A kind of anaerobic ammonium oxidizing bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier
Technical field
The present invention relates to water treatment field, particularly a kind of anaerobic ammonium oxidizing bacteria immobilization star biological active filling material preparations and applicatio based on mesh carrier.
Background technology:
Anammox technology (ANAMMOX) is biological denitrificaion approach the most economic known at present, and the research of Dutch Delft university Strous etc. shows, the bioprocesses comprising cell synthesis in anaerobic ammonium oxidation process can be expressed as formula (1)
NH
4 ++1.32NO
2‐+0.066HCO
3 ‐+0.13H
+→
1.02N
2+0.26NO
3‐+0.066CH
2O
0.5N
0.5+2.03H
2O(1)
As can be seen from the biological respinse feature of anaerobic ammonium oxidizing bacteria, ANAMMOX, compared with traditional nitration denitrification technology, has that working cost is low, oxygen requirement is low and do not need the advantages such as additional carbon.
Because the doubling time of anaerobic ammonium oxidizing bacteria is long, cell yield is lower, and (doubling time of generally acknowledging is 11d, and have the fastest doubling time of report also to reach 4.8d) biomass therefore in order to keep relative stability in reactor, the solid retention time that anaerobic ammonia oxidation reactor requires is relatively long., also find in the research of anaerobic ammonium oxidizing bacteria meanwhile, only at cell density higher than 10
10?10
11individual/mL time, anaerobic ammonia oxidizing bacteria just can show anaerobic ammonium oxidizing bacteria activity.This cell density characteristic of anaerobic ammonium oxidizing bacteria conforms to quorum sensing (Quorumsensing) phenomenon ubiquitous in bacterium.Quorum sensing is a kind of communication mechanism be prevalent between microorganism cells, and it has carrys out regulatory gene expression thus the function of control bacterial population behavior according to population density and surrounding environment change.Therefore, how to keep its cell density higher in the reactor and prevent valuable anaerobic ammonium oxidizing bacteria to run off from reactor having become the emphasis of current research.
Microorganism cells immobilization technology can increase substantially microorganism concn, microorganism is not easily run off, shortens the reactor start-up time, toxin immunity and acid and alkali-resistance, salt resistance ability obviously strengthen, the ecological dominance of energy purifying and creation characteristic bacterium, produce characteristic highly effective reaction, demonstrate good application prospect.The process for fixation that microorganism cells is conventional has absorption method, crosslinking and entrapping method.Wherein, conventional with entrapping method, be successfully used to microorganism cells embedding material have: polyvinyl alcohol, agar, K ?carrageenin, gelatin, sodium alginate, polyacrylamide, urethane etc.That above-mentioned embedded material has is good to microorganism nontoxicity, mass-transfer performance, not easily by biological decomposition, stable in properties, the feature such as physical strength is high, the life-span is long, price is low.
At present, traditional bacterium embedding method is combined at bacterium and embedded material, forms embedding body, such as microballoon, embedded block etc.This method is simple to operate, but limitation is large, cannot in the middle of ideal application to engineering reality.Experimental study shows, utilize the conventional carriers such as existing Raschig ring, Pall ring, cascade ring, suspension modified filler to combine obtained biological active filling material with embedding body by adherent fashion and all there is resistance to overturning difference, embedding body easily comes off, the problem such as cause that bacterium is run off.
For the problems referred to above, the anaerobic ammonium oxidizing bacteria immobilization star biological active filling material that a kind of resistance to overturning that we develop is good will be with a wide range of applications.
Summary of the invention:
The object of the invention is to develop a kind of anaerobic ammonium oxidizing bacteria immobilization star biological active filling material based on mesh carrier, present invention employs following technical scheme.
