CN101781019A - Anaerobic dephosphorizing method based on methanation, anaerobic ammonium oxidation and denitrification coupling process - Google Patents
Anaerobic dephosphorizing method based on methanation, anaerobic ammonium oxidation and denitrification coupling process Download PDFInfo
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Abstract
The invention belongs to the technical field of environment protection, in particular to an anaerobic dephosphorizing method. In the anaerobic dephosphorizing method based on methanation, anaerobic ammonium oxidation and denitrification coupling process, denitrification particle sludge serves as seeding sludge of which the concentration is 5-12 g/L in an air lift reactor; examination sewage is artificially prepared; following components are added into sewage: HCO3 of which the concentration is 0.2-1.8 g/L, H2PO4 of which the concentration is 0.05-0.30 g/L, NH4+ of which the concentration is 1.0-3.0 g/L, Mg2+ of which the concentration is 0.2-0.9 g/L, Fe2+ of which the concentration is 0.2-0.4 g/L, Ca2+ of which the concentration is 0.1-0.3 g/L, NO3- of which the concentration is 1.0-4.0 g/L and C6H12O6 of which the concentration is 0.7-2.5 g/L. The prepared sewage is pumped into the bottom of a reactor by a pipeline from the top of the reactor; under the anaerobic condition, the sludge is cultivated and acclimated to realize anaerobic ammonium oxidation, denitrification and methanation coupling. The invention has a practical guidance meaning to biological dephosphorization of sewage and water environment phosphorus load reduction.
Description
Technical field
The invention belongs to environment protection, sewage treatment area.Be specifically related to a kind of anaerobic dephosphorizing method based on methanation, Anammox and denitrification coupling process, its reactor types is the gas stripping type anaerobic reactor.
Background technology
Phosphoric acid salt reduction technique: the redox potential (as Fig. 2) of each possibility intermediate steps of phosphoric acid salt reduction process, find that none is a typical oxidizing agents in all phosphorus compounds, particularly under alkaline condition, therefore, the phosphoric acid salt reduction needs very strong reductive agent.And for PH
3Even very weak oxygenant can be a phosphoric acid salt with its exhaustive oxidation also.The reason that Here it is generally exists with highest oxidation state (+5) form at the occurring in nature phosphoric.
Be under 7.0 the standard conditions, to be electron donor with hydrogen or lactic acid at pH, phosphoric acid salt is reduced to phosphuret-(t)ed hydrogen, from the thermodynamics angle, is impossible take place.Under natural environmental condition, phosphine concentration order of magnitude degree is generally at ng/m
3In the scope.When pH is 7.0, the hydrogen dividing potential drop is 10
-3Atm, the phosphuret-(t)ed hydrogen dividing potential drop is 10
-9Atm, other compound concentration are 0.01mol/L, use Nernst equation to calculate, and can obtain phosphoric acid salt and be reduced into PH under field conditions (factors)
3Reaction be endergonic reaction.Therefore, under field conditions (factors), it is impossible that phosphoric acid salt is reduced to phosphuret-(t)ed hydrogen generation ATP.But when the ratio of phosphite and phosphoric acid salt less than 10
-8, pH is 7.0, H
2Dividing potential drop is 1atm, with H
2Be electron donor, the reaction that phosphoric acid salt is reduced to phosphite can take place.Require phosphite in case generate, transformed immediately.
The phosphoric acid salt reduction process is not to need specific product matter process but need energy in its process.Its prerequisite is: 1. anaerobism; 2. produce hydrogen, wherein producing hydrogen also is a sign of anaerobic environment.In butyric acid type fermenting process, NADH is superfluous, promptly has superfluous reducing power in microorganism, therefore has in reactor solution under the condition of phosphorus existence, may generate PH
3Ferredoxin may be relevant with phosphatic reduction, and sulphate reducing bacteria and ferrous ion can promote the generation of phosphine gas.
