CN106365307A - Magnetic nano-silicon-based aerobic granular sludge and culture method and application thereof - Google Patents
Magnetic nano-silicon-based aerobic granular sludge and culture method and application thereof Download PDFInfo
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- CN106365307A CN106365307A CN201610985393.5A CN201610985393A CN106365307A CN 106365307 A CN106365307 A CN 106365307A CN 201610985393 A CN201610985393 A CN 201610985393A CN 106365307 A CN106365307 A CN 106365307A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1205—Particular type of activated sludge processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses magnetic nano-silicon-based aerobic granular sludge and a culture method and application thereof. The magnetic nano-silicon-based aerobic granular sludge contains magnetic nanospheres Fe3O4/SiO2. The culture method of the magnetic nano-silicon-based aerobic granular sludge includes the following step that the magnetic nanospheres Fe3O4/SiO2 are put into an active sludge system to form the magnetic nano-silicon-based aerobic granular sludge, and the magnetic nano-silicon-based aerobic granular sludge is used for wastewater treatment. The magnetic nano-silicon-based aerobic granular sludge has the advantages that formation is quick, the wastewater denitrification and dephosphorization capacity is high, magnetic nanometer materials in excess sludge are recycled conveniently, and long-time stable operation of the aerobic granular sludge is improved.
Description
Technical field
The invention belongs to technical field of waste water processing, more particularly, to a kind of magnetic Nano silicon substrate aerobic particle mud and its training
Foster methods and applications.
Background technology
Aerobic particle mud is cell itself immobilization particle spontaneously forming under aerobic condition, due to itself and cotton-shaped dirt
Mud is compared, and has that settling property is good, sludge concentration is high it is easy to solid-liquid separation, is easy to improve sewage treating efficiency, reduces at sewage
The advantages of reason cost, become the focus that sewage disposal circle scholars study in recent years.Aerobic particle mud technique is therefore also recognized
For being one of most promising dirty water living creature processing technique on our times.But aerobic particle mud quick particle
And its stable operation always limits the maximum bottleneck of its practical application.Some researchs show, some inert carriers can in recent years
Using " nucleation " material being formed as aerobic particle mud well；These nucleation carriers have good surface property, and have
Effect increases its capacity of resisting impact load, so as to increase the runnability steady in a long-term of aerobic particle mud.Wherein, nanometer Magnet
Powder (fe3o4) it is exactly a kind of good nucleation carrier.Nanometer magnetic iron powder (fe is loaded in activated Sludge System3o4), can not only improve
Sludge organism activity, moreover it is possible to the secretion of induction extracellular polymeric (eps), promotes sludge coagulating, beneficial to granular sludge.Meanwhile,
Suitable magnetics effect can balance the growth of microorganism and death in mud, and effectively suppresses sludge bulking, improves its stability.
Especially, the excellent magnetic characteristic of magnetic Nano material makes it just be can reach recovery, be repeated by externally-applied magnetic field in excess sludge
Use, this neither changes the component of mud, is easy to recycling again.But, unmodified magnetic nanoparticle fe3o4In water
In easily there is chemical change and reuniting effect so as to the application in sewage treatment area is restricted, and by magnetic material fe3o4
It is coated on formation magnetic silicon-based nano ball (fe in nano silicon spheres3o4/sio2) it is a kind of effectively change fe3o4Bad dispersibility effective
Approach.Therefore, the present invention is based on the ultimate principle of aerobic particle mud " nucleation hypothesis " and " micro- biological effect of magnetic field ", and from
Externally-applied magnetic field can be separated recycling angle and be considered to magnetic material, add magnetic nano-balls in activated Sludge System
fe3o4/sio2To accelerate granular sludge and its stable operation characteristic as main purpose.
Content of the invention
The invention provides a kind of magnetic Nano silicon substrate aerobic particle mud is it is intended to solve, unmodified magnetic Nano
Grain fe3o4Easily there is chemical change and reuniting effect in water so as to the problem that is restricted of application in sewage treatment area.
