CN104909455B - Method for relieving anaerobic ammonium oxidation system salinity shock with betaine as additive - Google Patents
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Abstract
The invention relates to a method for relieving anaerobic ammonium oxidation system salinity shock with betaine as an additive. According to the invention, a successfully started anaerobic ammonium oxidation SBR reactor is used for processing salt-containing wastewater, wherein a volatile suspended sludge concentration is maintained at 6-9g/L, an inlet water NH4＜+＞-N concentration is 180-220mg/L, and the molar ratio of NH4＜+＞-N to NO2＜-＞-N is controlled at 1:1-1:1.32 through adding (NH4) 2SO4 and NaNO2; the betaine concentration in the reactor is maintained at 0.1-5mmol/L through adding betaine; with a heating band, the temperature of the reactor is controlled at 30-35 DEG C; DO is controlled at 0-0.1mg/L; inlet water pH is stabilized at 7.0-8.5 through dropping NaOH/HCl; anoxic stirring is carried out for 4-8h after water feeding; when stirring is finished, the material is allowed to stand and to precipitate; when precipitation is finished, a supernatant is discharged. With the method provided by the invention, anaerobic ammonium oxidation activity recovery time when the anaerobic ammonium oxidation system is under salinity load shock can be effectively shortened, nitrogen removal rate can be improved, and a higher total nitrogen removal rate can be realized.
Description
Technical field
The present invention relates to the new application of glycine betaine, salinity high in alleviating Anaerobic ammonium oxidation system as additive using glycine betaine
The method of suppression.
Background technology
Due to the production activity of the mankind, substantial amounts of municipal sewage, industrial wastewater and rural sewage are discharged, wherein containing
Nitrogen-containing pollutant very high causes Water element accumulation, and then causes body eutrophication, destroys the Nature original
The ecological balance, the Environmental capacity of water body nitrogen has become problem demanding prompt solution.
Biological denitrificaion method is existing denitrogenation of waste water method the most cost-effective, and its application is also the most extensive.Traditional
Wastewater biological denitrificaion technology refers mainly to nitrify a denitrification process.Technique elder generation is under conditions of aerobic by nitrifier by waste water
Ammoxidation be nitrate, after under anoxic conditions by denitrifying bacterium with organic matter as electron donor by nitrate reduction as nitrogen
Gas.But one denitrification process of nitrification has nitrifying process oxygen demand greatly, oxygenation energy consumption is big, and outer increasing is needed in denitrification process
The electron donor (organic matter) of amount, increased additional facilities and processing cost, can also cause sludge yield to increase.Anammox
Arisen at the historic moment as a kind of Process of Biological Nitrogen Removal.Anammox reaction equation is NH4 ++1.32NO2 -+0.066HCO3 -
+0.13H+→1.02N2+0.26NO3 -+0.066CH2O0.5N0.15+2.03H2O, anaerobic ammonia oxidizing bacteria is with NO under anoxic conditions2 --
N is electron acceptor, NH4 +- N carries out Anammox reaction for electron donor, without aeration and additional carbon.Anaerobic ammonia oxidizing bacteria
It is autotrophic bacterium, carbonate/carbon dioxide is the inorganic carbon source needed for its growth, so the oxidation of ammonia nitrogen is participated in without molecular oxygen,
Without organic carbon source, this will substantially reduce the operating cost of sewage aerobic biological denitrificaion for the reduction of nitrite nitrogen simultaneously；
The growth rate (doubling time is 11d) of Anammox microorganisms and yield (0.11g [VSS]/g [NH4 +]) it is low-down, therefore dirty
Mud yields poorly, but the conversion ratio of nitrogen is but 0.25mg [N]/(mg [SS] d), equal to each other with traditional aerobic nitrification；
Do not add under conditions of any chemicals, the operating cost of sewage treatment plant can be reduced, efficiently going for nitrogen can be realized again
Remove.