Summary of the invention
To having found the anaerobic dephosphorizing phenomenon in Anammox and methanation, the denitrification coupling process.The phosphine concentration of its discharge is up to the milligram level, thereby provides a kind of new approach for the removal of phosphor in sewage.
The objective of the invention is to be achieved through the following technical solutions:
Drop into denitrification granular sludge as seed sludge in the gas stripping type anaerobic reactor, sludge concentration is 5-10g/L in the anaerobic reactor.Then sewage is pumped into reactor, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating.
The startup of gas stripping type anaerobic reactor of the present invention with denitrification granular sludge as seed sludge, sludge concentration is about 5-12g/L in the inoculation post-reactor, test sewage is artificial preparation, then sewage is pumped into reactor bottom from reactor head by pipeline; The component that adds in the described sewage is: HCO
3Concentration be 0.2-1.8g/L, H
2PO
4Concentration be 0.05-0.30g/L, NH
4 +Concentration be 1.0-3.0g/L, Mg
2+Concentration be 0.2-0.9g/L, Fe
2+Concentration be 0.2-0.4g/L, Ca
2+Concentration be 0.1-0.3g/L, NO
3 -Concentration be 1.0-4.0g/L, C
6H
12O
6Concentration be 0.7-2.5g/L, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating.
The component concentrations that adds in described sewage as a kind of optimal way can be (g/L): NaHCO
30.2-1.8, KH
2PO
40.05-0.30, (NH
4)
2SO
41.0-3.0, MgSO
47H
2O 0.2-0.9, FeSO
47H
2O0.2-0.4, CaCl
20.1-0.3, KNO
31.0-4.0, C
6H
12O
60.7-2.5.
As the described FeSO of a kind of optimal way
47H
2The concentration of O is 0.3g/L.
Described water-quality COD 1.00-1.60g/L, ammonia nitrogen 0.16-0.25g/L, nitre attitude 0.16-0.35g/L, the phosphoric acid salt 0.22-0.25g/L that handles back sewage.Show NH
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, NH
3-N, TN, NO
3The clearance of-N, TP and COD can reach 40-65% (average 45%), 58-79% (average 69%), 86-99% (average 94%), 70-91% (average 75%) and 76-87% (average 81%), the PH of generation respectively
3Be 0.01146～0.3g/m
3
Said denitrification dephosphorization granule sludge is cultivated and is formed by aerobic/anaerobic, anaerobism/draining/anoxic, the culture method domestication of three stage of anaerobic/anoxic.The denitrification dephosphorization granule sludge contains denitrification phosphorus-collecting bacterium (Denitrifying Phosphorous removing Bacteria, DPB), DPB is meant that nitrate reductase is positive, contain poly-phosphorus particle in the thalline again, the bacterial classification of energy while denitrifying phosphorus uptake denitrogenation under anoxic condition, the quick excess of DPB energy in nitrate alienation reduction process absorbs the phosphorus in the sewage.
The present invention is with inorganic carbon NaHCO
3And CO
2Be carbon source, NaHCO
3Play the effect of conditioned reaction device pH value on the other hand, (NH
4)
2SO
4As the nitrogenous source of ammonia nitrogen, KNO
3As the nitrogenous source of nitric nitrogen, KH
2PO
4Be phosphorus source, FeSO
4Fe is provided
2+, simultaneously, need for guaranteeing institute's cultured microorganism growth, breeding, add suitable trace element as a supplement.
Processes such as mud process mud adaptation and transition phase, transitional period, stationary phase.The adaptation of mud and transition phase: water outlet NH
3-N instability presents bigger fluctuation and descends; With NH
3The removal effect difference of-N, NO
2-N growing amount is fluctuation and descends; With NO
2 -The NO of-N correspondence
3-N clearance reduces gradually, illustrates that nitrification weakens gradually; The TN removal takes the lead in, and then clearance is very low into negative value, does not remove substantially except that biology consumption; The COD clearance increases gradually.Transitional period: the NO of water outlet
3-N and NO
2-N sum is greater than the NO of water inlet
3-N, NH
3The clearance of-N presents and falls the trend that afterwards rises earlier, and the COD clearance progressively improves.Stationary phase: NH
3-N removal amount and NO
2-N growing amount begins to occur fluctuation and descends, and illustrates to have occurred anaerobic ammonia oxidizing bacteria in the reactor.Denitrification weakens gradually, and the Anammox effect strengthens gradually, has realized the coupling of Anammox and methane denitrification, shows NH
3-N, TN, NO
3The continual and steady removal of-N and COD.