A kind of anaerobic ammonium oxidizing bacteria immobilization star biological active filling material based on mesh carrier, it is characterized in that: with polyethylene, polyvinyl chloride, polypropylene or these macromolecular materials of ABS resin are main, add massfraction be 5% ?10% polyvinyl alcohol (PVA) as water wetted material, the tridimensional network carrier of sheet shape is made by hot melt, length range be 0.5 ?3cm, width range be 0.5 ?3cm, the edge of the mesh carrier of some shapes is sticked together by hot melt extruded or bonding mode, make multi-form stellate reticulum carrier, in same stellate reticulum carrier, the tridimensional network carrier angle of adjacent two panels shape is identical, such as three, four, five, six mesh carriers adopt 120 ° respectively, 90 °, 72 °, 60 °, different sheet number angles is different, according to Ju Yi Xi Chun ?boric acid secondary crosslinking method, by mix anaerobic ammonium oxidizing bacteria concentrated solution polyvinyl alcohol solution (polyvinyl alcohol mass concentration be 8% ?10%, gained embedding liquid also can comprise calcium carbonate) be uniformly coated on stellate reticulum carrier surface, put into saturated boric acid solution 1 ?after 3h, regulate boric acid solution pH to 8 ?10, crosslinked 4 ?24h.Taken out, clean remained on surface material, obtain star biological active filling material.This anaerobic ammonium oxidizing bacteria biological active filling material proportion 0.90 ?between 1.10.
The string diameter of above-mentioned tridimensional network carrier is 1mm.Cancellated design makes anaerobic ammonium oxidizing bacteria embed body on the mesh carrier of sheet shape, forms millimetre-sized membrane structure.
A kind of anaerobic ammonium oxidizing bacteria immobilization star biological active filling material based on mesh carrier of the present invention is used for water treatment.
The beneficial effect of the anaerobic ammonium oxidizing bacteria immobilization star biological active filling material based on mesh carrier of the present invention is mainly reflected in:
1. cancellated design, anaerobic ammonium oxidizing bacteria is made to embed body by mesh shape rivet clasp structure integrally, bacterium embedding body difficult drop-off, makes the anaerobic ammonium oxidizing bacteria biological active filling material resistance to overturning that obtains good, is conducive to keeping higher anaerobic ammonium oxidizing bacteria concentration.
2. mesh carrier is designed to star, this structure can make to be in fluffy state all the time between Anammox biological active filling material, there will not be filler, because surperficial Anammox microbial film thickens, problem and the current short circuit problem of lumen blockage occurs, be beneficial to the transmission of nutraceutical matrix and the release of nitrogen.It is minimum that the bacterium embedding body that simultaneously also ensure that between anaerobic ammonium oxidizing bacteria biological active filling material fin is subject to extraneous frictional force, and the embedding body on each fin to be subject to extraneous tangential friction force less, ensure that anaerobic ammonium oxidizing bacteria is at the higher bacterial concentration of regional area, be beneficial to and improve biological active filling material processing efficiency, ensure its stable performance.
3. experimental study shows, be the carrier immobilized anaerobic ammonium oxidizing bacteria biological active filling material obtained with conventional filler, poor stability, in 2 days, embedded material almost all comes off, and the anaerobic ammonium oxidizing bacteria immobilization star biological active filling material resistance to overturning obtained with mesh carrier immobilization is good, the filler life-span is more than 3 years.
4. the anaerobic ammonium oxidizing bacteria immobilization star biological active filling material that immobilization is obtained, proportion 0.90 ?between 1.10, fluidized state can be presented in the reactor, be beneficial to mass transfer.
5. mesh carrier is main raw by polyethylene, polyvinyl chloride, polypropylene, ABS resin, with the addition of polyvinyl alcohol (PVA) as water wetted material, improve the wetting ability of carrier, add carrier and bacterium and embed the intensity that body bonds, improve overall stability.
6. Anammox biological active filling material due to the existence of mesh skeleton structure make bacterium embed body can implementation structure thickness less while do not lose again the variability of one-piece construction to water treatment running environment, less thickness can realize higher mass-transfer efficiency and bacterium embeds the higher utilization ratio of body, is beneficial to the mass transfer of nutraceutical matrix and the release of nitrogen.If make thickness like this with bacterium embedding body own material cannot realize good carrier performance in water technology processing unit.
7. immobilization anaerobic ammonium oxidizing bacteria biological active filling material bag bacterium amount is large, and can form anaerobic ammonium oxidizing bacteria flora advantage, processing efficiency is high.
