CN104609549B - A kind of remove the method for ammonia nitrogen in waste water - Google Patents
A kind of remove the method for ammonia nitrogen in waste water Download PDFInfo
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Abstract
The present invention provides a kind of and removes the method for ammonia nitrogen in waste water, including following content: (1) is cultivated and obtained nitrifying granular activated sludge and denitrification granular sludge, and the particle diameter of nitrifying granular activated sludge is more than denitrification granular sludge；(2) two kinds of granule sludges are joined fluidized-bed reactor carries out grating, nitrifying granular activated sludge carries out nitration reaction at reactor lower part, denitrification granular sludge carries out denitrification denitrogenation on reactor top, and the dissolved oxygen concentration utilizing the oxygen content entrained by fluid bed fluidizing gas to control water inlet region is 1.0～4.0mg/L.The present invention utilizes fluid bed, the granule sludge of different size and different nitrogen removal performance is carried out grating in the reactor, nitrifying granular activated sludge and denitrification granular sludge is made to play nitrogen removal performance in the zones of different of same reactor, reduce and disturb to each other, it is achieved that efficient synchronous nitration and denitrification ammonia nitrogen removal process.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of remove the method for ammonia nitrogen in waste water.
Background technology
A large amount of ammonia-containing waters discharge because of its production technology characteristic, every day in Chemical Manufacture enterprise.If directly discharged, body eutrophication, algal blooms can be caused, not only reducing water body ornamental value, and making aquatile hypoxia death.Some algae protein toxin also can make people be poisoned through food chain, the serious harm mankind and biological existence.To this end, the ammonia nitrogen removed the most cost-effectively in waste water has become problem demanding prompt solution.
Biological denitrificaion is one of relatively inexpensive effective method removing nitrate pollution from waste water, generally comprises nitrifying process and denitrification process.Nitrifying process is to be NO by nitrifier by mineralized nitrogen2 -And NO3 -Course of reaction.Denitrification process is under anaerobic or hypoxia condition, NO3 -And NO2 -It is converted into the process of gaseous matter by micro-reduction, course of reaction needs using organic carbon as carbon source and the energy.No matter being tradition denitrification process or novel denitrification process, the microorganism being responsible for denitrogenation is mainly nitrifier and denitrifying bacterium.In actual applications, due to the difference of two kinds of thalli growth environment, it is usually and nitrifying process and denitrification process is separated, such as traditional A/O, A2, there is technique tediously long in/O technique, sewage treatment structure floor space is big, investment and many drawbacks such as operating cost is high.
Synchronous nitration denitrification denitrogenation refers to the novel process that nitration reaction and anti-nitration reaction are carried out in same reactor inter-sync, not only overcome the deficiency that traditional handicraft nitrification and denitrification process is carried out in two different reactors, and reducing the aspect such as energy consumption and material consumption, there is prominent advantage.For example, it is possible to reduce anti-nitration reaction equipment, save capital cost；The alkali that denitrification process produces can partly neutralize the acid that nitrifying process produces, and reduces the consumption of alkali liquor, can effectively keep pH in reactor stable.Therefore, synchronous nitration denitrification denitrogenation process, have become as the study hotspot of water treatment field.