Under anaerobic, on methanation, denitrification and Anammox coupled basis, anaerobic condition is that phosphoric acid salt is reduced into phosphuret-(t)ed hydrogen and has created envrionment conditions; The H that sulphate reducing bacteria (SRB) produces is quickened in adding of iron
2S, its production capacity is utilized by the phosphoric acid reduction process, produces a large amount of high reactivity PH
3
Advantage of the present invention and effect are:
(1) realizes Anammox, denitrification, methanation and anaerobic dephosphorizing coupling.In the gas stripping type anaerobic reactor, realize the removal of COD, total nitrogen, total phosphorus simultaneously.Reactor has successfully been realized Anammox, denitrification and methanation coupling through the operation of 280d, shows NH
4 +-N, TN, NO
3The continual and steady removal of-N and COD.NH wherein
3-N, TN, NO
3The clearance of-N, TP and COD can reach 40-65% (average 45%), 58-79% (average 69%), 86-99% (average 94%), 70-91% (average 75%) and 76-87% (average 81%) respectively
(2) part of the phosphorus in the sewage is removed in the mode of anaerobic dephosphorizing.Described water inlet TP mean concns is 4-12mg/L, and water outlet TP mean concns is 0.5-1.0mg/L, is 11.46～300mg/Nm with phosphine concentration in the ammonium molybdate spectrophotometry aerogenesis
3As shown in table 1.
Table 1 anaerobic reactor produces the gaseous state phosphine concentration
(3) added ferrous salt among the artificial distribution in technical scheme, the ferredoxin that its anaerobic condition forms is down optionally passed phosphorus and is formed PH as electron donor
3Added ferrous salt among the described artificial distribution, under anaerobic iron quickens the H that sulphate reducing bacteria (SRB) produces
2S, its production capacity is utilized by the phosphoric acid reduction process, produces a large amount of high reactivity PH
3
Description of drawings
The electrode potential figure of Fig. 1 inorganic phosphorous compound
Fig. 2 is the plot plan of the embodiment of the invention, wherein: 1. water-sealed drainage bottle; 2. air bag; 3. inlet chest; 4. water inlet peristaltic pump; 5. gas meter; 6. internal recycle air pump; 7. gas buffer bottle; 8. temperature control unit; 9. water outlet peristaltic pump; 10. thief hole; 11. outlet valve; 12. go out water collection tank; 13. aeration head.
Embodiment
Embodiment 1:
A kind of as shown in Figure 2 gas stripping type anaerobic reactor housing is made by synthetic glass, urceolus Φ 5.2 * 88 (diameter * long cm), and the reactor cubic capacity is 8.1L, useful volume is 6.4L.Built-in aeration head 13 utilizes internal recycle air pump 6 to carry out gas and proposes stirring; Temperature of reactor adopts real-time online control, and water temperature is 32 ± 1 ℃.To avoid illumination to be incubated simultaneously, peristaltic pump 4 is introduced reactor with the synthetic wastewaters in the inlet chest 3 from the top low discharge to reactor with black cloth parcel, and water outlet is discharged with peristaltic pump 9, and the synthetic sewage argon gas 30min that exposes to the sun before water inlet is to get rid of the oxygen in the water inlet.Adopt the mode of peristaltic pump 4 water inlets, can avoid the interior dissolved oxygen of reactor can not increase suddenly and change excessive with reactor temperature.Adopt peristaltic pump 9 timing drainages by opening outlet valve 11, during draining, gas is inhaled into reactor in the air bag 2, guarantees the stable of reactor internal gas pressure, has prevented entering of outside air.Water shoot will be tried one's best near the bucket end that goes out water collection tank 13, can utilize drainage water as water seal 1 like this, prevented that air from entering inside reactor from water shoot; A production well is arranged at reactor top, and production well links to each other with tracheae, is connecting an air bag 2 on the tracheae and (is filling CO to it discontinuously
2, guarantee that buffer air bag has gas always, for anaerobic ammonia oxidizing bacteria provides carbon source and the dissolved oxygen of getting rid of in the reactor), to guarantee the smooth and easy of Inlet and outlet water and to collect aerogenesis.Tail end links to each other with the water seal of making of vial, guarantees that gas overflows and completely cuts off external air, gas dosing employing gas meter 5.