The present invention is achieved in that a kind of magnetic Nano silicon substrate aerobic particle mud, and described magnetic Nano silicon substrate is aerobic
Magnetic nano-balls fe is contained in granule sludge3o4/sio2.
Another object of the present invention is to providing a kind of cultural method of described magnetic Nano silicon substrate aerobic particle mud, institute
The cultural method stating magnetic Nano silicon substrate aerobic particle mud comprises the following steps:
Step one, magnetic nano-balls fe in sequencing batch activated sludge reactor (sbr)3o4/sio2It is added to activity dirt
In mud system；In described activated sludge reactor, the volume of the ordinary activated sludge of inoculation is the body of described activated sludge reactor
Long-pending 40%～60%；Nanosphere dosage is 0.3g/l～1.0g/l.
Step 2, forms magnetic Nano silicon substrate aerobic particle mud, and processes waste water.
Further, described magnetic nano-balls fe3o4/sio2Preparation method comprise the following steps:
Step one, by 1.0gfe3o4Nanosphere is diluted in the mixed of 20ml distilled water, 60ml dehydrated alcohol and 1.5ml strong aqua ammonia
Close in liquid；
Step 2, then through supersonic vibration 3h in thermostatic water bath, Deca 0.45ml tetraethyl orthosilicate simultaneously continues magnetic force and stirs
Mix 12h, Magnet separates；
Step 3, with absolute ethanol washing 3 times, is dried and simultaneously dries, draw magnetic nano-balls fe3o4/sio2.
Another object of the present invention is to providing at a kind of waste water using described magnetic Nano silicon substrate aerobic particle mud
Reason system.
The present invention is by magnetic material fe3o4It is coated on formation magnetic silicon-based nano ball (fe in nano silicon spheres3o4/sio2), tool
There is following good characteristic: (1) good physical and chemical performance: fe3o4/sio2Primary partical size is little, specific surface area big, surface
Atomic number is many, surface energy and surface tension greatly and have quantum size effect, bulk effect, skin effect and macroscopic quantum tunnel
Channel effect etc..(2) dispersibility: sio2Condensation reaction gained is occurred by presoma in preparation process, forms network structure, system is handed over
Connection, there is certain hydrophobicity, and thus studied scholar when polymolecularity magnetic nanoparticle is prepared using microemulsion method
Use as modifying agent.(3) suitable magnetic performance.
The present invention is by fe3o4/sio2" nucleation " carrier being formed as aerobic particle mud, has following advantage: (1) can lead to
Cross magnetic force be good for, the effect such as magnetic force, Lorentz force and mangneto cavity effect, be greatly facilitated that mud gathers through magnetic, adsorption is enriched to
Its surface, beneficial to the slow biological retention of biological speed and attachment, it is to avoid because resistance to mass tranfer causes interior nuclear disruption；(2) good micro-
Biological effect of magnetic field, can induce the richness of the flcos producing bacteria group promoting extracellular polymeric (eps) to secrete, accelerate its mud granule
Change；(3) suitable magnetics effect can also balance the growth of microorganism and death in mud, and effectively suppresses sludge bulking, improves
Its stability；(4) this kind of magnetic Nano material can be reclaimed under additional magnetic field condition, repeat and utilize.
Embodiments provide a kind of culture of magnetic Nano silicon substrate aerobic particle mud and its application, main purpose
It is to accelerate the quick formation of aerobic particle mud, improve the removal ability of its denitrogenation of waste water dephosphorization, be easy to magnetic in excess sludge
Nano material reclaims and strengthens aerobic particle mud and runs steadily in the long term.
Brief description
Fig. 1 is the cultural method flow chart of magnetic Nano silicon substrate aerobic particle mud provided in an embodiment of the present invention.
Fig. 2 is that in reactor provided in an embodiment of the present invention, svi value changes over curve synoptic diagram.