Abroad having researcher that nitrifier and denitrifying bacterium are placed in same reactor mixed culture, though the synchronous nitration and denitrification of single reactor can be reached, but denitrification result is unsatisfactory, also has a certain distance from reality application.Holland's Olburgen Rhizoma Solani tuber osi processing waste water processing item uses short distance nitration and Anammox combination to realize synchronous nitration and denitrification, but owing to denitrification uses the anaerobic ammonium oxidizing bacteria of obligate anaerobic, this antibacterial is chronically in certain density aerobic environment, thus reduce the activity of anaerobic ammonium oxidizing bacteria to a certain extent, cause denitrification effect undesirable.Domestic some relevant research work are also carried out it, Geng Jinju etc. utilize denitrification flora and Autotrophic nitrification flora composition denitrogenation (application and environmental organism journal, 2002,8 (1): 78-82), although having preferable ammonia nitrogen removal ability, but impact resistance is more weak, ammonia nitrogen in high density higher than 300mg/L can suppress the growth of thalline, and when ammonia nitrogen concentration is higher than 200mg/L, after denitrogenation, ammonia nitrogen residual volume is more, synchronization does not tolerates high concentration organic carbon, and the organic carbon control of the concentration thalli growth of 500mg/L also reduces denitrification effect；All kinds of antibacterial culturing in this combination flora are inconsistent with growth conditions, and during a kind of function, another kind is but in inhibitory state, causes the most inharmonious, biological denitrificaion time lengthening, and cost increases, and nitric efficiency is affected.CN201210067682.9 discloses the sewage water treatment method of a kind of synchronous nitration and denitrification, by Biomass and biological species in biomembrane increasing reactor, it is ensured that the longest microorganism (such as nitrifier) existence, beneficially nitration reaction；Further, there is the gradient phenomenon of dissolved oxygen concentration in biofilm carrier from surface to inside, should have aerobic, anoxia and aerobic area state mutually, provide good environment for direct denitrogenation；In course of reaction, use oxygenate apparatus, form the most aerobic, anoxia section in facilitating reactor, form the macro environment of simultaneous nitrification and denitrification；Carry out nitrification and denitrification reaction simultaneously.But, this method needs to use bio-carrier to build different Biomass and the biomembrane of biological species, biofilm carrier needs to exist the gradient conditions of the dissolved oxygen concentration that should have aerobic, anoxia and aerobic area mutually from surface to inside, practical operation difficulty is relatively big, can not regulate and control nitrifier and the respective nitric efficiency of denitrifying bacterium.
Although synchronous nitration and denitrification has had bigger development at present, but generally there is the deficiencies such as load is less, and clearance is on the low side, fluctuation of service, it is impossible to effectively Ammonia-Containing Wastewater Treatment, and some technique being currently running does not considers the removal problem of total nitrogen.Which greatly limits development and the application of synchronous nitration and denitrification technique.Therefore, the most preferably provide suitable growth conditions, it is ensured that nitrification and denitrification can efficiently be carried out, and makes the operation that synchronous nitration and denitrification is steady in a long-term, the process accelerating the application of synchronous nitration denitrification denitrogenation process industry is had positive effect.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of and removes the method for ammonia nitrogen in waste water.The present invention utilizes fluid bed, the granule sludge of different size and different nitrogen removal performance is carried out grating in the reactor, nitrifying sludge granule and denitrification mud granule is made to play nitrogen removal performance in the zones of different of same reactor, reduce and disturb to each other, it is achieved that efficient synchronous nitration and denitrification ammonia nitrogen removal process.
The present invention removes the method for ammonia nitrogen in waste water, including following content: (1) is cultivated and obtained nitrifying granular activated sludge and denitrification granular sludge, and the particle diameter of nitrifying granular activated sludge is more than denitrification granular sludge；(2) two kinds of granule sludges are joined fluidized-bed reactor carries out grating, nitrifying granular activated sludge carries out nitration reaction at reactor lower part, denitrification granular sludge carries out denitrification denitrogenation on reactor top, and the dissolved oxygen concentration utilizing the oxygen content entrained by fluid bed fluidizing gas to control water inlet region is 1.0～4.0mg/L.
In the present invention, nitrifying granular activated sludge and denitrification granular sludge use mode well-known to those skilled in the art to cultivate.The particle diameter of nitrifying granular activated sludge is 2.0～5.0mm, and preferably 2.0～4.0mm, average density is 1.02～1.3g/cm3；The particle diameter of denitrification granular sludge is 1.0～4.0mm, and preferably 1.0～3.0mm, average density is 1.02～1.3g/cm3.In order to increase the stability of granule sludge, the activated carbon adding 0.1～1.0mm in nitrification and denitrification culturing sludge pond obtains granule sludge as absorption carrier, cultivation.The high efficiency of stability and denitrogenation in order to increase granule sludge further, preferably add different size of activated carbon as absorption carrier, in nitrifying sludge culture pond, add the activated carbon of 0.5～1.0mm as absorption carrier, denitrification culturing sludge pond adds the activated carbon of 0.1～0.5mm as absorption carrier.If relying on merely the size of granule sludge self to realize grating, then the adsorbance and the adsorption thickness that are positioned at the nitrifying granular activated sludge of fluid bed bottom are the biggest, and longtime running easily causes the phenomenon that surface thalline absorption is insecure and comes off.Irregular particle mud size refers generally to the Average equivalent diameter (i.e. having identical external surface area with spheroidal particle) of granule.In start-up course, two kinds of granule sludges packing volume mark in the reactor is 5%～30%, and the mass ratio of nitrifying granular activated sludge and denitrification granular sludge is 1:1～5:1.