8. the surface-area of anaerobic ammonium oxidizing bacteria biological active filling material is all useful area, avoids the waste of material.
Accompanying drawing explanation
Fig. 1 is star anaerobic ammonium oxidizing bacteria biological active filling material fin schematic diagram;
Fig. 2 be Fig. 1 Zhong Ⅰ ?I diagrammatic cross-section;
Fig. 3 be Fig. 1 Zhong Ⅱ ?II diagrammatic cross-section;
Fig. 4,5,6,7 is star anaerobic ammonium oxidizing bacteria biological active filling material schematic diagram.
1. twines in figure, 2. embed body
Embodiment
Below in conjunction with case study on implementation, the present invention is more specifically described, but embodiments of the present invention are not limited thereto.
1. the preparation of stellate reticulum carrier
Take polypropylene as main raw, add the polyvinyl alcohol (PVA) of massfraction 5%, system grows into 1.0cm, and wide is the sheet shape mesh carrier of 0.5cm, string diameter 1mm.By three sheet above shape carriers by hot melt, the stellate reticulum carrier of bonding formation angle 120 °.
2. the process of anaerobic ammonium oxidizing bacteria
Anaerobic ammonium oxidizing bacteria bacteria suspension after cultivating is carried out centrifugal concentrating, and obtaining bacterial concentration is 3.0 × 10
10the anaerobic ammonium oxidizing bacteria concentrated solution of individual/mL.
3. the acquisition of anaerobic ammonium oxidizing bacteria embedding liquid
Weighing polyvinyl alcohol 10.0g, high-temperature sterilization pot is put at 100 DEG C after adding 70ml ultrapure water, heating for dissolving 15min, put into high-temperature sterilization pot after taking-up stirs again and heat 5min at 100 DEG C, stir after taking-up and be cooled to 30 DEG C, by 70ml polyvinyl alcohol solution and the 30ml anaerobic ammonium oxidizing bacteria concentrated solution mixing prepared, and add 2.0g calcium carbonate, after stirring, make 100ml anaerobic ammonium oxidizing bacteria embedding liquid.
4. the combination of anaerobic ammonium oxidizing bacteria embedding liquid and stellate reticulum carrier
Anaerobic ammonium oxidizing bacteria is embedded liquid and be uniformly coated on mesh carrier surface, guarantee that stellate reticulum carrier surface is all covered evenly by bacterium embedding liquid.
5. the preparation of anaerobic ammonium oxidizing bacteria biological active filling material
The mesh carrier smearing embedding liquid in step (4) is put into saturated boric acid solution, it is made to be in submerged condition, leave standstill 3h, regulator solution pH to 9.0, standing 4h completes immobilization, cleaning, obtains anaerobic ammonium oxidizing bacteria biological active filling material, this anaerobic ammonium oxidizing bacteria biological active filling material proportion 0.94 ?between 1.03.
6. the application of anaerobic ammonium oxidizing bacteria biological active filling material activity
It is in the upward flow bio-reactor of 1L that above-mentioned Anammox biological active filling material is added to useful volume by reactor volume filling ratio 50%, and filler is in fluidized state under current drive, and is beneficial to the bubble of discharging and producing.Control water inlet water temperature (28 ± 2) DEG C, pH be 7.5 ?7.8, NH
4 +?N concentration at 100mg/L, NO
2 ??N concentration be 2h at 130mg/L, HRT.Water outlet monitoring result shows: reactor recovers anaerobic ammoxidation activity after running two weeks, after stable, and water outlet NH
4 +?N concentration be below 1.5mg/L, clearance is more than 98.5%, water outlet NO
2 ??N concentration be below 0.86mg/L, clearance is more than 99.3%.Reactor runs 1 year continuously, and Anammox biological active filling material embedding body serviceability rate is 94%, avoids the loss of anaerobic ammonium oxidizing bacteria, and comparatively traditional biological filter tank exhaust, mass transfer are good, and nitric efficiency is high, is beneficial to popularization.