CN104193002A - Method for efficiently treating nitrogen-containing wastewater based on zero-valent iron coupled anaerobic ammonia oxidation - Google Patents
Method for efficiently treating nitrogen-containing wastewater based on zero-valent iron coupled anaerobic ammonia oxidation Download PDFInfo
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Abstract
The invention discloses a method for efficiently treating nitrogen-containing wastewater based on zero-valent iron coupled anaerobic ammonia oxidation. The method comprises the steps of feeding sludge into a reaction region of an up-flow type anaerobic reactor, and then feeding zero-valent iron, wherein the feeding amount of zero-valent iron is that 0.5-5 g of zero-valent iron is fed into each gram of sludge; feeding the wastewater to be treated from the bottom of the up-flow type anaerobic reactor through a peristaltic pump, so that the sewage to be treated can stay in the up-flow type anaerobic reactor for 24-96 hours, wherein the sludge concentration after the wastewater to be treated is fed is 2,000-7,000 mg/L, and after the up-flow type anaerobic reactor runs for 40-110 days, sludge anaerobic ammonia oxidation reaction is successfully started to realize efficient removal of nitrogen from the sewage. According to the method disclosed by the invention, the starting time of an anaerobic ammonia oxidation technology can be effectively shortened, and the total nitrogen removal rate of the anaerobic ammonia oxidation technology can be greatly increased; when the fed water total nitrogen volumetric loading is about 620N mg/L/d, nano-level zero-valent iron is fed, so that the starting time of an anaerobic ammonia oxidation technology can be shortened by 33.3 percent, and the total nitrogen removal rate can be increased by 2-19 percent.
Description
Technical field
The present invention relates to a kind of method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, belong to biological wastewater treatment field.
Background technology
Anaerobic ammonia oxidation process is the in recent years flourish novel denitrification process of one, is particularly useful for high ammonia-nitrogen wastewater process field.This technique refers under anaerobism or anoxia condition, taking nitrite nitrogen as electron acceptor(EA), ammonia nitrogen is directly changed into nitrogen, thereby avoided the participation of organic carbon source and oxygen by anaerobic ammonia oxidizing bacteria, and denitrogenation cost is significantly reduced, and is only 1/10 of traditional technology method.Reaction formula:
NH
4 ++ 1.32NO
2 -+ 0.06HCO
3 -+ 0.13H
+→ 1.02N
2+ 0.26NO
3 -+ 0.066CH
2o
0.5n
0.15+ 2.03H
2o (1), therefore the efficient cheapness of anaerobic ammonia oxidation process obtains people and pays close attention to widely.
But the anaerobic ammonium oxidizing bacteria doubling time reaches 11 days, poor growth, has seriously limited the industrialization development of anaerobic ammonia oxidation process, makes this technology at present substantially in laboratory theoretical research stage and industrial application is less.Be limited by the growing amount of the middle nitre nitrogen of this technique simultaneously, the theoretical nitrogen removal rate of anaerobic ammonia oxidation process is difficult to reach 90%, under the background of high ammonia-nitrogen content, in its water outlet, residual total nitrogen content is higher, and water outlet total nitrogen index is difficult to meet urban wastewater treatment firm pollutant emission primary standard (GB18918-2002).
Summary of the invention
For the deficiencies in the prior art, the present invention relates to a kind of method of processing nitrogenous effluent based on Zero-valent Iron coupling Anammox technique to high-efficiency.
Term explanation:
Zero-valent Iron, is also fe, and conventional Zero-valent Iron comprises iron powder, iron filings, sponge iron, micron order Zero-valent Iron and extraction and nanometer iron metal.
Technical scheme of the present invention is as follows:
A method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) mud is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, and described mud is selected from one of active sludge, inactivation anaerobic grain sludge, inactivation Anammox mud or arbitrary combination;
(2) add Zero-valent Iron to adding in the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of described Zero-valent Iron is that every gram of mud adds Zero-valent Iron 0.5～5g;
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24～96 hours, the sludge concentration passing into after pending waste water is 2000～7000mg/L, adopt heating rod or constant temperature circulating bath device to make flow lifting type anaerobic reactor internal temperature maintain 30～35 degree simultaneously, and pass into nitrogen to maintain anaerobic environment, pass into carbonic acid gas and make pH remain on 7.1～7.7;
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 40～110 days, realized efficiently removing the nitrogen in sewage.
