CN105692893B - A kind of method for treating water that emerging organic matter micropollutants are removed based on sulfate reducing bacteria - Google Patents
A kind of method for treating water that emerging organic matter micropollutants are removed based on sulfate reducing bacteria Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to water-treatment technology fields, specifically disclose a kind of method for treating water that emerging organic matter micropollutants are removed based on sulfate reducing bacteria.The present invention is realized and organic matter is effectively removed by absorption and biodegradation of the SRB activated sludge to emerging organic micro-pollutants.SRB is as the function bacterium in reactor, using sulfate and other oxidation state sulphur compounds as the electron acceptor in its metabolic activity, using the gas chromatography including alkane, long chain fatty acids and aromatic compound as electron donor, sulfate reduction is completed, so as to achieve the purpose that removal organic polluter.The present invention uses SRB activated sludge processes, realize the removal of typical micro emerging organic micro-pollutants (Sulfamethoxazole) in sewage, low energy consumption for this method material consumption, sludge yield is low, it is the technical method that a kind of popularizing application prospect preferably removes micro emerging organic micro-pollutants in sewage without follow-up excess sludge treatment process.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to one kind is micro- based on the emerging organic matter of sulfate reducing bacteria removal
The method for treating water of pollutant.
Background technology
With economic growth and the development of pharmaceutical sector, drug is with personal care articles as a kind of emerging organic micro-pollutants
(Pharmaceuticals and Personal Care Products, PPCP) is widely used the mankind, strong to meet
Health and nursing demand and be applied to agriculture and animal husbandry enterprise for promote poultry growth and safeguard poultry health.PPCP types are varied, packet
Include various medicinal compounds, such as antibiotic, analgesics anti-inflammatory, central stimulant, antiepileptic, contraceptive etc. and daily
Nursing materials, such as personal skincare product and a series of chemical combination of cosmetics, paint scrubber, aromatic, opacifier, hair style finalization agent
Object.
PPCP types are various, widely used, in daily life PPCP it is a large amount of using and with daily life and
Activity has directly or indirectly been entered in water environment, and wherein sewage treatment plant is that it enters the important channel of environment, due to this
Pollutant persistence generally existing in water environment, damages to aquatic ecosystem and human health.
The processing method of removal PPCP comparative maturities is mainly physical chemistry processing method at present, such as：Activated carbon adsorption, chlorine
Disinfection, membrane filtration and advanced oxidation processes etc., but these processing method generally existing financial cost height and secondary pollution problems, from
Long term growth angle sees not to be best processing method.Traditional sewage treatment plant's technique also can not be by this kind of organic contamination
Object effectively removes, and therefore, should actively seek the new method for effectively removing PPCP in water body.
And microbial method can effectively remove PPCP by biological adsorption and biodegradation, be at present in contrast more
Environmental-friendly and low-cost method.
Invention content
To solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the invention is to provide a kind of based on sulfate
Reducing bacteria (abbreviation SRB) removes the method for treating water of emerging organic matter micropollutants (i.e. emerging organic micro-pollutants).
Another object of the present invention is to provide the application of above-mentioned method for treating water.