Under conditions of Low-salinity, anaerobic ammonium oxidizing bacteria can be by adjusting the osmotic pressure of itself for anaerobic ammonia oxidation process
To alleviate salinity shock, and when Variation of Salinity Condition is higher than this scope, the regulation of itself cannot effectively alleviate salinity shock, cause
The activity reduction of Anammox reaction.Often there is salinity higher in industrial wastewater, microbial cell can be directly contributed and oozed
The change of pressure thoroughly, causes microbial cell to rupture or suppress it and grows, and causes sludge settling property to decline, and then destroys whole raw
The operation of thing processing system.Due to the unstability in industrial processes, salinity may increase suddenly, and this is biological treatment
During a difficult point.Currently, saliferous industrial wastewater is mainly processed by the following method：(1) it is this to being diluted
Method operational administrative is simple, but can increase wastewater treatment scale, correspondingly needs huger treatment facility, causes capital construction to be thrown
The raising of money and operating cost, while can also cause the huge waste of water resource；(2) salinity high is processed by acclimated microorganism to give up
Water, by the selection index system of environment, the microorganism survival of the fittest, largely propagation turns into advantage to salt-durable microbe in microbiologic population
Strain, enables microbiologic population stably to exist in saline environment, but the domestication required time is more long, even across tame and docile
Changing micropopulation also cannot fully adapt to environment；(3) by application biological reinforcing technology, using salt-durable microbe or the micro- life of thermophilic salt
Thing improves conventional microbiological contaminant removal capacity of the group under hypersaline environment, can significantly improve the biochemistry of high salinity waste water
Treatment effeciency, but the optimization process state that the salt-durable microbe that is utilized of biological reinforcing technology or halophilic microorganism are adapted to is not
Together, this to result in processing system unstable in reply salinity shock wave vibration relief fruit.
Also known as betaine or trimethylglycine, molecular structural formula is CH to glycine betaine3N+(CH3)2CH2COO-, with
Methionine, choline chemical constitution are more similar, belong to quaternary amine alkaloids, and Scheibler in 1869 is by this from beet
It is separating obtained, be referred to as " glycine betaine " with quatemay ammonium inner salt structure or the compound for making ammonium structure, then research find its
Many animals and plants and the internal of microorganism are widely present.Glycine betaine mainly has following aspect in the effect of biological field：Because sweet
Dish alkali contains three active methyls, therefore some methionine reduction feed cost can be directly substituted as feed addictive；Promote fat
Fat metabolism and protein synthesize, and improve lean meat percentage, the effectively generation of prevention fatty liver；There is good taste to many aquatic livestocks
Feeling stimulates and phagostimulating effect, and phagostimulant is used as in aquatic animal feed, greatly improves efficiency of feed utilization；Bipolar the two of glycine betaine
Property ion characteristic and water-soluble well, be a kind of important permeation protective agent for animal and plant cells, it is internal with regulation
Osmotic pressure, relax stress effect.When by saline and alkaline or water stress, a large amount of Organic osmoticas are accumulated in cytoplasm for example sweet
Dish alkali, maintains osmotic equilibrium, this avoid cytoplasm high concentration inorganic ion-pair enzyme and the murder by poisoning of metabolism.In sewage disposal neck
Domain, studies have found that under conditions of salinity high, addition 1mmol glycine betaines are conducive to pure methane Sarcina and pure methane silk
The existence of shape bacterium.Foreign countries have researcher to find, under 35gNaCl/L salinity shock environment, by adding glycine betaine, can make to detest
Oxygen digestion reactor methane production improves three times.Now, people, by chemical synthesis process, are original by trimethylamine and monoxone
Material, is synthesized in aqueous, then obtains glycine betaine using method separating-purifyings such as recrystallizations, low production cost, and
And can mass produce.
The content of the invention
It is an object of the invention to provide a kind of anaerobic ammonia oxidation process, when salinity load impact high is tackled, fast quick-recovery is high
The method for imitating stable operation.It is used to overcome the current domestication Anammox under the conditions of saliferous dirty as additive by the use of glycine betaine
The mud shortcoming that time-consuming.The method operation is flexibly simple, the salinity load impact being subjected to according to anaerobic ammonia oxidation reactor
Size, adds glycine betaine in right amount, so as to realize that anaerobic ammoxidation activity recovers faster, improves nitrogen removal rate (NRR), and
Realize nitrogen removal rate higher.