Fig. 3 is tn clearance change curve schematic diagram in each reactor provided in an embodiment of the present invention.
Fig. 4 is tp clearance change curve schematic diagram in reactor provided in an embodiment of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
Below in conjunction with the accompanying drawings the application principle of the present invention is explained in detail.
As shown in figure 1, the preparation method of magnetic nano-balls provided in an embodiment of the present invention comprises the following steps:
S101: magnetic nano-balls fe3o4/sio2It is added in activated Sludge System；
S102: form magnetic Nano silicon substrate aerobic particle mud, and process waste water.
With reference to contrast experiment, the application effect of the present invention is explained in detail.
1st, magnetic nano-balls fe3o4Preparation
Fe is prepared using chemical coprecipitation3o4Nanosphere.Concrete grammar: by 0.02molfecl3·6h2O and
0.01molfecl2·4h2O is dissolved in 100ml distilled water, is subsequently adding in three neck round bottom (250ml), at 90 DEG C, n2
(fe generating is prevented under atmosphere3o4It is converted into fe2o3) stirring 1h, being slowly added to 10ml strong aqua ammonia and adjusting ph is 8.5～10, cold
But to room temperature, Magnet uses distilled water cyclic washing after separating.
2nd, magnetic nano-balls fe3o4/sio2Preparation
Concrete grammar: by 1.0gfe3o4Nanosphere is diluted in 20ml distilled water, 60ml dehydrated alcohol and 1.5ml strong aqua ammonia
In mixed liquor, then through supersonic vibration 3h in thermostatic water bath, it is slowly added dropwise 0.45ml teos (tetraethyl orthosilicate) and continues magnetic
Power stirs 12h, and Magnet separates, and with absolute ethanol washing 3 times, is dried and simultaneously dries, draw sample.
3rd, nanosphere sio2Preparation
1.02gctab (cetyl trimethylammonium bromide) is dissolved in 480ml distilled water, adds the 2mol/l of 3.5ml
Naoh solution, after 80 DEG C of oil baths stirring 0.5h, Deca 5mlteos (tetraethyl orthosilicate), continue stirring 24h at 80 DEG C, after
Hydrothermal treatment consists 48h at 100 DEG C, filtering and washing, it is dried overnight at 100 DEG C, draw sample.
4th, experimental provision and service condition
Reaction unit: carry out in sequencing batch activated sludge reactor (sbr)；The reaction temperature of described reactor be 15 DEG C～
30 DEG C, dissolved oxygen do >=3.0mg/l.Described reactor is sequencing batch operation mode, circulates 2～3 cycles, each cycle daily
For 480min～720min, wherein, the flooding time in each cycle is 5min～10min, aeration time be 240min～
700min, the sedimentation time is 1min～10min, and remaining time is idle.The common work of inoculation in described activated sludge reactor
The volume of property mud is the 40%～60% of the volume of described activated sludge reactor；Nanosphere dosage be 0.3g/l～
1.0g/l.
Inoculation of activated-sludge used by experiment: take from double-current air harbor sewage treatment plant, sludge volume index svi is
202.15ml/g, sludge concentration mlss is 4279mg/l.
4 identical sbr reactors do parallel test, and dischargeable capacity is 1l, and wherein 1 is not add the general of any sample
As controlled trial, remaining 3 nano material dosage is 0.5g/l to logical activated sludge, for ease of mutually comparing, 4 is filled
Put numbering, 1#Device is the blank control group not adding any sample, 2#Device adds sio2Nanosphere, 3#Device adds fe3o4
Nanosphere, 4#The fe adding3o4/sio2Nanosphere.