The object of the invention is achieved through the following technical solutions：
A kind of method for treating water that emerging organic micro-pollutants are removed based on SRB, is comprised the following steps：
(1) startup of reaction unit：
1. start the first stage：SRB activated sludge (i.e. sulfate reducing bacteria activity sludge) is added in into reactor, is adjusted
Reaction system pH, control system containing carbon source, nitrogen source, sulphur source, phosphorus source, contain the artificial synthesized of trace element in anaerobic environment
Waste water enters reactor and carries out sludge acclimatization (i.e. acclimated microorganism adapts to situation existing for sulphur source)；It is reactor start-up initial stage, whole
Adding without emerging organic micro-pollutants during a, main purpose is in the changing effect for improving sulphur, particularly sulfate reduction
Effect, time are 1.5~2 months, carbon in water inlet, nitrogen, phosphorus mass concentration ratio be 100:10:1；
2. start second stage：Work as SO4 2-Removal rate reach 85%, when reaching 90% to the removal rate of COD, addition is new
In emerging organic micro-pollutants to water inlet, into second stage is started, start second stage to anaerobism sulfate-reducing activity sludge
Further domestication culture is carried out, the time is 1.0~2 months；Wherein, containing carbon source, sulphur source, phosphorus source, nitrogen source, trace element and
Emerging organic micro-pollutants water inlet enters the i.e. beginning anaerobism sulfate reduction of reactor and goes the removal organic polluter stage, at this stage
Emerging organic micro-pollutants concentration ratio in water inlet is relatively low (for 100 μ g/L), carbon in water inlet, nitrogen, phosphorus mass concentration ratio be
100:10:1, to achieve the purpose that microbial acclimation, so as to complete the startup of reaction unit；
Start the first stage and the process condition of startup second stage is：Inlet and outlet water is controlled by peristaltic pump, water inlet
Flow Q is 2.6L/d, while is uniformly mixed muddy water by interior cycle, is inside circularly set as 5 Q, reaction temperature 20~35
DEG C, inlet flow-patterm is 6.9~7.1, hydraulic detention time 10h；
(2) microbial augmentation of emerging organic micro-pollutants is removed based on SRB activated sludge：
1. after start completion, water inlet keep carbon, nitrogen, phosphorus mass concentration ratio be 100:10:1, while add and emerging have
In machine micropollutants to water inlet, the concentration of emerging organic micro-pollutants is gradually increased by low concentration (by 500 in intaking at this stage
μ g/L are gradually increased to 2000 μ g/L), to strengthen removal of the SRB activated sludge to emerging organic micro-pollutants, by directly dropping
Solution or Co metabolism effect carry out sulfate reduction using the organic pollution of addition；1. process condition is step：Disengaging
Water is controlled by peristaltic pump, and flow of inlet water Q is 2.6L/d, while is uniformly mixed muddy water by interior cycle, and interior cycle is set
5 Q, 20~35 DEG C of reaction temperature are set to, inlet flow-patterm is 6.9~7.1, hydraulic detention time 10h；Emerging organic micro-pollutants increase
The concentration gradient added is：500 μ g/L, 1000 μ g/L, 1500 μ g/L, 2000 μ g/L are maintained two weeks under each concentration conditions；
2. the mass concentration ratio of water inlet holding carbon, nitrogen, phosphorus is 100:10:1, while add emerging organic micro-pollutants and arrive
In water inlet, a concentration of 1000 μ g/L into organic pollutants are maintained at this stage, hydraulic detention time are gradually shortened, with strong
Change and the sulfate reducing bacteria of degradable organic pollutant is come as major function microorganism with sulfate-reducing activity sludge；Work as SO4 2-
Removal rate be 85%, COD removal rate be 90%, when stablizing to the removal effect of organic pollution, complete dirty with SRB activity
Mud removes the strengthening process of the microorganism of removal organic polluter, so set up based on SRB activated sludge go water removal in it is emerging organic
The process for stabilizing environment of micropollutants；
2. process condition is step：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is gradually increased from 2.6L/d
Muddy water is uniformly mixed to 6.48L/d, while by interior cycle, is inside circularly set as 5 Q, 20~35 DEG C of reaction temperature, into
Water pH is 6.9~7.1, and hydraulic detention time is gradually shortened by 10h to 4h, often adjusts a hydraulic detention time and maintains two weeks again
Carry out variable adjustment；
(3) stable operation of waste water treatment system：
The waste water treatment system of stable operation is passed through using pending waste water as water inlet, removes carbon source, sulphur in pending waste water
Source and emerging organic micro-pollutants；
Step (3) process condition is：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is 4.32L/d, simultaneously
Be uniformly mixed muddy water by interior cycle, be inside circularly set as 6 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm for 6.9~
7.1, hydraulic detention time 6h, carbon in water inlet, nitrogen, phosphorus mass concentration ratio be 100:10:1.
Reactor described in step (1) is up flow type sulfate reduction anaerobic mud bed reactor (Sulfate
Reduction up-flow sludge bed abbreviation SRUSB), material is organic glass, by water-in and water-out system, reaction zone and
Internal circulation system forms, and the present apparatus is discharged using overflow, bottom water inlet.By sampling valve, probe tube, inlet bucket, out of the bucket, water inlet
Pump, water outlet pump, internal circulation pump, water inlet pipe, outlet pipe, inner circulating tube, inlet valve, ORP probes, pH probes, ORP hosts, pH master
Machine and reactor body composition.
Reactor reaction volume described in step (1) is preferably 1.08L, and artificial synthesized influent waste water is preferably 5L, water inlet
Entered by peristaltic pump with certain reacted device bottom of flow velocity, be discharged and excluded in a manner of overflow by outlet pipe through peristaltic pump；
SRB activated sludge feed postition is mixed for muddy water, dosage 300mL.