The purpose of the present invention is achieved through the following technical solutions:
By the use of glycine betaine anaerobic ammonia oxidation process fast quick-recovery when salinity load impact high is tackled is caused as additive
The method of efficient stable operation, refers to the fast quick-recovery anaerobism ammonia under conditions of salinity load impact high (this experiment is 30g/L)
The activity of oxidation, improves nitrogen removal rate (NRR) and nitrogen removal rate.
A kind of Anammox for investigating the Anaerobic ammonium oxidation system influence for a long time for adding glycine betaine to being subjected to salinity shock
SBR devices, it is characterised in that：
As shown in figure 1, the device is by raw water box, SBR anaerobic ammonia oxidation reactors are in series.Raw water box passes through water inlet pipe
It is connected with peristaltic pump with SBR anaerobic ammonia oxidation reactors；SBR anaerobic ammonia oxidation reactors top be provided with mechanical stirring device and
Exhaust outlet, the top of exhaust outlet is connected with alkali lye bottle, gas flowmeter.SBR anaerobic ammonia oxidation reactors are set from top to bottom
Water intaking valve, sampling valve, draining valve.Temperature sensor is provided with reactor, temperature control heating band is with outward, be connected with temperature control box.
The matching of SBR anaerobic ammonia oxidation reactors is provided with DO instrument, ORP instrument and pH instrument
Add glycine betaine using said apparatus investigation influences for a long time on the Anaerobic ammonium oxidation system for being subjected to salinity shock, and it is special
Levy is to comprise the following steps：
The startup of SBR anaerobic ammonia oxidation process, device includes the Anammox sbr reactor device of sealing, its anaerobism ammonia oxygen
Change sludge and take from an Anammox UASB reactor for stable operation；SBR water inlets are synthetic wastewater, by addition
NaNO2(NH4)2SO4Control NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32, control the temperature of reactor to be by heating tape
30~35 DEG C, control DO for 0~0.1mg/L, inlet flow-patterm is by being added dropwise NaOH/chlorination stabilized hydrogen 7.0~8.5；Water inlet
4~8h of anoxia stirring, stirs after terminating, 0.5~2h of quiescent setting afterwards, and precipitation discharges supernatant after terminating, and draining ratio is 25
~50%；Initial start stage NH4 +- N and NO2 -The concentration of-N is controlled to 60~70mg/L, continuous culture to water outlet NH4 +- N and
NO2 -When-N concentration is below 20mg/L, water inlet NH is improved4 +- N and NO2 -- N concentration, until water inlet NH4 +- N concentration be 180~
220mg/L, NO2 -- N concentration is according to NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32 prepare, and complete Anammox SBR anti-
Answer the startup of device；
The Anammox sbr reactor device that will have been successfully started up is used to process brine waste, and volatility suspended sludge is dense
Degree VSS maintains 6~9g/L；Water inlet NH4 +- N concentration is 180~220mg/L, by adding (NH4)2SO4And NaNO2Control NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32；By adding a certain amount of glycine betaine, Anammox sbr reactor device is maintained
Interior beet alkali concn is 0.1~5mmol/L；Heating tape controls temperature of reactor for 30~35 DEG C, controls DO for 0~0.1mg/L,
Inlet flow-patterm is by being added dropwise NaOH/HCl stabilizations 7.0~8.5；4~8h of anoxia stirring after water inlet, after stirring terminates, quiescent setting
0.5~2h, precipitation discharges supernatant after terminating, and draining ratio is 25~50%.
It is of the invention to cause that anaerobic ammonia oxidation process is tackling salinity load punching high as additive by using glycine betaine
When hitting the method for fast quick-recovery efficient stable operation compared with prior art, with following advantages:
(1) method of the present invention using exogenous betaine is added, is experimentally confirmed, and the method can effectively shorten anaerobism
The time of ammoxidation sludge activation recovering under the conditions of salinity high, improve nitrogen removal rate (NRR) and nitrogen removal rate.
(2) compared to the method to being diluted, constructed this method avoid more massive sewage disposal is built
Thing, so as to save capital expenditure and operating cost, simplifies handling process, while also avoid the huge waste of water resource.