5th, implement contrast
(1) granulating aspect
In system operation process, with digit microscope, the form of mud in each reactor is observed.In reality
Test when carrying out 20d, can be observed 1#Reactor mud flocculent structure is compared with consolidation, but no substantially granular sledge is formed；2#Reactor
It can be found that the change of obvious mud, partly define particle diameter and be about the macroscopic granule sludge of 0.3～1.0mm, it is dirty
Mud structural integrity, full closely knit, granular sludge degree substantially, is because sio2Nanosphere has good dispersion in the liquid phase
Property and stability, and surface has higher surface energy and larger specific surface area, thus there is powerful absorption to make to mud
With changing the original loose structure of mud so as to form preferable granule sludge；3#Reactor can be seen least a portion of
The formation of grain mud, but Distribution of sludge is uneven, this is because fe3o4Though magnetic nano-balls have the adsorptivity stronger to mud,
Assemble tendency because it is interparticle, easily reunite after synthesis, cause it not reach with mud and sufficiently mix, only one small part
Granular sludge；4#In reactor, most of mud can be observed visually and granulate, Dominant particle mud particle diameter distribution exists
0.3～1.0mm, through sio2Fe after cladding3o4Magnetic nano-balls with the raising of its dispersibility, its mud its granulate degree
Also it is better than exposed fe3o4Magnetic nano-balls.
(2) sludge settling property
Svi value is an important indicator judging sludge settling property, is the important ginseng judging system operation situation quality
Number, its svi value is lower, illustrates that system settling property is better.As seen from Figure 2, in the mud of four reactors of initial reaction stage
All in 200ml/g, this is because the floc sludge of initial vaccination is loosely organized, settleability is poor for svi value, but is as reacting
Carrying out, the svi value of four systemses is in downward trend, this is because under conditions of reactor operational excellence, system sludge
Flocculent structure make moderate progress, sludge settling property increases.The mud average svi value of blank control group 1# reactor is more than
Its excess-three reactor svi value, demonstrates that nanosphere is less due to particle diameter, has larger specific surface area, easily with zoogloea
Combine, increase the proportion of mud flco, improve the settling property of mud；Mud svi value changes in 2# and 4# reactor
Larger, in the reactor stable operation later stage, its svi value is maintained in 35ml/g substantially, this and most of aerobic particle mud svi
It is worth what the situation for 20～70ml/g matched.The mud svi value of 3# reactor is slightly above the mud svi value of 4# reactor, this
It is due to fe3o4There is magnetic attracting force and Van der Waals force between magnetic nano-balls particle, being easy between particle reunite, thus leading to
Its mix with activated sludge uneven, incomplete to sludge absorption, cause its settling property be slightly below 4# reactor.Thus may be used
See, by sio2Parcel improve fe3o4The dispersibility of magnetic nano-balls and its stability, thus relatively improve mud
Settling property.
(3) denitrogenation dephosphorizing aspect
Reactor to the clearance of tn as shown in figure 3, in the case that water inlet tn is about 43.39～50.28mg/l, experiment
Period 1# and 2# reactor are little to the average removal rate difference of tn, and sio is described2Nanosphere to add the removal to tn no obvious
Effect.3# and 4# reactor is significantly improved compared with matched group 1# reactor to the removal of tn.3# reactor is put down to waste water tn
All clearances have reached 56.95% about；Improve 11.73% compared with 1# reactor；4# reactor reaches to the average removal rate of tn
To 61.74% about, improve 16.52% compared with 1# reactor.Illustrate magnetic nanoparticle add the removal to tn have bright
The aobvious effect promoting.Wherein, in 4# reactor, tn average removal rate improves 4.4% than 3# reactor, and this is also by modified magnetic
The raising of property nano-particle dispersibility and stability brings.