Carbon source is provided by sodium acetate in step (1) the artificial synthesized waste water, and sulphur source is provided by anhydrous sodium sulfate, phosphorus source by
K2HPO4And KH2PO4It provides, nitrogen source is by NH4Cl is provided, the trace element trace elements such as including Fe, Cu, Mn, Zn, Co, K, I；Institute
It is about 500mg/L, SO to state COD in artificial synthesized waste water4 2-- S concentration is about 275mg/L or so, P-HPO4 2-、H2PO4 -It is initial
Concentration is 5mg/L, N-NH4 +Initial concentration be 50mg/L；The artificial synthesized wastewater pH is preferably 7.0.
Step (1), (2), the emerging organic micro-pollutants described in (3) are Sulfamethoxazole (SMX).
SRB activated sludge concentrations are 17.59g MLSS/L, SRB activated sludge in reaction system described in step (1)
MLVSS/MLSS=0.81, COD:S=1.8；The reaction system pH hydrochloric acid and sodium hydroxide solution are adjusted, reaction system
PH is adjusted to 6.5~8.0.
Anaerobic environment N described in step (1)2The air being aerated in cleaning reaction system, with control system in anaerobism ring
Border, N2The time of aeration is subject to the air in cleaning reaction system, preferably 1~30min.
The hydraulic detention time that is gradually shortened described in step (2) refers to through the gradient with 10h, 8h, 6h, 4h come gradually
Shorten hydraulic detention time, hydraulic detention time is gradually shortened by 10h to 4h, a hydraulic detention time is often adjusted and maintains two
Week carries out variable adjustment again；2. concrete operations are step：Water inlet keep carbon, nitrogen, phosphorus mass concentration ratio be 100:10:1, together
In the emerging organic micro-pollutants to water inlet of Shi Tianjia, a concentration of 1000 μ g/L into organic pollutants are maintained at this stage,
Hydraulic detention time is gradually shortened by the gradient with 10h, 8h, 6h, 4h, a cycle is maintained two weeks under each variable.
Emerging a concentration of 100 μ g/L of organic micro-pollutants in pending waste water described in step (3).
The above-mentioned method for treating water that emerging organic micro-pollutants are removed based on SRB is given up in processing containing emerging organic micro-pollutants
Application in water.
The principle of the present invention：Sulfate reducing bacteria (Sulfate-Reducing Bacteria, SRB) is as anti-in system
The function bacterium in device is answered, using sulfate and other oxidation state sulphur compounds as the electron acceptor in its metabolic activity, with
Gas chromatography including alkane, long chain fatty acids and aromatic compound is electron donor, and it is anti-to complete sulfate reduction
Should, so as to achieve the purpose that removal organic polluter.The present invention passes through absorption of the SRB activated sludge to emerging organic micro-pollutants
And it is biodegradable, it realizes and organic matter is effectively removed.
Sulfate reduction：
100gCOD+150.2g SO4 2-+47.3g H2O→53.2g H2S+1.9gslugde+190.9g HCO3 -
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) using up flow type sulfate reduction anaerobic mud bed reactor (SRUSB), reaction process is anaerobism, and technique is transported
Row is simple and easy to operation.
(2) when starting reactor, the domestication of sulfate reducing bacteria sulphate reducing is first carried out stage by stage, then in sulphur also
Remove the domestication of emerging organic micro-pollutants on the basis of original to sulfate reducing bacteria, such domestication process ensure that the later stage with
Sulphur reduction removes the stability of emerging organic micro-pollutants effect.
(3) microorganism for removing emerging organic micro-pollutants using SRB activated sludge strengthen and be strengthened to organic
The process for stabilizing environment of the removal of pollutant.
(4) SRB activated sludge has preferable degradation capability to emerging organic micro-pollutants (Sulfamethoxazole) in the present invention,
To the Sulfamethoxazole of 1mg/L, in the short time (48h), removal rate reaches 33.2%, and specific removal rate is 3.0 μ g-SMX/g-
MLSS/h, and removal completely was realized in 6 days.
(5) present invention realizes typical micro emerging organic micro-pollutants (sulfanilamide (SN) in sewage using SRB activated sludge processes
Jia oxazoles) removal, low energy consumption for this method material consumption, and sludge yield is low, is a kind of popularization without follow-up excess sludge treatment process
Application prospect preferably removes the technical method of micro emerging organic micro-pollutants in sewage.