The present invention is preferred, the preferred inactivation Anammox of described mud mud.
The present invention is preferred, described active sludge take from sewage work discharge mud after filtration, screening, make after cultivating early stage, by filtering, the leaf in mud is removed in screening, discarded paper, the impurity such as waste plastic, then mud is added to the reaction zone of flow lifting type anaerobic reactor, utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24～96 hours, keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the mud of removing floating and expanding, the operation of flow lifting type anaerobic reactor is after 3-7 days, collect bottom settlings mud and be active sludge.
The present invention is preferred; described inactivation anaerobic grain sludge is anaerobic reactor overproduction or discarded granule sludge and/or goes out sewage sludge and make; by anaerobic reactor overproduction or discarded granule sludge and/or go out sewage sludge and collect; using the organic plastics bottle of clean and good leak tightness as preserving container; needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:2～4; at normal temperatures sealing preserve 1～2 year for subsequent use; inactivation anaerobic grain sludge color is black or grey; granularity is 0.5～3mm, and moisture percentage in sewage sludge is more than or equal to 98wt%.
The present invention is preferred; described inactivation Anammox mud is anaerobic ammonia oxidation reactor overproduction or discarded mud and/or goes out sewage sludge and make; by anaerobic ammonia oxidation reactor overproduction or discarded granule sludge and/or go out sewage sludge and collect; using the vial of clean and good leak tightness as preserving container; needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:2～4; 3～4 DEG C of lower seals preserve 6～8 months for subsequent use; inactivation Anammox mud color is red-brown or brown color, and moisture percentage in sewage sludge is more than or equal to 98wt%.
The present invention is preferred, and in step (2), the dosage of Zero-valent Iron is that every gram of mud adds Zero-valent Iron 1～2g.
The present invention is preferred, and the sludge concentration passing in step (3) after pending waste water is 2500～5000mg/L.
The present invention is preferred, airway and the rising pipe of described flow lifting type anaerobic reactor are equipped with water seal, prevent that extraneous oxygen from entering, within 10～20 minutes, maintained its anaerobic environment every 4～10 hours to logical nitrogen in flow lifting type anaerobic reactor, aeration intensity is 2～10ml/ (Lmin);
The present invention is preferred, and described Zero-valent Iron is iron filings, sponge iron, micron order Zero-valent Iron or nanoscale zero-valent iron powder.Wherein consider the best preferably extraction and nanometer iron metal for the treatment of effect from treatment effect; Consider from treatment effect and processing cost, preferably iron filings, sponge iron.Described extraction and nanometer iron metal is the ball shaped nano iron of particle diameter 100-200nm, and described micron order Zero-valent Iron is the micron order iron powder of particle diameter 120-150 μ m.
The present invention is preferred, for treatment sewage is fully contacted with mud, is provided with gravel bed in the bottom of flow lifting type anaerobic reactor, and the thickness of gravel bed is 3～5cm, and the mean diameter of gravel is 2～10mm, and water inlet pipe is laid in gravel bed.
The present invention is preferred, and the reactor of flow lifting type anaerobic reactor is vertical type cylinder shape, and useful volume is 3～150L, and reactor water inlet flow velocity is 0.10～1L/h, and treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 30～60 hours.
The present invention is preferred, described pending waste water breeding wastewater, Metallurgical Waste Water, petrochemical wastewater nitrogen-containing wastewater.
The application of efficiently processing the method for nitrogenous effluent based on Zero-valent Iron coupling Anammox of the present invention, is applicable to remove the ammonia nitrogen in breeding wastewater, Metallurgical Waste Water, petrochemical wastewater, is particularly useful for the waste water that ammonia nitrogen concentration is higher and COD concentration is lower.