(3) compared to simple domestication anaerobic ammonium oxidation sludge treatment high salinity waste water, the method effectively shortens anaerobism ammonia
The time of oxidized sludge domestication, time cost is saved.
(4) it is to improve conventional micro- by adding salt-durable microbe or halophilic microorganism compared to application biological reinforcing technology
Disposal ability of the biota under hypersaline environment, the method has preferably stability when salinity fluctuation is tackled, because beet
The cost of alkali is relatively low, and raw material is easy to get, and greatlys save processing cost.
Brief description of the drawings：
Fig. 1 is to investigate to add SBR schematic device of the glycine betaine on the long-term influence of Anaerobic ammonium oxidation system.
In Fig. 1：1- storage tanks；2- intake pumps；3- water intaking valves；4-SBR anaerobic ammonia oxidation reactors；5- mechanical agitations are filled
Put；6- heating tapes；7- temperature control boxs；8- temperature sensors；9-DO instrument；10-pH instrument；11-ORP instrument；12- draining valves；13- is sampled
Valve；14- exhaust outlets；15- alkali lye bottle；16- gas flowmeters；
Fig. 2 is the design sketch of the Anaerobic ammonium oxidation system influence for a long time for adding glycine betaine to being subjected to salinity shock.
Specific embodiment：
The present invention is further detailed in conjunction with drawings and Examples：
As shown in figure 1, the device is by raw water box 1, SBR anaerobic ammonia oxidation reactors 4 are in series.Raw water box 1 pass through into
Water pipe and peristaltic pump 2 are connected with SBR anaerobic ammonia oxidation reactors 4；The top of SBR anaerobic ammonia oxidation reactors 4 is provided with machinery and stirs
Device 5 and exhaust outlet 14 are mixed, the top of exhaust outlet 14 is connected with alkali lye bottle 15, gas flowmeter 16, further afterwards real
The aerogenesis that SBR anaerobic ammonia oxidation reactors can be collected by gas flowmeter is tested, gas componant situation is analyzed.SBR anaerobism ammonia
Oxidation reactor 4 sets water intaking valve 3, sampling valve 13, draining valve 12 from top to bottom.Temperature sensor 8 is provided with reactor, outward
Temperature control heating band 6 is with, is connected with temperature control box 7.SBR anaerobic ammonia oxidation reactors matching be provided with DO instrument 9, ORP instrument 10 and
PH instrument 11.
Raw water enters SBR anaerobic ammonia oxidation reactors 4 by peristaltic pump 2 by raw water box 1 from water inlet 3；Water inlet 10min,
Then mechanical stirring device 5 starts stirring, during the course of the reaction by heating tape controlling reaction temperature stabilization at 30~35 DEG C, together
When note DO concentration, pH value and ORP value in monitoring reactor, anoxia stirring 5h after water inlet end, quiescent setting 1h, precipitation terminates
Afterwards, supernatant is discharged by draining valve 12, draining ratio is 40%.
Wherein raw water box volume is 20L, and SBR anaerobic ammonia oxidation reactors internal diameter is 19cm, and external diameter is 20cm, 30cm high,
Dischargeable capacity is 6L.
The startup of SBR anaerobic ammonia oxidation process：
One sealing Anammox sbr reactor device (50L), its anaerobic ammonium oxidation sludge take from one it is steady in a long-term
The Anammox UASB reactors of operation.SBR water inlets are synthetic wastewater, by adding (NH4)2SO4And NaNO2Control NH4 +-N
And NO2 -- N mol ratios are 1:1~1:1.32, temperature of reactor is controlled for 30~35 DEG C by heating tape, control DO be 0~
0.1mg/L, inlet flow-patterm is by being added dropwise NaOH/HCl stabilizations 7.0~8.5.Anoxia stirring 5h after water inlet, quiescent setting 1h, precipitation
Supernatant is discharged after end, draining ratio is 40%.Initial start stage NH4 +- N and NO2 -The concentration of-N is controlled to 60~70mg/
L, continuous culture to water outlet NH4 +- N and NO2 -When-N concentration is below 20mg/L, according to NH4 +- N and NO2 -- N mol ratios are 1:1~
1:1.32 come improve water inlet NH4 +- N and NO2 -- N concentration, until improving water inlet NH4 +- N concentration is 180~220mg/L, NO2 -- N is dense
Degree is according to NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32 prepare, and by the operation of four months, complete Anammox
Start.