Description of the drawings
Fig. 1 is the structure diagram of SRUSB reactors of the present invention.
Fig. 2 is absorption and degradation distribution map of the SMX in SRB activated sludge.
Fig. 3 is interpretation of result figures of the different pH to the SMX influences removed.
Fig. 4 is interpretation of result figures of the different HRT to the SMX influences removed.
Fig. 5 is the interpretation of result of the influence to SMX removals under different SMX concentration loads.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Waste water described in the embodiment of the present invention is artificial synthetic wastewater, and component mainly has sulfamethoxazole
1) and micro member (Stock storing solutions are shown in Table for (Sulfamethoxazole, SMX), sodium sulphate, various nutrients
(2) Trace storing solutions, are shown in Table element；
Table 1 nutrient storing solution (Stock) component table
Micro- storing solution (Trace) component table of table 2
3 influent quality table of table
SRB activated sludge described in the embodiment of the present invention is derived from Hong Kong secondary sedimentation tank of sewage treatment work.Due to Hong Kong profit
With seawater toilet-flushing, thus sulfate concentration is higher in sanitary sewage, and there are abundant SRB in sludge.Primary stage of inoculation sludge is Huang
Brown, in bulky batt shape, MLVSS/MLSS=0.42.The sludge color transition black after the SRB enrichment cultures of two weeks
It is cotton-shaped, MLVSS/MLSS=0.61, using the sludge in this stage as the seed sludge of SRUSB reactors.
It is inoculated with post-reactor influent quality：Using artificial synthesized waste water, using glucose, sodium acetate as carbon source, COD is about
500mg/L or so；Anhydrous sodium sulfate is added as sulphur source, SO4 2-- S concentration is about 224mg/L or so；With K2HPO4And KH2PO4
As phosphorus source, NH4Cl is as nitrogen source, C：N：P=100:10:1；To prevent from being acidified at any time into water, stablize inlet flow-patterm, add carbon
Sour hydrogen sodium makes pH stable 7 or so；Simultaneously to meet the needs of microorganism growth process, be additionally added in synthetic wastewater Fe,
The trace elements such as Cu, Mn, Zn.Temperature is at 20~35 DEG C or so.
Embodiment 1 is based on the process for stabilizing ring that SRB (sulfate reducing bacteria) activated sludge removes emerging organic micro-pollutants
The foundation in border
(1) start reaction unit：
1. the initial sludge concentrations of 300mL are added in up flow type sulfate reduction anaerobic mud bed reactor (SRUSB) is
The muddy water mixed solution of the SRB activated sludge of 17.59g MLSS/L, by peristaltic pump by certain flow rate through water inlet pipe into reactor
Sludge acclimatization continuously is carried out into the artificial synthesized waste water of 5L, it is micro- to improve its simultaneously with environment existing for acclimated microorganism adaptation sulfate radical
Bioactivity；The artificial synthesized waste water contains carbon source, nitrogen source, sulphur source, phosphorus source and trace element, and the carbon source is by vinegar
Sour sodium provides；COD initial concentrations are 500mg/L in artificial synthesized waste water；The sulphur source is provided by sodium sulphate, artificial synthesized useless
SO in water4 2-The initial concentration of-S is about 275mg/L, and the phosphorus source is provided by dipotassium hydrogen phosphate and potassium dihydrogen phosphate；It is artificial to close
The P-HPO into waste water4 2-, H2PO4-Initial concentration be 5mg/L；The nitrogen source is provided by ammonium chloride, N- in artificial synthesized waste water
NH4 +Initial concentration be 50mg/L；The startup first stage of reactor to strengthen sulfate reduction, does not throw in whole process
Add emerging organic micro-pollutants；Process condition is：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is 2.6L/d, together
When by interior cycle be uniformly mixed muddy water, be inside circularly set as 5 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm for 6.9~
7.1, hydraulic detention time 10h.