The reductive action of the Zero-valent Iron adding described in the present invention utilizes can be accelerated the startup of Anammox, removes remaining dissolved oxygen in reactor, makes reactor maintain a comparatively environment for anaerobism; Simultaneously Zero-valent Iron is as the trace element of Anammox bacteria growing necessity, can promote formation and the part of its cellularstructure anammoxosome etc. to need the cyto-architectural formation of iron, thereby accelerate the Growth and reproduction of anaerobic ammonia oxidizing bacteria; The ferrous iron of the oxidized generation of Zero-valent Iron and ferric iron also can improve the secretion of anaerobic ammonia oxidizing bacteria extracellular polymeric, and then increase sludge settling, to reduce sludge loss, preserve biomass, to play the effect of accelerating startup.
The principle that the present invention improves Anammox nitrogen removal rate is to utilize the reductive action of Zero-valent Iron, by the NO generating in Anammox reaction
3 -be converted into NH
4 +, make it again participate in Anammox reaction and NO
2 -reaction, thus NH improved
4 +, NO
2 -removal, reduce NO in water outlet total nitrogen
3 -content so that remaining total nitrogen content reaches urban wastewater treatment firm pollutant emission primary standard (GB18918-2002) in water outlet.Described NO
3 -, NH
4 +conversion formula is:
4Fe
0+NO
3 -+10H
+→NH
4 ++3H
2O+4Fe
2+ (2)
2.82Fe
0+0.75Fe
2++NO
3 -+2.25H
2O→1.19Fe
3O
4+NH
4 ++0.5OH
- (3)
Technical characterstic of the present invention and advantage:
1) method of the present invention can effectively shorten the start time of anaerobic ammonia oxidation process, and can significantly improve the nitrogen removal rate of anaerobic ammonia oxidation process: when water inlet total nitrogen volumetric loading is during in 620N mg/L/d left and right, adding nanoscale zero-valent iron powder can make anaerobic ammonia oxidation process can shorten 33.3% start time, nitrogen removal rate can improve 2～19%, as shown in Figure 1, 2, 3;
2) it is cheap and easy to get that main raw material Zero-valent Iron of the present invention can be used iron filings, sponge iron or micron order Zero-valent Iron, is convenient to heavy industrialization and uses;
3) method reaction conditions gentleness of the present invention, just can carry out, at normal temperatures and pressures without specified conditions; And resultant is without hazardous and noxious substances, environmentally safe harmless;
4) one aspect of the present invention is utilized the biological promoter action of the Zero-valent Iron in the present invention, accelerates the startup of anaerobic ammonia oxidation process; Utilize on the other hand the chemical reduction effect of Zero-valent Iron to impel the nitre nitrogen transformation of generation to become ammonia nitrogen, the ammonia nitrogen generating can participate in Anammox reaction again, to improve nitrogen removal rate, reduce residual total nitrogen content, to meeting urban wastewater treatment firm pollutant emission primary standard.
Brief description of the drawings
Fig. 1 is that application experiment example adds Zero-valent Iron and do not add the change curve of Inlet and outlet water ammonia nitrogen concentration in the reactor of Zero-valent Iron.
Fig. 2 is that application experiment example adds Zero-valent Iron and do not add the change curve of Inlet and outlet water nitrite nitrogen concentration in the reactor of Zero-valent Iron.
Fig. 3 is that application experiment example adds Zero-valent Iron and do not add total nitrogen in the reactor of Zero-valent Iron the change curve of removing load.
Embodiment
Below by embodiment and with reference to accompanying drawing, the present invention is described in detail.It is important to point out that embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
In embodiment, use micron order zeroth order iron powder, nanoscale zero-valent iron powder all purchased from Aladdin reagent company, be analytical pure.Peristaltic pump is purchased from Baoding LanGe constant flow pump Co., Ltd, and model is BT100-2J.
Aeration high pure nitrogen used is purchased from Jinan Deyang Special Gas Co., Ltd., and specification is 99.999%.
Heating rod, water inlet pipe and water outlet pipe, airway are conventional commercial equipment.