In the present invention, according to fluidization ultimate principle, granule sludge is main by gravity, buoyancy and drag force in fluid bed, wherein, the average density of granule and particle diameter decide the stressing conditions of granule, i.e. variable grain has different average densitys and particle diameter, and its stress in fluid bed is different, therefore the height suspended is the most different.According to above-mentioned principle, in the case of granule sludge average density is close, cultivate and obtain different size of granule sludge, just can realize the grating of the granule sludge of two kinds of difference in functionalitys in fluidized-bed reactor, reduce along Flow of Goods and Materials direction particle size, the nitrifying granular activated sludge that then particle diameter is relatively large is positioned at reactor lower part, and the relatively small denitrification granular sludge of particle diameter is positioned at reactor top.First the ammonia-containing water entered from reactor bottom carries out nitration reaction with nitrifying granular activated sludge, and mineralized nitrogen becomes nitrate nitrogen or nitrite nitrogen；Then waste water entrance upper area carries out denitrification denitrogenation under the effect of denitrification granular sludge, and nitrate nitrogen or nitrite nitrogen are changed into nitrogen.According to mud and the characteristic of waste water, controlling waste water flow velocity is 1～10mm/s, and preferably 3～6mm/s, the time of staying is 10～24h, preferably 12～20h.
In the present invention, the dissolved oxygen concentration utilizing the oxygen content entrained by fluid bed fluidizing gas to control water inlet region is 1.0～3.0mg/L.Along with the direction of Flow of Goods and Materials, oxygen is utilized effectively in nitrification zone, enters upper area dissolved oxygen concentration relative deficiency, beneficially denitrification and carries out under anaerobic or hypoxia condition.When fluctuation occurs in dissolved oxygen concentration, by the content of the oxygen entrained by regulation fluidizing gas, to ensure that the concentration of dissolved oxygen is in suitable value.The temperature controlling wastewater treatment system is 20 DEG C～40 DEG C, and pH value is 6～9.
In the present invention, fluidized-bed bottom sets air inlet and water inlet, and top sets air vent and outlet.Arranging cyclone separator, cyclone hydraulic separators in reactor top or can carry out the multiphase separator of gas-liquid-solid separation, waste water and gas after preventing mud from going out and processing separate.The condition of nitrifying sludge and denitrification mud that other operating condition of fluid bed processes waste water routinely controls.The determinator of cultivating system dissolved oxygen content is set, adjusts the oxygen concentration in air inlet as required.There is provided pH electrode detection, in order to add acid by external source, alkali realizes system pH and controls simultaneously.Temperature controls as internal coil pipe mode of heating or arranges temperature control chuck outside reactor to maintain required temperature.
In the present invention, in wastewater treatment process, control nitrifying granular activated sludge sludge concentration be 2.0～8.0g/L, the sludge concentration of denitrification granular sludge is 1.0～5.0g/L, when mud not enough or superfluous time, be adjusted by online displacement apparatus.Ammonia-containing water be all applicable Biochemical method containing COD and the waste water of ammonia nitrogen, ammonia nitrogen concentration is generally 100～1000mg/L.The nutrient substance needed for active sludge treatment ammonia-containing water can be added, to improve its reactivity.The proportioning of nutrient substance is: Fe2+Concentration is 0.01～0.06g/L, K+Concentration is 0.05～0.5g/L, Ca2+Concentration is 0.01～0.1g/L, Mg2+Concentration is 0.05～0.5g/L；PH value is 6.5～7.5.