2. start second stage：Work as SO4 2-Removal rate reach 85%, when reaching 95% to the removal rate of COD, addition is new
In emerging organic micro-pollutants to water inlet, into second stage is started, second stage is to be tamed and dociled on the basis of sulfate reduction
Change microorganism and remove emerging organic micro-pollutants, the mass concentration holding ratio constant (100 of carbon, nitrogen, phosphorus in stage water inlet:
10:1), in water inlet emerging organic micro-pollutants a concentration of 100 μ g/L, waste water connects by water inlet pipe through peristaltic pump with certain flow rate
It is continuous to enter in reactor, that is, start anaerobism sulfate reduction and go the removal organic polluter stage.Microorganism, which utilizes, at this stage adds
The carbon source and organic pollution entered carries out sulfate reduction, to achieve the purpose that microbial acclimation, so as to complete reaction unit
Start；Process condition is：Inlet and outlet water is controlled by peristaltic pump, flow of inlet water Q be 2.6L/d, while by it is interior cycle come
Muddy water is uniformly mixed, is inside circularly set as 5 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm is 6.9~7.1, during hydraulic retention
Between 10h, time first stage be 1.5~2 months, the second stage time be 1.0~2 months；
(2) microbial augmentation of emerging organic micro-pollutants is removed based on SRB activated sludge：
1. after start completion, water inlet keeps the ratio constant (100 of carbon, nitrogen, phosphorus:10:1) it, while in intaking adds emerging
Organic contamination source, to strengthen removal of the SRB activated sludge to emerging organic micro-pollutants；By directly degrade or Co metabolism act on
Sulfate reduction is carried out using the organic pollution of addition, the concentration into organic pollutants is gradually increased by 500 μ g/L
To 2000 μ g/L；Process condition is：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is 2.6L/d, while by interior
Cycle is uniformly mixed muddy water, is inside circularly set as 5 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm is 6.9~7.1, waterpower
Residence time 10h, the emerging increased concentration gradient of organic micro-pollutants are：500 μ g/L, 1000 μ g/L, 1500 μ g/L, 2000 μ
G/L is maintained two weeks under each concentration conditions；
2. a concentration of 1000 μ g/L into organic pollutants are maintained at this stage, by with the ladder of 10h, 8h, 6h, 4h
It spends that hydraulic detention time is gradually shortened, a cycle is maintained two weeks under each variable, to strengthen with sulfate-reducing activity dirt
The sulfate reducing bacteria that mud carrys out degradable organic pollutant becomes major function microorganism；Work as SO4 2-Removal rate be 85%, COD
Removal rate is 90%, when stablizing the removal effect of emerging organic micro-pollutants, completes to remove organic contamination with SRB activated sludge
The strengthening process of the microorganism of object, and then set up the process for stabilizing that emerging organic micro-pollutants are removed based on SRB activated sludge
Environment (waste water treatment system for setting up stable operation)；The process condition in this stage is：Inlet and outlet water passes through wriggling
It pumps to control, flow of inlet water Q is gradually increased to 6.48L/d, while be uniformly mixed muddy water by interior cycle from 2.6L/d, interior
Be circularly set as 5 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm is 6.9~7.1, hydraulic detention time by 10h be gradually shortened to
4h。
Up flow type sulfate reduction anaerobic mud bed reactor (SRUSB) described in embodiment is main in this technique
Processing unit, reactor body is made of organic glass, internal diameter 50mm, and total a height of 555mm, total dischargeable capacity is 1.08L.
Water inlet is prepared using manual simulation's mode, replaces to ensure that water quality does not have too big variation, and it is defeated by its to pass through peristaltic pump daily
Be sent in reactor with SRB activated sludge haptoreactions, be discharged in a manner of overflow from outlet pipe flow out.To make SRB activity dirty
Mud can be better mixed with sewage and contact, and improve mass transfer effect, and reactor is provided with internal circulation system, by internal circulation pump by portion
It separates water to flow back into reactor, simultaneous reactions device is connected to ORP and pH on-Line Monitor Devices.
Embodiment 2SRB activated sludge is to the cutting mechanisms of organic micro-pollutants emerging in water
(1) SRB tamed activated sludge is taken to be added separately in the serum bottle of 6 500mL from reactor, is added artificial
Water distribution (consistent with reactor) is diluted to graduation mark.Wherein 3 are tested for biodegradable, another 3 plus 0.1%NaN3For pressing down
Microbial activity processed, is subsequently used for adsorption experiment.0.5mL sulfamethoxazole storing solutions (100mg/ is added in into each serum bottle
L) cause the final concentration of 100 μ g/L of SMX in reaction system, be consistent with the sulfate reduction device of SANI techniques；
(2) it is 7.0 to adjust each reaction system pH respectively；Use N2The air being aerated in each reaction system of 1min removings,
Each system is controlled in anaerobic environment；Lid is tightened, and serum bottle is wrapped up to avoid degradation of the light to SMX with masking foil；
(3) under the conditions of 25 DEG C of room temperature, more preferable to mix muddy water in each reactor, each reaction system is kept stirring shape
State, wherein rotating speed are 230rpm, reaction time 6d；
(4) above-mentioned each reaction system takes respectively in 0,0.5,1.1.5,2,2.5,3,3.5,4,4.5,5,5.5,6d
The supernatant of 0.5mL is filled into the PTFE filters of 0.22um in the sample bottle of 2mL browns, is stored in 4 DEG C of refrigerators, and in
The same day tests and analyzes the variation of SMX contents with UPLC-DAD.