Embodiment 1
A method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) active sludge is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, the useful volume of described flow lifting type anaerobic reactor is 4.75L, top is provided with triphase separator, it is the gravel bed that the diameter of 3cm is 5mm that bottom is covered with thickness, and water inlet pipe is laid in gravel bed, active sludge be take from Jinan City one municipal wastewater treatment plant discharge mud after filtration, screening, make after cultivating early stage, by filtering, the leaf in mud is removed in screening, discarded paper, the impurity such as waste plastic, then mud is added to the reaction zone of flow lifting type anaerobic reactor, utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24 hours, keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the mud of removing floating and expanding, the operation of flow lifting type anaerobic reactor is after 7 days, collect bottom settlings mud and be active sludge.
(2) to the extraction and nanometer iron metal that adds particle diameter 100nm in step (1) has added the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of extraction and nanometer iron metal is that every gram of mud adds extraction and nanometer iron metal 2.5g.
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, controlling water inlet flow velocity is that 0.10L/h stops treatment sewage 48 hours in flow lifting type anaerobic reactor, the sludge concentration passing into after pending waste water is 2700mg/L, adopt heating rod to make flow lifting type anaerobic reactor internal temperature maintain 32 degree simultaneously, passed into nitrogen aeration 15min every 8 hours to flow lifting type anaerobic reactor, aeration intensity is 10mL/ (Lmin), preferably, before passing into again pending waste water, also carry out nitrogen aeration 15min, aeration intensity is 10mL/ (Lmin), to maintain anaerobic environment, passing into carbonic acid gas makes pH remain on 7.1.
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 84 days, realization efficiently removes the nitrogen in sewage, then enters the Anammox steady stage.During steady running, total nitrogen is removed to load and is reached 590 ± 25mg N/L/d.
Embodiment 2
A method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) inactivation anaerobic grain sludge is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, the useful volume of described flow lifting type anaerobic reactor is 10L, top is provided with triphase separator, it is the gravel bed that the diameter of 4cm is 6mm that bottom is covered with thickness, and water inlet pipe is laid in gravel bed; Inactivation anaerobic grain sludge is that anaerobic reactor is produced discarded granule sludge, discarded granule sludge is collected, using the organic plastics bottle of clean and good leak tightness as preserving container, needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:2, sealing is at normal temperatures preserved and is made for 1 year, inactivation anaerobic grain sludge color is black or grey, and granularity is 0.5mm, and moisture percentage in sewage sludge is more than or equal to 98wt%.
(2) to the micron order zeroth order iron powder that adds particle diameter 150 μ m in step (1) has added the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of micron order zeroth order iron powder is that every gram of mud adds micron order zeroth order iron powder 5g.
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, controlling water inlet flow velocity is 0.20L/h, treatment sewage is stopped 48 hours in flow lifting type anaerobic reactor, the sludge concentration passing into after pending waste water is 5500mg/L, adopt heating rod to make flow lifting type anaerobic reactor internal temperature maintain 33 degree simultaneously, passed into nitrogen aeration 15min every 6 hours to flow lifting type anaerobic reactor, aeration intensity is 10mL/ (Lmin), preferably, before passing into again pending waste water, also carry out nitrogen aeration 15min, aeration intensity is 10mL/ (Lmin), to maintain anaerobic environment, passing into carbonic acid gas makes pH remain on 7.4.
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 92 days, realization efficiently removes the nitrogen in sewage, then enters the Anammox steady stage.It is 600 ± 20mg N/L/d that steady stage total nitrogen is removed load.
Embodiment 3
A method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) inactivation Anammox mud is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, the useful volume of described flow lifting type anaerobic reactor is 4.75L, top is provided with triphase separator, it is the gravel bed that the diameter of 5cm is 8mm that bottom is covered with thickness, and water inlet pipe is laid in gravel bed; Inactivation Anammox mud is that anaerobic ammonia oxidation reactor is produced discarded mud and made, anaerobic ammonia oxidation reactor is produced to discarded granule sludge to be collected, using the vial of clean and good leak tightness as preserving container, needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:3, preserve and make for 7 months at 4 DEG C of lower seals, inactivation Anammox mud color is red-brown or brown color, and mud MLSS is 10500mg/L, and moisture percentage in sewage sludge is more than or equal to 98wt%.