Embodiment 2:
A kind of based on methanation, Anammox reaction coupled anaerobic dephosphorizing method, concrete steps are as follows: the startup of embodiment 1 described gas stripping type anaerobic reactor with denitrification granular sludge as seed sludge, sludge concentration is about 10g/L in the inoculation post-reactor, test sewage is artificial preparation, then sewage is pumped into reactor bottom from reactor head by pipeline; The component that adds in described sewage is (g/L): NaHCO
31.8, KH
2PO
40.30, (NH
4)
2SO
43.0, MgSO
47H
2O 0.9, FeSO
47H
2O 0.4, CaCl
20.3, KNO
34.0, C
6H
12O
62.5, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating; The sewage that generation is handled well, described sewage quality is: COD 1600mg/L, ammonia nitrogen 250mg/L, nitric nitrogen 350mg/L, phosphoric acid salt 50mg/L.Show NH
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, wherein NH
3-N, TN, NO
3The clearance of-N, TP and COD can reach 65%, 79%, 99%, 91% and 87% respectively; The PH in the exhaust of gas stripping type anaerobic reactor wherein
3Gas concentration reaches 300mg/Nm
3
Embodiment 3:
A kind of based on methanation, Anammox reaction coupled anaerobic dephosphorizing method, concrete steps are as follows: the startup of embodiment 1 described gas stripping type anaerobic reactor with denitrification granular sludge as seed sludge, sludge concentration is about 5g/L in the inoculation post-reactor, test sewage is artificial preparation, then sewage is pumped into reactor bottom from reactor head by pipeline; The component that adds in described sewage is (g/L): NaHCO
30.2, KH
2PO
40.05, (NH
4)
2SO
41.0, MgSO
47H
2O 0.2, FeSO
47H
2O 0.2, CaCl
20.1, KNO
31.0, C
6H
12O
60.7, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating; The sewage that generation is handled well, described sewage quality is: COD 1000mg/L, ammonia nitrogen 160mg/L, nitric nitrogen 160mg/L, phosphoric acid salt 20mg/L; Show NH
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, wherein NH
3-N, TN, NO
3The clearance of-N, TP and COD can reach 40%, 58%, 86%, 70%, 76% respectively; The PH in the exhaust of gas stripping type anaerobic reactor wherein
3Gas concentration reaches 196mg/Nm
3
Embodiment 4:
A kind of based on methanation, Anammox reaction coupled anaerobic dephosphorizing method, concrete steps are as follows: the startup of embodiment 1 described gas stripping type anaerobic reactor with denitrification granular sludge as seed sludge, sludge concentration is about 8g/L in the inoculation post-reactor, test sewage is artificial preparation, then sewage is pumped into reactor bottom from reactor head by pipeline; The component that adds in described sewage is (g/L): NaHCO
30.8, KH
2PO
40.1, (NH
4)
2SO
42.0, MgSO
47H
2O 0.4, FeSO
47H
2O 0.3, CaCl
20.2, KNO
30.2, C
6H
12O
61.0, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating; The sewage that generation is handled well, described sewage quality is: COD 1200mg/L, ammonia nitrogen 180mg/L, nitric nitrogen 180mg/L, phosphoric acid salt 100mg/L.Show NH
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, wherein NH