Fig. 2 is absorption of the SMX in SRB activated sludge and biodegradable variation.As it can be seen that SRB activated sludge removes SMX
Except mainly being realized by biodegradation, SRB activated sludge is weaker to the suction-operated of SMX.
Under 3 difference pH of embodiment, the method for treating water that emerging organic micro-pollutants are removed based on SRB activated sludge (is passed through
The waste water treatment system for the stable operation that embodiment 1 is established handle the waste water of different pH value)
Influences of the pH to reactor operational effect is inquired by adjusting reactor inlet flow-patterm, it is contemplated that the pH tolerances of SRB
Ranging from 5.5~9.0, the water inlet pH gradient of setting is 6.0,6.5,7.0,7.5,8.0,8.5,9.0, and influent quality is shown in Table 3,
He is set as service condition：HRT (hydraulic detention time) is 5h, interior cycle 6Q, a concentration of 100 μ g/L of SMX of intaking, each to intake
PH reactors operation 8d or so, periodically takes the supernatant of reactor, the sample of 2mL browns is filled into 0.22 μm of PTFE filters
It in bottle, is stored in 4 DEG C of refrigerators, and in the same day variation of UPLC-DAD detection and analysis SMX contents.
Fig. 3 is different pH to the interpretation of result figures of the SMX influences removed, as seen from the figure, with the variation of inlet flow-patterm,
The removal rate fluctuation of SMX is very big.When inlet flow-patterm is 6.0~7.0, the larger and removal rate of removal rate fluctuation of SMX is relatively low；Water inlet
When between 7.0~9.0, SMX removal rates have the tendency that gradually rising pH, illustrate that the activity of SRB enzymes is opposite in the range of this pH
It is higher；As pH higher, these drugs mainly exist in the form of hydrophobicity, can preferably be adsorbed in sludge to be conducive into one
Step is biodegradable.Since the reduction process of sulfate is along with the increase of basicity, pH is adjusted to 7, but with reaction in water inlet
Progress, the pH in reactor moves closer to 8, is ideal reaction environment, therefore the water inlet pH value of the present invention is preferably
7.0。
Under 4 difference HRT of embodiment, the method for treating water that emerging organic micro-pollutants are removed based on SRB activated sludge (is passed through
The waste water treatment system for the stable operation that embodiment 1 is established handles waste water under different HRT)
The influence of emerging pollutant effect is removed to SRB activated sludge to inquire into HRT, influent quality is shown in Table 3, adjusts simultaneously
HRT gradients are：5th, 6,7,8,9h, other service conditions：Inlet flow-patterm is 7.0, water inlet SMX a concentration of 100 μ g/L, interior cycle 6Q.
Each HRT operations 8d, periodically takes the supernatant of reactor, is filled into the sample bottle of 2mL browns with 0.22 μm of PTFE filters,
It is stored in 4 DEG C of refrigerators, and in the same day variation of UPLC-DAD detection and analysis SMX contents.At the same time period sampling measuring
Inlet and outlet water pH, ORP, sulfide, SO4 2-, the indexs such as TOC, SMX, and extract EPS, analyze the fortune of reactor under the conditions of different HRT
Row effect.
Fig. 4 show the situation of change of SMX in system under the conditions of different HRT.As seen from the figure, with the extension of HRT,
The removal rate of SMX and there is rising than removal amount.HRT extends to 9h by 5h, and removal rate increases to 50% by 23%, than
Removal amount increases to 9.25 μ g/gMLSSd by 7.52 μ g/gMLSSd, increases 18.7%.Analysis the reason is that due to
The extension of HRT increases SMX and the time of contact of microorganism in system, is conducive to biodegradation of the microorganism to SMX.Consider
The effective volume of reactor can be increased to long HRT, increase cost and improve cost, too short HRT is also due in reactor
The time of contact of microorganism and pollutant is insufficient, and the removal effect of the excessively high influence microbe of organic loading causes
Reactor outlet effect is deteriorated, therefore the preferred 6h of HRT in the present invention.