(2) to the nanoscale zero-valent iron powder that adds particle diameter 150nm in step (1) has added the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of nano grade iron powder is that every gram of mud adds nanoscale zero-valent iron powder 1g.
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, controlling water inlet flow velocity is 0.19L/h, treatment sewage is stopped 24 hours in flow lifting type anaerobic reactor, the sludge concentration passing into after pending waste water is 3000mg/L, adopt heating rod to make flow lifting type anaerobic reactor internal temperature maintain 30 degree simultaneously, passed into nitrogen aeration 15min every 10 hours to flow lifting type anaerobic reactor, aeration intensity is 10mL/ (Lmin), preferably, before passing into again pending waste water, also carry out nitrogen aeration 15min, aeration intensity is 10mL/ (Lmin), to maintain anaerobic environment, passing into carbonic acid gas makes pH remain on 7.6.
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 48 days, realization efficiently removes the nitrogen in sewage, then enters the Anammox steady stage.It is 1150 ± 50mg N/L/d that steady stage total nitrogen is removed load.
Embodiment 4
A method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) inactivation Anammox mud and active sludge are added to the reaction zone of flow lifting type anaerobic reactor, the useful volume of flow lifting type anaerobic reactor is 10L, top is provided with triphase separator, it is the gravel bed that the diameter of 2cm is 3mm that bottom is covered with thickness, and water inlet pipe is laid in gravel bed; The mass ratio of inactivation Anammox mud and active sludge is: 1:1,
Inactivation Anammox mud is that anaerobic ammonia oxidation reactor is produced discarded mud and made, anaerobic ammonia oxidation reactor is produced to discarded granule sludge to be collected, using the vial of clean and good leak tightness as preserving container, needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:3, preserve and make for 7 months at 4 DEG C of lower seals, inactivation Anammox mud color is red-brown or brown color, and mud MLSS is 10500mg/L, and moisture percentage in sewage sludge is more than or equal to 98wt%.
Active sludge be take from Jinan City one municipal wastewater treatment plant discharge mud after filtration, screening, make after cultivating early stage, by filtering, the leaf in mud is removed in screening, discarded paper, the impurity such as waste plastic, then mud is added to the reaction zone of flow lifting type anaerobic reactor, utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24 hours, keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the mud of removing floating and expanding, the operation of flow lifting type anaerobic reactor is after 7 days, collect bottom settlings mud and be active sludge.
(2) to the nanoscale zero-valent iron powder that adds particle diameter 200nm in step (1) has added the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of nanoscale zero-valent iron powder is that every gram of mud adds nanoscale zero-valent iron powder 2g.
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, controlling water inlet flow velocity is 0.27L/h, treatment sewage is stopped 36 hours in flow lifting type anaerobic reactor, the mixing sludge concentration passing into after pending waste water is 4150mg/L, adopt heating in water bath to make flow lifting type anaerobic reactor internal temperature maintain 32 degree simultaneously, passed into nitrogen aeration 15min every 8 hours to flow lifting type anaerobic reactor, aeration intensity is 10mL/ (Lmin), preferably, before passing into again pending waste water, also carry out nitrogen aeration 15min, aeration intensity is 10mL/ (Lmin), to maintain anaerobic environment, passing into carbonic acid gas makes pH remain on 7.5.
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 66 days, realization efficiently removes the nitrogen in sewage, then enters the Anammox steady stage.It is 990 ± 30mg N/L/d that steady stage total nitrogen is removed load.