Sealing SBR (6L) using two identicals is used to investigate the long-term influence of glycine betaine.Seed sludge is taken from and has been stablized
The Anammox sbr reactor device of operation, VSS maintains 7.5g/L.Two SBR water inlets are identical synthetic wastewater NH4 +-N
Concentration is 180~220mg/L, NO2 -- N concentration is according to NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32 prepare, one of them
1mmol/L glycine betaines are added, another, without any compatible material, is designated as R1 and R2 respectively as control group.R1 and
The method of operation of R2 is anoxia stirring 5h, quiescent setting 1h after water inlet, and precipitation discharges supernatant after terminating, and draining ratio is
40%.Run 210 days under conditions of salinity is 30g/L.Sludge is cleaned three with synthetic wastewater before every phase experiments start
The secondary medium so as to maintain stabilization, by adding a certain amount of glycine betaine, the beet alkali concn in holding R1 reactors is
1mmol/L。
Each stage is measured by sampling NH4 +-N、NO2 --N、NO3 -- N concentration and VSS, calculate NRR, TN clearances.By Fig. 2
A () understands, tests the incipient stage, due to the salinity shock by 30g/L, significant decline occurs in the NRR in R1 and R2, with
Afterwards as anaerobic ammonium oxidation sludge is gradually recovered to the adaptation of saline environment.However, the recovery time of R1 is 78 days, and R2
Recovery time is 177 days, and the former is shorter than the latter 2.27 times.From Fig. 2 (a), at the 78th day, the NRR of R1 and R2 distinguished
It is 2.11kgN/m3/ d and 1.14kgN/m3/ d, 84.3% He is respectively from the TN clearances of Fig. 2 (b), R1 and R2
61.6%, 7.68g/L and 6.13g/L are respectively from the VSS of Fig. 2 (c), R1 and R2.
According to this study test result indicate that:It is sweet compared with Anaerobic ammonium oxidation system is tamed merely without glycine betaine
Adding for dish alkali substantially shortens the anaerobic ammonia oxidation process reply salinity shock load domestication time, effectively increase NRR and
TN clearances, shorten the recovery time of VSS.
Claims (1)
1. the method for alleviating Anaerobic ammonium oxidation system salinity shock as additive by the use of glycine betaine, Anaerobic ammonium oxidation system dress
Put by raw water box (1), SBR anaerobic ammonia oxidation reactors (4) are in series；Raw water box (1) by water inlet pipe and peristaltic pump (2) with
SBR anaerobic ammonia oxidation reactors (4) are connected；SBR anaerobic ammonia oxidation reactors (4) top be provided with mechanical stirring device (5) and
Exhaust outlet (14), the top of exhaust outlet (14) is connected with alkali lye bottle (15), gas flowmeter (16)；SBR Anammoxs are anti-
Answer device (4) that water intaking valve (3), sampling valve (13), draining valve (12) are set from top to bottom；Temperature sensor is provided with reactor
(8) temperature control heating band (6), is with outward, is connected with temperature control box (7)；SBR anaerobic ammonia oxidation reactors matching be provided with DO instrument (9),
ORP instrument (10) and pH instrument (11)；
It is characterised in that it includes following steps:
The startup of SBR anaerobic ammonia oxidation process, device includes the Anammox sbr reactor device of sealing, and its Anammox is dirty
Mud takes from an Anammox UASB reactor for stable operation；SBR water inlets are synthetic wastewater, by adding NaNO2With
(NH4)2SO4Control NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32, it is 30~35 to control temperature of reactor by heating tape
DEG C, control DO for 0~0.1mg/L, inlet flow-patterm is by being added dropwise NaOH/chlorination stabilized hydrogen 7.0~8.5；Anoxic after water inlet