Under 5 difference SMX concentration loads of embodiment, the water process of emerging organic micro-pollutants is removed based on SRB activated sludge
Method (waste water treatment system for the stable operation established by embodiment 1 handle the waste water of different SMX concentration)
During reactor start-up, in water inlet the fluctuation of SMX concentration can fluctuate its removal rate, existing sewage disposal
The variation of emerging organic pollutant concentration can also make removal rate have larger difference in factory's water inlet, illustrate different influent load meetings
Influence the removal effect of this pollutant.Therefore, this research by adjust intake in SMX concentration study reactor in difference
Operational effect under SMX loads.Influent quality is shown in Table 3, in setting water inlet the concentration gradient of SMX be 5,25,75,100,150,
200 μ g/L, other service conditions：HRT is 6h, interior to recycle as 6Q, inlet flow-patterm 8.0.Likewise, each load gradient reactor
8d is run, the supernatant of reactor is periodically taken, is filled into the sample bottle of 2mL browns with the PTFE filters of 0.22um, is stored in 4
In DEG C refrigerator, and tested and analyzed with UPLC-DAD in the same day variation of SMX contents.
Fig. 5 is shown under different SMX loading condictions to the situation of change of SMX removal effects.It can be seen from the figure that with
The removal rate of the increase SMX of concentration is substantially reduced, and is then significantly increased than removal amount.Influent concentration is increased to 200 μ by 5 μ g/L
During g/L, removal rate falls below 27% from 100%, and 16.2 μ g/gMLSS are risen to by 1.4 μ g/gMLSSd than removal amount
D increases 91.4%.It can also be seen that SRUSB has preferable removal effect to the SMX of low concentration from experimental result,
And the residual concentration of SMX is relatively low in existing sanitary sewage, and it is mostly horizontal in ng/L, also only have a few μ g/L under higher concentration,
Therefore it can speculate that SRUSB has good removal effect to the SMX in sanitary sewage, ideally removal rate is reachable
100%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of method for treating water that emerging organic micro-pollutants are removed based on SRB, which is characterized in that comprise the following steps：
(1) startup of reaction unit：
Start the first stage：SRB activated sludge is added in into reactor, adjusts reaction system pH, control system in anaerobic environment,
Artificial synthesized waste water containing carbon source, sulphur source, phosphorus source, nitrogen source and trace element enters reactor and carries out sludge acclimatization, and the time is
1.5~2 months；
Start second stage：Work as SO4 2-Removal rate reach 85%, when reaching 90% to the removal rate of COD, addition it is emerging organic
In micropollutants to water inlet, make into a concentration of 100 μ g/L of emerging organic micro-pollutants in water, further acclimation sludge, time
It is 1.0~2 months；
Start the first stage and the process condition of startup second stage is：Inlet and outlet water is controlled by peristaltic pump, feed water flow
Amount Q is 2.6L/d, while is uniformly mixed muddy water by interior cycle, is inside circularly set as 5 Q, 20~35 DEG C of reaction temperature,
Inlet flow-patterm is 6.9~7.1, hydraulic detention time 10h, carbon in water inlet, nitrogen, phosphorus mass concentration ratio be 100:10:1；
(2) microbial augmentation of emerging organic micro-pollutants is removed based on SRB activated sludge：
1. after start completion, water inlet keep carbon, nitrogen, phosphorus mass concentration ratio be 100:10:1, while add emerging organic micro-
In pollutant to water inlet, emerging organic micro-pollutants are gradually increased to by the concentration gradient of setting by 500 μ g/L in making into water
2000μg/L；1. process condition is step：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is 2.6L/d, is led to simultaneously
Crossing interior cycle is uniformly mixed muddy water, is inside circularly set as 5 Q, and 20~35 DEG C of reaction temperature, inlet flow-patterm is 6.9~7.1,
Hydraulic detention time 10h；The emerging increased concentration gradient of organic micro-pollutants is：500 μ g/L, 1000 μ g/L, 1500 μ g/L,
2000 μ g/L are maintained two weeks under each concentration conditions；
2. the mass concentration ratio of water inlet holding carbon, nitrogen, phosphorus is 100:10:1, while add emerging organic micro-pollutants and make into water