In the present invention, being the organic carbon source that 3:1～10:1 adds needed for denitrification according to carbon-nitrogen mass ratio, organic carbon source can be sodium succinate, sodium acetate, methanol, glucose or ligno-cellulose hydrolysate etc..Supplement organic carbon source with batch or continuation mode, carry out stream preferably based on the depletion rate of organic carbon source and add, to reduce the organic carbon source impact on nitrifying sludge.
Compared with prior art, the present invention has a feature highlighted below:
1, fluidization technology is utilized, it is suspended in diverse location carries out grating according to different nitrogen removal performances are different with different size of granule sludge stress in fluid bed, nitrifying granular activated sludge and denitrification granular sludge is made to play nitrogen removal performance in the zones of different of same reactor, granule sludge is at the most individually space behavior, reducing and disturb to each other, overcoming prior art needs use multiple reactor or nitrifying sludge and denitrification mud directly carry out the deficiency of mixed processing ammonia-containing water.
2, nitrifying sludge is different to the demand of dissolved oxygen with denitrification mud, although aerobic denitrification mud has an oxygen-resistant ability, but its under low oxygen conditions nitrogen removal performance higher, therefore two kinds of mud are directly mixed and carry out denitrogenation and there is drawback.The oxygen content that the present invention utilizes fluid bed fluidizing gas to carry controls to enter the dissolved oxygen concentration of nitrification zone, and oxygen is utilized effectively in nitrification zone, enters the dissolved oxygen relative deficiency of denitrification zone, beneficially denitrification mud and plays nitrogen removal performance.With two kinds of mud direct mixed phase ratios, the present invention can provide different oxygen environment, make nitrifying sludge and denitrification mud grow under the most suitable dissolved oxygen conditions, be effectively improved nitrifying sludge and the denitrification activity of denitrification mud, improve the efficiency of synchronous nitration and denitrification.
3, the ammonia nitrogen during nitrifying sludge utilizes waste water carries out nitration reaction, and the nitrate nitrogen of generation and/or nitrite nitrogen can enter the denitrification zone, the top nutrient substance as denitrification mud, and nitrate nitrogen and/or nitrite nitrogen are changed into gas and constantly discharge by denitrification mud.Along with the flowing of reaction mass with denitrifying carry out, nitrate nitrogen and/or nitrite nitrogen can constantly enter upper area and meet the needs of denitrification mud；Simultaneously because the reduction of nitrification zone product inhibition, being favorably improved process and the effect of nitration reaction, the two complements each other and promotes, it is achieved that the efficient removal of total nitrogen.
4, along with the carrying out of nitration reaction, need to add alkali liquor and maintain the pH of suitable growth, and the alkali that denitrification process produces can partly neutralize the acid that nitrifying process produces, and reduces the consumption of alkali liquor, can effectively keep pH in reactor stable, meets the requirement of energy-saving and emission-reduction.
5, the inventive method flow process is simple, structure of reactor simple, space reactor utilization rate is high, and technological operation is steady, motility is high, may be used for the process of various ammonia-containing water.
Accompanying drawing explanation
Fig. 1 is a kind of fluidized-bed reactor schematic diagram of the inventive method；
Wherein: 1-nitrifying granular activated sludge, 2-denitrification granular sludge, 3-nitrification zone, 4-denitrification zone, 5-water inlet, 6-cloth QI KOU, 7-gas outlet, 8-outlet, 9-material-feeding port, 10-mends carbon mouth, 11-separator, 12-nitrifying sludge on-line control mouth；13-denitrification mud on-line control mouth.