3-N, TN, NO
3The clearance of-N, TP and COD can reach 50%, 60%, 90%, 80% and 83% (average 81%) respectively; The PH in the exhaust of gas stripping type anaerobic reactor wherein
3Gas concentration is up to 266mg/Nm
3
Embodiment 5:
A kind of based on methanation, Anammox reaction coupled anaerobic dephosphorizing method, concrete steps are as follows: the startup of embodiment 1 described gas stripping type anaerobic reactor with denitrification granular sludge as seed sludge, sludge concentration is about 9g/L in the inoculation post-reactor, test sewage is artificial preparation, then sewage is pumped into reactor bottom from reactor head by pipeline; The component that adds in described sewage is (g/L): NaHCO
31.6, KH
2PO
40.25, (NH
4)
2SO
42.5, MgSO
47H
2O 0.7, FeSO
47H
2O 0.3, CaCl
20.2, KNO
32.0, C
6H
12O
61.9, after reactor successfully starts, realized Anammox, denitrification and methanation coupling through cultivating; The sewage that generation is handled well, described sewage quality is: COD 1400mg/L, ammonia nitrogen 200mg/L, nitric nitrogen 300mg/L, phosphoric acid salt 220mg/L.Show NH
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, wherein NH
3-N, TN, NO
3The clearance of-N, TP and COD can reach 55% (average 45%), 69%, 94%, 75% and 81% respectively; The PH in the exhaust of gas stripping type anaerobic reactor wherein
3Gas concentration is up to 288mg/Nm
3
Claims (3)
1. anaerobic dephosphorizing method based on the reaction of methanation, Anammox, denitrification coupling process is characterized in that:
A, in the gas stripping type reactor, as seed sludge, described seed sludge concentration is 5-12g/L with denitrification granular sludge, test sewage be manually to prepare, the component that adds in the described sewage is: HCO
3Concentration be 0.2-1.8g/L, H
2PO
4Concentration be 0.05-0.30g/L, NH
4 +Concentration be 1.0-3.0g/L, Mg
2+Concentration be 0.2-0.9g/L, Fe
2+Concentration be 0.2-0.4g/L, Ca
2+Concentration be 0.1-0.3g/L, NO
3 -Concentration be 1.0-4.0g/L, C
6H
12O
6Concentration be 0.7-2.5g/L, the sewage for preparing is pumped into reactor bottom from reactor head by pipeline; Under anaerobic carry out the cultivation domestication of mud, realize Anammox, denitrification and methanation coupling;
B, described Anammox, denitrification and methanation coupling show NH after realizing
3-N, TN, NO
3The continual and steady removal of-N, TP and COD, NH
3-N, TN, NO
3The clearance of-N, TP and COD is respectively 40-65%, 58-79%, 86-99%, 70-91% and 76-87%, the PH of generation
3Be 0.01146～0.3g/Nm
3
2. the anaerobic dephosphorizing method based on methanation, denitrification and Anammox coupling process according to claim 1 is characterized in that: the component that described sewage adds is NaHCO
3Concentration be 0.2-1.8g/L, KH
2PO
4Concentration be 0.05-0.30g/L, (NH
4)
2SO
4Concentration be 1.0-3.0g/L, MgSO
47H
2The concentration of O is 0.2-0.9g/L, FeSO
47H
2The concentration of O is 0.2-0.4g/L, CaCl
2Concentration be 0.1-0.3g/L, KNO
3Concentration be 1.0-4.0g/L, C
6H
12O
6Concentration be 0.7-2.5g/L.