Comparative example 1
Anammox is efficiently processed a method for nitrogenous effluent, comprises that step is as follows:
(1) active sludge is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, the useful volume of described flow lifting type anaerobic reactor is 4.75L, top is provided with triphase separator, it is the gravel bed that the diameter of 3cm is 5mm that bottom is covered with thickness, and water inlet pipe is laid in gravel bed, active sludge be take from Jinan City one municipal wastewater treatment plant discharge mud after filtration, screening, make after cultivating early stage, by filtering, the leaf in mud is removed in screening, discarded paper, the impurity such as waste plastic, then mud is added to the reaction zone of flow lifting type anaerobic reactor, utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24 hours, keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the mud of removing floating and expanding, the operation of flow lifting type anaerobic reactor is after 7 days, collect bottom settlings mud and be active sludge, the sludge concentration of active sludge is 5700mg/L.
(2) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, controlling water inlet flow velocity is 0.10L/h, treatment sewage is stopped 48 hours in flow lifting type anaerobic reactor, the sludge concentration passing into after pending waste water is 4000mg/L, adopt heating rod to make flow lifting type anaerobic reactor internal temperature maintain 32 degree simultaneously, passed into nitrogen aeration 15min every 8 hours to flow lifting type anaerobic reactor, aeration intensity is 10mL/ (Lmin), preferably, before passing into again pending waste water, also carry out nitrogen aeration 15min, aeration intensity is 10mL/ (Lmin), to maintain anaerobic environment, passing into carbonic acid gas makes pH remain on 7.1.
(3) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 84 days, realization efficiently removes the nitrogen in sewage, then enters the Anammox steady stage.The operation of flow lifting type anaerobic reactor successfully starts anaerobic ammonia oxidation process for 126 days, and realization efficiently removes the nitrogen in sewage, and during steady running, total nitrogen is removed to load and reached 532 ± 25mg N/L/d.
Application experiment example
In the method for embodiment 1-4 and comparative example 1, pass into synthetic waste water, waste water is processed, utilized the water inlet of peristaltic pump control Continuous Flow, controlling hydraulic detention time is 48 hours, and utilize peristaltic pump control effluent recycling, controlling upflow liquid velocity in reactor is 0.5m/h per hour; The concrete composition of described synthetic waste water is: 594mg (NH
4)
2sO
4/ L, 746mg NaNO
2/ L, 500mg KHCO
3/ L, 27.2mg KH
2pO
4/ L, 120mg MgSO
47H
2o/L, 180mg CaCl
22H
2o/L, 1mL trace element/L.The concrete composition of described trace element is 20000mg EDTA/L, 430mg ZnSO
47H
2o/L, 240mg CoCl
26H
2o/L, 990mg MnCl
24H
2o/L, 250mg CuSO
45H
2o/L, 220mg NaMoO
42H
2o/L, 190mg NiCl
26H
2o/L, 210mg NaSeO
46H
2o/L, 14mg H
3bO
4/ L.
Within every 1～7 day, measure a Different Nitrogen Concentration, assessing reactor running status and Anammox start effect accordingly.
Comparative example 1 does not add the operation of Zero-valent Iron UASB reactor and within 126 days, successfully starts anaerobic ammonia oxidation process, and it is 532 ± 25mg N/L/d that steady stage total nitrogen is removed load; And embodiment of the present invention 1-4 adds extraction and nanometer iron metal UASB reactor operation and within 48-92 days, successfully starts anaerobic ammonia oxidation process, shorten 26.9～61.2% start time, it is 590～1150 ± 20mg N/L/d that steady stage total nitrogen is removed load, has improved 30～600mg N/L/d.
Claims (10)
1. a method of efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox, comprises that step is as follows:
(1) mud is added to the reaction zone of flow lifting type anaerobic reactor, moisture percentage in sewage sludge is more than or equal to 99wt%, and described mud is selected from one of active sludge, inactivation anaerobic grain sludge, inactivation Anammox mud or arbitrary combination;
(2) add Zero-valent Iron to adding in the reaction zone of flow lifting type anaerobic reactor of mud, it is mixed with sludge agitation, make mixing sludge, the dosage of described Zero-valent Iron is that every gram of mud adds Zero-valent Iron 0.5～5g;
(3) utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, according to the volume-adjustment peristaltic pump rotating speed of flow lifting type anaerobic reactor with control water inlet flow velocity, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24～96 hours, the sludge concentration passing into after pending waste water is 2000～7000mg/L, adopt heating rod or constant temperature circulating bath device to make flow lifting type anaerobic reactor internal temperature maintain 30～35 degree simultaneously, and pass into nitrogen to maintain anaerobic environment, pass into carbonic acid gas and make pH remain on 7.1～7.7;
(4) keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the operation of flow lifting type anaerobic reactor successfully started sludge anaerobic oxidative ammonolysis after 40～110 days, realization efficiently removes the nitrogen in sewage, then enters next Anammox reaction.
2. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, is characterized in that the preferred inactivation Anammox of described mud mud.
3. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, described active sludge take from sewage work discharge mud after filtration, screening, make after cultivating early stage, by filtering, the leaf in mud is removed in screening, discarded paper, the impurity such as waste plastic, then mud is added to the reaction zone of flow lifting type anaerobic reactor, utilize peristaltic pump to pass into pending waste water from the bottom of flow lifting type anaerobic reactor, making treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 24～96 hours, keep the Water discharge flow speed of flow lifting type anaerobic reactor identical with water inlet flow velocity, the mud of removing floating and expanding, the operation of flow lifting type anaerobic reactor is after 3-7 days, collect bottom settlings mud and be active sludge.
4. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, described inactivation anaerobic grain sludge is anaerobic reactor overproduction or discarded granule sludge and/or goes out sewage sludge and make, by anaerobic reactor overproduction or discarded granule sludge and/or go out sewage sludge and collect, using the organic plastics bottle of clean and good leak tightness as preserving container, needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:2～4, at normal temperatures sealing preserve 1～2 year for subsequent use, inactivation anaerobic grain sludge color is generally black or grey, granularity is 0.5～3mm, moisture percentage in sewage sludge is more than or equal to 98wt%.
5. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, described inactivation Anammox mud is anaerobic ammonia oxidation reactor overproduction or discarded mud and/or goes out sewage sludge and make, by anaerobic ammonia oxidation reactor overproduction or discarded granule sludge and/or go out sewage sludge and collect, using the vial of clean and good leak tightness as preserving container, needing the sludge volume of preserving and the volumetric ratio of preserving container is 1:2～4, 3～4 DEG C of lower seals preserve 6～8 months for subsequent use, inactivation Anammox mud color is red-brown or brown color, moisture percentage in sewage sludge is more than or equal to 98wt%.
6. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, in step (2), the dosage of Zero-valent Iron is that every gram of mud adds Zero-valent Iron 1～2g, and the sludge concentration passing in step (3) after pending waste water is 2500～5000mg/L.
7. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, airway and the rising pipe of described flow lifting type anaerobic reactor are equipped with water seal, prevent that extraneous oxygen from entering, within 10～20 minutes, maintained its anaerobic environment every 4～6 hours to logical nitrogen in flow lifting type anaerobic reactor, aeration intensity is 2～10ml/ (Lmin).
8. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, described Zero-valent Iron is iron filings, sponge iron, micron order Zero-valent Iron or nanoscale zero-valent iron powder, described extraction and nanometer iron metal is the ball shaped nano iron of particle diameter 100-200nm, and described micron order Zero-valent Iron is the micron order iron powder of particle diameter 120-150 μ m.
9. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, it is characterized in that, bottom at flow lifting type anaerobic reactor is provided with gravel bed, the thickness of gravel bed is 3～5cm, the mean diameter of gravel is 2～10mm, water inlet pipe is laid in gravel bed, the reactor of flow lifting type anaerobic reactor is vertical type cylinder shape, virtual height is 6-12m, in reactor, upflow liquid velocity is 0.5～1.5m per hour, and treatment sewage hydraulic detention time in flow lifting type anaerobic reactor is 30～60 hours.
10. the method for efficiently processing nitrogenous effluent based on Zero-valent Iron coupling Anammox according to claim 1, is characterized in that described pending waste water breeding wastewater, Metallurgical Waste Water, petrochemical wastewater nitrogen-containing wastewater.
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