Detailed description of the invention
Shown in Fig. 1, in a fluidized bed reactor, nitrifying granular activated sludge 1 is in formation nitrification zone, reactor lower part region 3, and denitrification granular sludge 2 forms denitrification zone 4 at the upper area of reactor.Reactor bottom is provided with water inlet 5 and air inlet 6, and reactor top is provided with gas outlet 7 and outlet 8.Nitrification zone sets material-feeding port 9, by material-feeding port to add control sour, that alkali realizes system pH.Denitrification zone sets benefit carbon mouth 10, adds the organic carbon source needed for denitrification by mending carbon mouth.Reactor head can arrange separator 11, separator is cyclone separator, cyclone hydraulic separators or the multiphase separator that can carry out gas-liquid-solid separation, waste water and gas after being possible to prevent mud to go out and processing separate, and now gas outlet 7 and outlet 8 are arranged on separator.When mud not enough or superfluous time, can be adjusted by nitrifying sludge on-line control mouth 12 and denitrification mud on-line control mouth 13.
First cultivation acquisition particle diameter is between 2.0～5.0mm, and average density is 1.02～1.3g/cm3Nitrifying granular activated sludge, and particle diameter is between 1.0～4.0mm, and average density is 1.02～1.3g/cm3Denitrification granular sludge.Two kinds of granule sludges packing volume mark in the reactor is 5%～30%, and adds in fluidized-bed reactor according to the ratio of 1:1～5:1.According to mud and the characteristic of waste water, controlling waste water flow velocity is 1～10mm/s, and preferably 3～6mm/s, the time of staying is 10～24h, preferably 12～20h.
Starting after fluidized-bed reactor, waste water is first into nitrification zone, carries out nitration reaction under the nitrifying granular activated sludge effect with oxygen, mineralized nitrogen is become nitrate nitrogen or/and nitrite nitrogen.The dissolved oxygen concentration utilizing the oxygen content entrained by fluid bed fluidisation to control nitrification zone water inlet is 1.0～4.0mg/L.When fluctuation occurs in denitrification space dissolved oxygen concentration, by the oxygen content entrained by regulation fluid bed fluidisation, to ensure that dissolved oxygen concentration is for 1.0～4.0mg/L.The temperature controlling wastewater treatment system is 20 DEG C～40 DEG C, and pH value is 6～9.
Waste water through nitrification zone arrives the denitrification zone on top, under the effect of denitrification granular sludge, by nitrate nitrogen or/and nitrite nitrogen changes into nitrogen.Along with the direction of reaction mass flowing, oxygen is utilized effectively in nitrification zone, enters upper area dissolved oxygen relative deficiency, the most denitrifying efficiently carries out.Simultaneously in wastewater treatment process, supplement the organic carbon source needed for denitrification.
Waste water after nitration denitrification processes carries out three phase separation with remaining gas and a small amount of mud through multiphase separator, and mud can be back to reactor, and waste water and remaining gas discharge reactor respectively.
Below by embodiment, the present invention is described in further details.But it is not so limited the present invention.
Embodiment 1
Using the fluid bed shown in Fig. 1 of the present invention, the effective volume of reactor is 10L, is provided with the controllers such as temperature, pH, dissolved oxygen in reactor, and the ratio of height to diameter of fluid bed is 10:1.
The particle diameter of the nitrifying granular activated sludge that cultivation obtains is between 2.0～3.0mm, and average density is 1.1～1.2g/cm3, the particle diameter of aerobic denitrification particle sludge is between 1.0～2.0mm, and average density is 1.1～1.2g/cm3, two kinds of granule sludges packing volume mark in the reactor is 15%, and adds in fluidized-bed reactor according to the ratio of 2:1.Then adding in reactor by water inlet by ammonia-containing water, ammonia nitrogen concentration is 400mg/L, and controlling waste water flow velocity is 6mm/s, and the time of staying is 12h.
In wastewater treatment process, the dissolved oxygen concentration controlling water inlet region is 2.0～3.0mg/L, and the dissolved oxygen concentration detecting denitrification zone after system run all right is 0.5～1.0mg/L.The sludge concentration controlling nitrifying granular activated sludge is 3.0～4.0g/L, and the sludge concentration of aerobic denitrification particle sludge is 2.0～3.0g/L.PH value in detection processing system, regulates pH to 7.5 simultaneously.Temperature controls to heat for temperature control chuck, and controlling temperature is 30 DEG C.Organic carbon source uses methanol, and carbon-nitrogen mass ratio is 5:1, carries out stream according to the depletion rate of organic carbon source and adds.When mud growth is superfluous, exceeding required sludge concentration, mud can be discharged a part, processed waste water is discharged by outlet.