A concentration of 1000 μ g/L of middle organic pollution, are gradually shortened hydraulic detention time, work as SO4 2-Removal rate for 85%, COD
Removal rate is for 90%, when stablizing to the removal effect of emerging organic micro-pollutants, it is established that is gone in water removal based on SRB activated sludge
The process for stabilizing environment of emerging organic micro-pollutants；2. process condition is step：Inlet and outlet water is controlled by peristaltic pump, into
Water flow Q is gradually increased to 6.48L/d from 2.6L/d, while by interior cycle be uniformly mixed muddy water, it is 5 to be inside circularly set
A Q, 20~35 DEG C of reaction temperature, inlet flow-patterm are 6.9~7.1, and hydraulic detention time is gradually shortened by 10h to 4h；
(3) stable operation of waste water treatment system：
The waste water treatment system of stable operation is passed through using pending waste water as water inlet, removes carbon source, sulphur source in pending waste water
And emerging organic micro-pollutants；
Step (3) process condition is：Inlet and outlet water is controlled by peristaltic pump, and flow of inlet water Q is 4.32L/d, is passed through simultaneously
Interior cycle is uniformly mixed muddy water, is inside circularly set as 6 Q, 20~35 DEG C of reaction temperature, inlet flow-patterm is 6.9~7.1, water
Power residence time 6h, carbon in water inlet, nitrogen, phosphorus mass concentration ratio be 100:10:1；Step (1), (2), emerging described in (3)
Organic micro-pollutants are Sulfamethoxazole.
2. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
Reactor described in step (1) is up flow type sulfate reduction anaerobic mud bed reactor.
3. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
Carbon source is provided by sodium acetate in step (1) the artificial synthesized waste water, and sulphur source is provided by anhydrous sodium sulfate, and phosphorus source is by K2HPO4With
KH2PO4It provides, nitrogen source is by NH4Cl is provided, and trace element includes Fe, Cu, Mn, Zn, Co, K and I；In the artificial synthesized waste water
COD is 500mg/L, SO4 2-- S a concentration of 275mg/L, P-HPO4 2-、H2PO4 -Initial concentration be 5mg/L, N-NH4 +It is initial
A concentration of 50mg/L；The artificial synthesized wastewater pH is 7.0.
4. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
SRB activated sludge concentrations are the MLVSS/MLSS of 17.59g MLSS/L, SRB activated sludge in reaction system described in step (1)
=0.81, COD:S=1.8；The reaction system pH hydrochloric acid and sodium hydroxide solution are adjusted, and reaction system pH is adjusted to
6.5~8.0.
5. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
Anaerobic environment N described in step (1)2The air being aerated in cleaning reaction system, with control system in anaerobic environment.
6. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
The hydraulic detention time that is gradually shortened described in step (2) refers to waterpower is gradually shortened by the gradient with 10h, 8h, 6h, 4h
Hydraulic detention time is gradually shortened by 10h to 4h, often adjusts a hydraulic detention time and maintain carry out again for two weeks by the residence time
Variable adjusts.
7. the method for treating water according to claim 1 that emerging organic micro-pollutants are removed based on SRB, which is characterized in that
Emerging a concentration of 100 μ g/L of organic micro-pollutants in pending waste water described in step (3).
8. the method for treating water that claim 1 to 7 any one of them removes emerging organic micro-pollutants based on SRB contains in processing
Application in emerging organic micro-pollutants waste water.
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| CN110078209B (en) * | 2019-05-16 | 2021-11-16 | 桂林电子科技大学 | Method for forming cadmium sulfur ore by reducing sulfate with microorganism |
| CN113716689B (en) * | 2021-08-11 | 2023-06-16 | 中国长江三峡集团有限公司 | Mixed nutrition type denitrification method based on sulfur reduction and sulfur autotrophic denitrification |
| CN113845217A (en) * | 2021-11-02 | 2021-12-28 | 中山大学 | Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement |
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| KR20000065415A (en) * | 1999-04-02 | 2000-11-15 | 윤덕용 | Biological Treatment Method of Wastewater Containing Heavy Metals |
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| CN1537814A (en) * | 2003-10-23 | 2004-10-20 | 哈尔滨工业大学 | Microorganism metabolism type regulate and control method, in sulphate waste water treatment |
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