Reactor is as shown in Figure 4 to the change curve of tp clearance.As shown in Figure 4, intake as 3.42～3.91mg/ in tp
In the case of l, 4 reactors all have the trend extending and being incremented by with run time, wherein 1# reactor and 2# to tp clearance
In reactor, tp clearance is equally matched, and the clearance compared to matched group 1# reactor tp for the 3# and 4# reactor has certain proposing
Rise: 3# reactor tp average removal rate has reached 57.5%, improves 8.67% compared to 1# reactor；4# reactor tp is average
Clearance has reached 60.5%, improves 11.69% compared to 1# reactor.Adding also to tp's of magnetic nanoparticle is described
Remove and create certain positive role.Therefore, magnetic nanoparticle removes work improvement in tn as previously mentioned in addition,
Can rationally speculate, this is because the distinctive magnetic biological effect of magnetic nanoparticle, the unsaturated activity of the coordination that its surface exposes
Site is many, possesses excellent catalysis activity.On the one hand, under the catalytic action of magnetic nanoparticle, beneficial to phosphorous acid substance
Catalyzed conversion；Another aspect magnetic nanoparticle utilizes its larger specific surface area, active adsorption phosphate, reduces it
Content.In 4# reactor, tp average removal rate improves 3.02% than 3# reactor, can speculate that modified magnetic nano-particle divides
Scattered property and stability-enhanced its catalysis activity simultaneously there has also been a certain degree of improvement.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (4)
1. a kind of magnetic Nano silicon substrate aerobic particle mud is it is characterised in that in described magnetic Nano silicon substrate aerobic particle mud
Containing magnetic nano-balls fe3o4/sio2.
2. a kind of cultural method of magnetic Nano silicon substrate aerobic particle mud as claimed in claim 1 is it is characterised in that described magnetic
The cultural method of the nano silicon-based aerobic particle mud of property comprises the following steps:
Step one, magnetic nano-balls fe in sequencing batch activated sludge reactor3o4/sio2It is added in activated Sludge System；
In described activated sludge reactor, the volume of the ordinary activated sludge of inoculation is the 40% of the volume of described activated sludge reactor
～60%；Nanosphere dosage is 0.3g/l～1.0g/l；
Step 2, forms magnetic Nano silicon substrate aerobic particle mud, and processes waste water.
3. the cultural method of magnetic Nano silicon substrate aerobic particle mud as claimed in claim 2 is it is characterised in that described magnetic
Nanosphere fe3o4/sio2Preparation method comprise the following steps:
Step one, by 1.0gfe3o4Nanosphere is diluted in the mixed liquor of 20ml distilled water, 60ml dehydrated alcohol and 1.5ml strong aqua ammonia
In；
Step 2, then through supersonic vibration 3h in thermostatic water bath, Deca 0.45ml tetraethyl orthosilicate simultaneously continues magnetic agitation
12h, Magnet separates；
Step 3, with absolute ethanol washing 3 times, is dried and simultaneously dries, draw magnetic nano-balls fe3o4/sio2.
4. the Waste Water Treatment of magnetic Nano silicon substrate aerobic particle mud described in a kind of utilization claim 1.
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Cited By (4)
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| CN107235552A (en) * | 2017-07-21 | 2017-10-10 | 山东大学 | A kind of method for applying nanometer magnet to promote cotton-shaped active sludge granulation |
| CN109485145A (en) * | 2018-12-28 | 2019-03-19 | 大连海事大学 | The coupling integrated reinforcing phosphorus-containing wastewater processing system of magnetization load activated sludge and its processing method |
| CN112624327A (en) * | 2020-12-18 | 2021-04-09 | 中国农业大学 | Method for promoting formation of anaerobic granular sludge |
| CN112794437A (en) * | 2020-12-30 | 2021-05-14 | 山东大学 | Method for strengthening remediation of polycyclic aromatic hydrocarbon polluted water body by modifying aerobic granular sludge through cyclodextrin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107235552A (en) * | 2017-07-21 | 2017-10-10 | 山东大学 | A kind of method for applying nanometer magnet to promote cotton-shaped active sludge granulation |
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| CN112794437A (en) * | 2020-12-30 | 2021-05-14 | 山东大学 | Method for strengthening remediation of polycyclic aromatic hydrocarbon polluted water body by modifying aerobic granular sludge through cyclodextrin |
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