After running 15 days continuously, in water outlet, ammonia nitrogen concentration is less than 5mg/L, and ammonia nitrogen removal frank is up to more than 98.8%.Total nitrogen concentration is less than 20mg/L, and nitrogen removal rate is up to more than 95%.COD concentration is less than 50mg/L, does not has excess, be not result in that water outlet COD increases while ensureing organic carbon source supply.Result is as shown in table 1.
Embodiment 2
Using the fluid bed shown in Fig. 1 of the present invention, the effective volume of reactor is 10L, is provided with the controllers such as temperature, pH, dissolved oxygen in reactor, and the ratio of height to diameter of fluid bed is 10:1.
Adding the activated carbon that particle diameter is 0.8～1.0mm in nitrifying sludge culture apparatus, cultivation acquisition particle diameter is between 2.0～3.0mm, and average density is 1.2～1.3g/cm3Nitrifying granular activated sludge；The activated carbon of 0.2～0.5mm is added, it is thus achieved that particle diameter is between 1.0～2.0mm, and average density is 1.2～1.3g/cm in aerobic denitrification culturing sludge device3Aerobic denitrification particle sludge.Two kinds of granule sludges packing volume mark in the reactor is 15%, and adds in fluidized-bed reactor according to the ratio of 2:1.Then adding in reactor by water inlet by ammonia-containing water, ammonia nitrogen concentration is 400mg/L, and controlling waste water flow velocity is 6mm/s, and the time of staying is 12h.
In wastewater treatment process, owing to the dissolved oxygen of reactor zones of different is different, the dissolved oxygen concentration therefore controlling water inlet region is 2.0～3.0mg/L, and the dissolved oxygen concentration detecting denitrification zone after system run all right is 0.5～1.0mg/L.The sludge concentration controlling nitrifying granular activated sludge is 3.0～4.0g/L, and the sludge concentration of aerobic denitrification particle sludge is 2.0～3.0g/L.PH value in detection processing system, regulates pH to 7.5 simultaneously.Temperature controls to heat for temperature control chuck, and controlling temperature is 30 DEG C.
Organic carbon source uses methanol, and carbon-nitrogen mass ratio is 5:1, carries out stream according to the depletion rate of organic carbon source and adds.When mud growth is superfluous, exceed required sludge concentration, mud can be discharged a part.Processed waste water is discharged by outlet.
After running 15 days continuously, in water outlet, ammonia nitrogen concentration is less than 5mg/L, and ammonia nitrogen removal frank is up to more than 98.8%.Total nitrogen concentration is less than 21mg/L, and nitrogen removal rate is up to more than 94.8%.COD concentration is less than 50mg/L, does not has excess, be not result in that water outlet COD increases while ensureing organic carbon source supply.Compared with water outlet with embodiment 1, in water outlet, suspension content declines.Result is as shown in table 1.
Embodiment 3
Using the fluid bed shown in Fig. 1 of the present invention, the effective volume of reactor is 10L, is provided with the controllers such as temperature, pH, dissolved oxygen in reactor, and the ratio of height to diameter of fluid bed is 10:1.
Adding the activated carbon that particle diameter is 0.8～1.0mm in nitrifying sludge culture apparatus, cultivation acquisition particle diameter is 3.0～4.0mm, and average density is 1.2～1.3g/cm3Nitrifying granular activated sludge；The activated carbon of 0.2～0.5mm is added, it is thus achieved that particle diameter is 2.0～3.0mm, and average density is 1.2～1.3g/cm in anaerobic denitrifying culturing sludge device3Anaerobic denitrifying granule sludge, two kinds of granule sludges packing volume mark in the reactor is 30%, and adds in fluidized-bed reactor according to the ratio of 3:1.Then adding in reactor by water inlet by ammonia-containing water, ammonia nitrogen concentration is 800mg/L, and controlling waste water flow velocity is 3mm/s, and the time of staying is 20h.