4~8h of stirring, after stirring terminates, 0.5~2h of quiescent setting, precipitation discharges supernatant after terminating, and draining ratio is 25~50%；
Initial start stage NH4 +- N and NO2 -The concentration of-N is controlled to 60~70mg/L, continuous culture to water outlet NH4 +- N and NO2 -- N concentration
When being below 20mg/L, water inlet NH is improved4 +- N and NO2 -- N concentration, until water inlet NH4 +- N concentration is 180~220mg/L, NO2 --
N concentration is according to NH4 +- N and NO2 -- N mol ratios are 1:1~1:1.32 prepare, and complete the startup of Anammox sbr reactor device；
The Anammox sbr reactor device that will have been successfully started up is used to process brine waste, volatility suspended sludge concentration VSS
Maintain 6~9g/L；Water inlet NH4 +- N concentration is 180~220mg/L, by adding (NH4)2SO4And NaNO2Control NH4 +- N and
NO2 -- N mol ratios are 1:1~1:1.32；By adding a certain amount of glycine betaine, beet in Anammox sbr reactor device is maintained
Alkali concn is 0.1~5mmol/L；Heating tape controls temperature of reactor for 30~35 DEG C, controls DO for 0~0.1mg/L, inlet flow-patterm
By the way that NaOH/HCl stabilizations are added dropwise 7.0~8.5；4~8h of anoxia stirring after water inlet, after stirring terminates, quiescent setting 0.5~
2h, precipitation discharges supernatant after terminating, and draining ratio is 25~50%.
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| CN106745698A (en) * | 2016-11-24 | 2017-05-31 | 西南交通大学 | A kind of method of aerobic treatment high-salt wastewater under low temperature |
| CN106966496B (en) * | 2017-04-28 | 2020-09-29 | 青岛大学 | Reinforcer and method for high-salt low-temperature wastewater treatment |
| CN108557997A (en) * | 2018-04-04 | 2018-09-21 | 大连理工大学 | A kind of preparation of sludge lysate and its application in high-salt wastewater Anaerobic Treatment |
| CN109081432A (en) * | 2018-07-25 | 2018-12-25 | 杭州师范大学 | The method for improving anaerobic ammonia oxidation reactor processing high temperature ammonia-containing water nitrogen removal performance |
| CN109160602A (en) * | 2018-09-04 | 2019-01-08 | 知合环境（北京）有限责任公司 | Glycine betaine is alleviating low ph value to the application in the active inhibition of anaerobic ammonium oxidation sludge |
| CN109160600A (en) * | 2018-09-04 | 2019-01-08 | 知合环境（北京）有限责任公司 | Glycine betaine is alleviating high concentration free ammonia to the application in the active inhibition of anaerobic ammonium oxidation sludge |
| CN109160601A (en) * | 2018-09-04 | 2019-01-08 | 知合环境（北京）有限责任公司 | Glycine betaine is alleviating the free nitrous acid of high concentration to the application in the active inhibition of anaerobic ammonium oxidation sludge |
| CN109970216B (en) * | 2019-04-26 | 2020-10-27 | 西安交通大学 | Culture method for promoting anaerobic ammonium oxidation sludge granulation by PVA-based gel beads |
| CN114426335B (en) * | 2020-10-29 | 2023-07-04 | 中国石油化工股份有限公司 | Co-enrichment method of nitrifying bacteria and denitrifying phosphorus accumulating bacteria |
| CN114426332B (en) * | 2020-10-29 | 2023-07-28 | 中国石油化工股份有限公司 | Method for rapidly starting SBR system to realize denitrification and dephosphorization |
| CN112504910B (en) * | 2020-11-03 | 2023-02-07 | 上海应用技术大学 | Evaluation device and evaluation method for anaerobic biochemical effect of wastewater |
| CN114684916B (en) * | 2020-12-30 | 2023-07-04 | 中国石油化工股份有限公司 | Sewage denitrification and dephosphorization method |
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| CN102276059B (en) * | 2011-05-24 | 2013-04-24 | 杭州师范大学 | Application of betaine for maintaining normal temperature stable operation of anammox system |
| CN103214092B (en) * | 2013-05-09 | 2018-05-08 | 中国科学院生态环境研究中心 | A kind of biological denitrification apparatus |
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