3. the anaerobic dephosphorizing method based on methanation, denitrification and Anammox coupling process according to claim 2 is characterized in that: add FeSO in the described sewage
47H
2The concentration of O is 0.3g/L.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101718A (en) * | 2011-01-11 | 2011-06-22 | 彭永臻 | Sludge hydrolysis acidification coupling denitrification device and treatment method thereof |
| CN104098172A (en) * | 2014-07-09 | 2014-10-15 | 中山大学 | Culture method of sulfur synergy denitrification simultaneous nitrogen and phosphorous removal granular sludge |
| CN107487841A (en) * | 2017-09-18 | 2017-12-19 | 安徽华骐环保科技股份有限公司 | A kind of denitrification integrates coupling dephosphorization and the waste water treatment process of Anammox |
| CN108358311A (en) * | 2018-02-01 | 2018-08-03 | 昆明理工大学 | A kind of method that charcoal coupling micro-current strengthens anaerobic waste water biological phosphate-eliminating |
| CN111410303A (en) * | 2020-01-14 | 2020-07-14 | 中国石油大学(华东) | Rapid forming method for coupling denitrification anaerobic methane oxidation and anaerobic ammonia oxidation to granular sludge |
| CN111517591A (en) * | 2020-06-11 | 2020-08-11 | 北京工业大学 | Device and method for treating oxidized nitrogen wastewater by using ferroalloy in combination with anaerobic ammonium oxidation bacteria |
| CN111573822A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Bioelectrochemical treatment process for high-ammonia-nitrogen high-sulfate wastewater |
| CN114906926A (en) * | 2022-04-20 | 2022-08-16 | 北京工业大学 | Starting method of hydrolytic acidification short-range denitrification anaerobic ammonia oxidation coupling system |
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2010
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|---|---|---|---|---|
| CN102101718A (en) * | 2011-01-11 | 2011-06-22 | 彭永臻 | Sludge hydrolysis acidification coupling denitrification device and treatment method thereof |
| CN102101718B (en) * | 2011-01-11 | 2012-09-05 | 彭永臻 | Sludge hydrolysis acidification coupling denitrification device and treatment method thereof |
| CN104098172A (en) * | 2014-07-09 | 2014-10-15 | 中山大学 | Culture method of sulfur synergy denitrification simultaneous nitrogen and phosphorous removal granular sludge |
| CN104098172B (en) * | 2014-07-09 | 2015-10-28 | 中山大学 | A kind of sulphur works in coordination with the cultural method of denitrification synchronous denitrification dephosphorizing granule sludge |
| CN107487841A (en) * | 2017-09-18 | 2017-12-19 | 安徽华骐环保科技股份有限公司 | A kind of denitrification integrates coupling dephosphorization and the waste water treatment process of Anammox |
| CN107487841B (en) * | 2017-09-18 | 2021-07-06 | 安徽华骐环保科技股份有限公司 | Wastewater treatment process integrating denitrification, coupling phosphorus removal and anaerobic ammonia oxidation |
| CN108358311B (en) * | 2018-02-01 | 2021-06-18 | 昆明理工大学 | Method for enhancing wastewater anaerobic biological phosphorus removal by biochar coupling micro-current |
| CN108358311A (en) * | 2018-02-01 | 2018-08-03 | 昆明理工大学 | A kind of method that charcoal coupling micro-current strengthens anaerobic waste water biological phosphate-eliminating |
| CN111410303A (en) * | 2020-01-14 | 2020-07-14 | 中国石油大学(华东) | Rapid forming method for coupling denitrification anaerobic methane oxidation and anaerobic ammonia oxidation to granular sludge |
| CN111573822A (en) * | 2020-05-22 | 2020-08-25 | 盐城工学院 | Bioelectrochemical treatment process for high-ammonia-nitrogen high-sulfate wastewater |
| CN111517591A (en) * | 2020-06-11 | 2020-08-11 | 北京工业大学 | Device and method for treating oxidized nitrogen wastewater by using ferroalloy in combination with anaerobic ammonium oxidation bacteria |
| CN111517591B (en) * | 2020-06-11 | 2022-05-24 | 北京工业大学 | Device and method for treating oxidized nitrogen wastewater by using ferroalloy and anaerobic ammonium oxidation bacteria |
| CN114906926A (en) * | 2022-04-20 | 2022-08-16 | 北京工业大学 | Starting method of hydrolytic acidification short-range denitrification anaerobic ammonia oxidation coupling system |
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