In wastewater treatment process, owing to the dissolved oxygen of reactor zones of different is different, the dissolved oxygen concentration therefore controlling water inlet region is 1.0～2.0mg/L, detects the dissolved oxygen concentration of denitrification zone for less than 0.3mg/L after system run all right.The sludge concentration controlling nitrifying granular activated sludge is 4.0～5.0g/L, and the sludge concentration of anaerobic denitrifying granule sludge is 3.0～4.0g/L.Add the nutrient substance needed for nitrifying sludge and anaerobic denitrifying Treatment of Sludge waste water, to improve its reactivity.The proportioning of nutrient substance is: Fe2+Concentration is 0.01g/L, K+Concentration is 0.5g/L, Ca2+Concentration is 0.1g/L, Mg2+Concentration is 0.05g/L；PH value is 7.0.PH value in detection processing system, the pH to 8.0 of regulation waste water simultaneously.Temperature controls to add heat pipes heat for inside, and controlling temperature is 35 DEG C.
Organic carbon source uses methanol, and carbon-nitrogen mass ratio is 4:1, carries out stream according to the depletion rate of organic carbon source and adds.When mud growth is superfluous, exceed required sludge concentration, mud can be discharged a part.Processed waste water is discharged by outlet.
After running 20 days, in water outlet, ammonia nitrogen concentration is less than 13mg/L, and ammonia nitrogen removal frank is up to more than 98.4%.Total nitrogen concentration is less than 54mg/L, and nitrogen removal rate is up to more than 93.3%.COD concentration is less than 40mg/L, is ensureing that organic carbon source supply does not has excess simultaneously, is being not result in that water outlet COD increases.Result is as shown in table 1.
Comparative example 1
Using reactor same as in Example 1 and process conditions, difference is not use fluid bed, uses common biochemical aeration tank to realize back-mixing, carries out synchronous nitration and denitrification.After running 15 days, in water outlet, ammonia nitrogen concentration is about 25mg/L, and ammonia nitrogen removal frank is 93.8%.Nitrate nitrogen concentration is 24mg/L, and nitrite nitrogen concentration is 42 mg/L, and total nitrogen concentration is 90mg/L, and nitrogen removal rate is 77.5%.COD concentration is 101mg/L, owing to nitrate nitrogen and nitrite nitrogen have accumulation, thus results in the accumulation of COD.Result is as shown in table 1.
Comparative example 2
Use reactor same as in Example 1 and process conditions, difference is that the particle diameter cultivating nitrifying granular activated sludge and the aerobic denitrification particle sludge obtained is all between 2.0～4.0mm, granule sludge carries out grating in fluid bed, but nitrifying sludge and denitrification mud do not have single action space.After running 15 days, in water outlet, ammonia nitrogen concentration is about 20mg/L, and ammonia nitrogen removal frank is 95%.Nitrate nitrogen concentration is 22mg/L, and nitrite nitrogen concentration is 38mg/L, and total nitrogen concentration is 80mg/L, and nitrogen removal rate is 80%.COD concentration is 90mg/L, owing to nitrate nitrogen and nitrite nitrogen have accumulation, thus results in the accumulation of COD.Result is as shown in table 1.
Comparative example 3
Use reactor same as in Example 1 and process conditions, difference is in nitrification and denitrification culturing sludge device to add the activated carbon of particle diameter 0.5mm, cultivates nitrifying granular activated sludge and the aerobic denitrification particle sludge of particle diameter 2.0～3.0mm obtaining particle diameter 3.0～4.0mm.After running 15 days, in water outlet, ammonia nitrogen concentration is less than 5mg/L, and ammonia nitrogen removal frank is 98.8%.Nitrate nitrogen concentration is 7mg/L, and nitrite nitrogen concentration is 13 mg/L, and total nitrogen concentration is about 25mg/L, and nitrogen removal rate is 93.4%.COD concentration is about 50mg/L, owing to nitrate nitrogen and nitrite nitrogen have accumulation, thus results in the accumulation of COD.
