0~6.0.Stirring ii-9 (100 revs/min) is opened, is run reactor 8,90~100 days
After terminate a cycle.Supernatant is discharged by drain valve 12 after standing 2 days, rejoins nitrogenous effluent later, entrance is next
A denitrogenation period.If not using the reactor, sludge can be discharged by mud valve 16.
Claims (2)
1. a kind of device of the ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving, it is characterised in that: stirred equipped with being fixedly arranged above
The sample inlet pool (1) of (2) device i is mixed, connect the sample inlet pool (1) with pipeline i (6) one end of peristaltic pump (5) equipped with valve i (3)
The feed inlet (7) of lower section side and the top of other end connection fermentor (8), the upper cover of the fermentor (8) are equipped with out upwards
Tracheae (11) and the bottom for being fixed with blender ii (9) fermentor (8) downwards is fixed with aerator (10), the fermentation
The downside of tank (8) is equipped with mud valve (16) and is equipped with drain valve (12) in middle downside；Equipped with being fixedly arranged above blender iii (14)
Nitrate solution pond (13), (15) one end pipeline ii equipped with valve ii (4) connect the valve i (3) and peristaltic pump (5) it
Between connecting pin and the other end connects the downside of the nitrate solution pond (13).
2. a kind of ammonia nitrogen anaerobism in-situ treatment method for being used to drive based on ferrikinetics using device described in claim 1, packet
Include following steps:
1), prepared by Feammox microorganism provenance mud mixture: stirring i (2) (100 revs/min) is opened in sample inlet pool (1),
Provenance sludge containing Feammox microorganism is mixed to get mud mixture with culture solution, the culture solution by nutrient solution and
Trace element solution is mixed and is obtained, composition and ratio MgCl2·6H2O (0.4g/L), CaCl2·H2O (0.1g/L), NH4Cl
(0.027g/L), KH2PO4(0.6g/L), vitamin 1ml/L, microelement 1ml/L and bicarbonate buffer 30mmol/L, this
The solid content of mud mixture controls between 5%~6%；
2), Feammox microorganism adapts to and is enriched with: Open valve i (3), closes valve ii (4), starts peristaltic pump (5) for sample introduction
I (6) is pumped into anaerobic reaction-pot (8) from injection port (7) and carries out microorganism enrichment by the road for mud mixture in pond (1)；It opens
Dynamic reactor agitating device ii (9) (100 revs/min) open aerator (10) and expose N2The dissolved oxygen into mud mixture
(DO) < 0.02mg/L, wherein N2Flow is 5L/min, and oxygen in reactor etc. is discharged through exhaust valve (11), in reactor
At 25~35 DEG C, supernatant is discharged through drain valve (12) after 5.0~6.0, five days in pH control for temperature control, and addition equivalent is new
Above-mentioned culture solution, so circulation complete 5~7 periods；
3), reactor runs (denitrogenation) stage.Open valve i (3) is closed valve ii (4), is started peristaltic pump (5), is passed through pipeline
High concentration nitrogen-containing waste water in sample inlet pool (1) is added to anaerobic reactor (8) by i (6), and ensures the muddy water in reactor (8)
Mixture total volume is between the 1/2~2/3 of total measurement (volume)；In nitrate solution pond (13), open agitating device iii (14)
(100 revs/min), prepare the sodium nitrate solution of 2mol/L；It closes valve i (3), Open valve ii (4), starts peristaltic pump (5),
Quantitative nitrate solution was added into reactor by pipeline ii (15) every 4~6 days, the ultimate density of nitrate in reactor
For 3.5~4.5mmol/L, total iron content is controlled in 700~900mg/L, solid content 1.5%~2.5%；DO in reactor
< 0.02mg/L, running temperature are 25~35 DEG C, and pH is controlled 5.0~6.0；Open stirring ii (9) (100 revs/min), operation
Reactor (8) terminates a cycle after 90~100 days, supernatant is discharged by drain valve (12) after standing 2 days, later again
Nitrogenous effluent is added, into next denitrogenation period；If not using the reactor, can be discharged by mud valve (16) dirty
Mud.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943353A (en) * | 2020-07-08 | 2020-11-17 | 广东工业大学 | Method for identifying and quantifying ammoxidation path of anaerobic iron in reservoir sediment |
| CN112897835A (en) * | 2021-02-23 | 2021-06-04 | 沈阳建筑大学 | Preparation device and domestication method for domesticating anaerobic digestion sludge into Feammox functional sludge |
| CN113912179A (en) * | 2021-10-15 | 2022-01-11 | 北京工业大学 | Rapid culture method for anaerobic ferric salt oxidized ammonia nitrogen and synchronous denitrification sludge |
| CN115124142A (en) * | 2022-07-28 | 2022-09-30 | 兰州资源环境职业技术大学 | Device for removing nitrogen in sewage by utilizing ferric ammonium oxidation and denitrification process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943353A (en) * | 2020-07-08 | 2020-11-17 | 广东工业大学 | Method for identifying and quantifying ammoxidation path of anaerobic iron in reservoir sediment |
| CN111943353B (en) * | 2020-07-08 | 2022-03-04 | 广东工业大学 | Method for identifying and quantifying ammoxidation path of anaerobic iron in reservoir sediment |
| CN112897835A (en) * | 2021-02-23 | 2021-06-04 | 沈阳建筑大学 | Preparation device and domestication method for domesticating anaerobic digestion sludge into Feammox functional sludge |
| CN112897835B (en) * | 2021-02-23 | 2023-08-25 | 沈阳建筑大学 | Preparation device and domestication method for domesticating anaerobic digested sludge into Feamox functional sludge |
| CN113912179A (en) * | 2021-10-15 | 2022-01-11 | 北京工业大学 | Rapid culture method for anaerobic ferric salt oxidized ammonia nitrogen and synchronous denitrification sludge |
| CN113912179B (en) * | 2021-10-15 | 2023-09-29 | 北京工业大学 | Rapid culture method for anaerobic ferric salt oxidized ammonia nitrogen and synchronous denitrification sludge |
| CN115124142A (en) * | 2022-07-28 | 2022-09-30 | 兰州资源环境职业技术大学 | Device for removing nitrogen in sewage by utilizing ferric ammonium oxidation and denitrification process |
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