Table 1 embodiment and the result of comparative example
As shown in Table 1, although the ammonia nitrogen removal effect of comparative example 1 and comparative example 2 is up to more than 93%, but owing to the treatment effect in denitrification region is the best, therefore nitrogen removal rate is unsatisfactory.And although comparative example 3 can also reach preferable treatment effect, but the size that the grating being because granule sludge fully relies on self realizes, the sludge quantity of the granule sludge absorption being positioned at reactor lowermost layer is more, and surface easily comes off, and causes the float in water outlet more of a relatively high.
Claims (13)
1. one kind removes the method for ammonia nitrogen in waste water, it is characterised in that include following content: (1) is cultivated and obtained nitrifying granular activated sludge and denitrification granular sludge, and the particle diameter of nitrifying granular activated sludge is more than denitrification granular sludge；(2) two kinds of granule sludges are joined fluidized-bed reactor carries out grating, nitrifying granular activated sludge carries out nitration reaction at reactor lower part, denitrification granular sludge carries out denitrification denitrogenation on reactor top, and the dissolved oxygen concentration utilizing the oxygen content entrained by fluid bed fluidizing gas to control water inlet region is 1.0～4.0mg/L.
Method the most according to claim 1, it is characterised in that: the particle diameter of nitrifying granular activated sludge is 2.0～5.0mm, and average density is 1.02～1.3g/cm3；The particle diameter of denitrification granular sludge is 1.0～4.0mm, and average density is 1.02～1.3g/cm3。
Method the most according to claim 2, it is characterised in that: the particle diameter of nitrifying granular activated sludge is 2.0～4.0mm, and the particle diameter of denitrification granular sludge is 1.0～3.0mm.
4. according to the method described in claim 1,2 or 3, it is characterised in that: in start-up course, two kinds of granule sludges packing volume mark in the reactor is 5%～30%, and the mass ratio of nitrifying granular activated sludge and denitrification granular sludge is 1:1～5:1.
5. according to the method described in claim 1,2 or 3, it is characterised in that: the activated carbon adding 0.1～1.0mm in nitrification and denitrification culturing sludge pond obtains granule sludge as absorption carrier, cultivation.
Method the most according to claim 5, it is characterized in that: add different size of activated carbon as absorption carrier, in nitrifying sludge culture pond, add the activated carbon of 0.5～1.0mm as absorption carrier, denitrification culturing sludge pond adds the activated carbon of 0.1～0.5mm as absorption carrier.
Method the most according to claim 1, it is characterised in that: according to mud and the characteristic of waste water, controlling waste water flow velocity is 1～10mm/s, and the time of staying is 10～24h.
Method the most according to claim 7, it is characterised in that: controlling waste water flow velocity is 3～6mm/s, and the time of staying is 12～20h.
Method the most according to claim 1, it is characterised in that: the temperature controlling wastewater treatment system is 20 DEG C～40 DEG C, and pH value is 6～9.
Method the most according to claim 1, it is characterized in that: arrange cyclone separator, cyclone hydraulic separators on fluidized-bed reactor top or can carry out the multiphase separator of gas-liquid-solid separation, waste water and gas after preventing mud from going out and processing separate.
11. methods according to claim 1, it is characterized in that: in wastewater treatment process, the sludge concentration controlling nitrifying granular activated sludge is 2.0～8.0g/L, and the sludge concentration of denitrification granular sludge is 1.0～5.0g/L, when mud not enough or superfluous time, be adjusted by online displacement apparatus.
12. according to the method described in claim 1 or 11, it is characterised in that: adding the nutrient substance needed for active sludge treatment ammonia-containing water, the proportioning of nutrient substance is: Fe2+Concentration is 0.01～0.06g/L, K+Concentration is 0.05～0.5g/L, Ca2+Concentration is 0.01～0.1g/L, Mg2+Concentration is 0.05～0.5g/L；PH value is 6.5～7.5.
13. according to the method described in claim 1 or 11, it is characterised in that: being the organic carbon source that 3:1～10:1 adds needed for denitrification according to carbon-nitrogen mass ratio, organic carbon source can be sodium succinate, sodium acetate, methanol, glucose or ligno-cellulose hydrolysate.
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