CN101186909A - Embedding immobilization method for anaerobic ammoxidation mixed culture - Google Patents
Embedding immobilization method for anaerobic ammoxidation mixed culture Download PDFInfo
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- CN101186909A CN101186909A CNA2007100325319A CN200710032531A CN101186909A CN 101186909 A CN101186909 A CN 101186909A CN A2007100325319 A CNA2007100325319 A CN A2007100325319A CN 200710032531 A CN200710032531 A CN 200710032531A CN 101186909 A CN101186909 A CN 101186909A
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Abstract
The invention discloses an entrapping immobilization method of mixed anaerobic ammonium oxidation culture, which comprises the steps of obtaining embedding medium, mixing the embedding medium and sludge, obtaining immobilized anaerobic ammonium oxidation beads, activating the immobilized anaerobic ammonium oxidation beads, and the like. The obtaining of the embedding medium is to weigh polyvinyl alcohol and sodium alginate to be made into solution, according to the mass percent, the concentration of the polyvinyl alcohol is 6%-10wt% and the concentration of the sodium alginate is 1%-2wt%, and the polyvinyl alcohol and the sodium alginate are well stirred to make into mixed embedding medium. The method is simple in technique, simple in operation and low in costs. The entrapping of immobilized ANAMMOX mixed culture can be successful, the method can design an anaerobic ammonia oxidation reactor which is highly effective and specific in action, and the anaerobic ammonia oxidation reactor and a lead nitrosation reactor can be combined to form a high-efficiency stable biological denitrification system, which is adaptable for commercial manufacture and can bring about perfect economic and environmental benefits.
Description
Technical field
The present invention relates to environmental engineering, water pollution control and restoration of the ecosystem engineering field, particularly a kind of realization of immobilization anaerobic ammonium oxidation process.
Background technology
Nineteen ninety, the Kluyver Biotechnology Experiment chamber of Dutch Delft polytechnical university has been found the Anammox phenomenon first, and becomes the research focus of whole world water treatment field very soon.-denitrification biological denitrogenation method nitrated with tradition compared, and anaerobic ammonia oxidation process has the following advantages: anaerobic ammonia oxidizing bacteria is an autotrophic bacteria, need not to add organism as electron donor, but both cost savings can prevent secondary pollution again; In Anammox reaction, only ammonia oxidation need be become nitrite, the tradition of comparing is nitrated-denitrification process, oxygen-consumption descends 62.5%, therefore greatly reduces the oxygen supply energy consumption; Tradition is nitrated-need to add the soda acid medicament in the denitrification process, and the Anammox reaction is nearly neutral reaction, and the bio-acidification amount is very low, in therefore can saving and the medicament expense; Because the anaerobic ammonia oxidizing bacteria poor growth so sludge yield is few, can be saved the sludge treatment disposal costs greatly.The Anammox technology can effectively overcome the shortcoming of traditional biological denitrification process, therefore has the excellent development application prospect in the wastewater biological denitrificaion field.
But existing achievement shows that it is the complicated microorganisms symbiosis system that ANAMMOX bacterium, anerobe, amphimicrobe and aerobic bacteria are formed that ANAMMOX mixes the training thing, and just has activity under high cell concentration.The accumulation of ANAMMOX living microorganism biomass is very slow, and yield coefficient is low, and activity is subject to oxygen quenching, poor growth and difficult the cultivation.As seen, how obtaining the mixed training of q.s ANAMMOX thing is the major technique bottleneck of realizing and keep stable anaerobic ammonium oxidation process, thereby concerning new and effective Anammox biological denitrificaion, ANAMMOX mixes the training thing and just had huge technology and commercial value.Meanwhile, in the reactor operational process, keeping ANAMMOX mud not run off, is the important techniques key equally.For the harsh anaerobic ammonium oxidation process of operational conditions, if adopt common activated sludge process technique of backflow to keep its biomass, to cause ANANMMOX to mix the destruction of training thing and to the impact of reactor condition, and will make valuable ANAMMOX mix the training logistics to lose.Particularly in the anaerobism peace oxidising process of organic waste water, heterotrophic bacterium grows faster than autotrophic bacteria, and the ANAMMOX bacterium of autotrophy can be eliminated because of the inferior position in the energy utilization, even if adopt the also unavoidable sludge loss of ASBR reactor.
Summary of the invention
In order to solve the weak point that above-mentioned prior art exists, the objective of the invention is to utilize immobilized microorganism technique, make microorganism have higher density in FX, alleviate or eliminate the loss of the mixed training of ANAMMOX thing biomass, improve speed of response, be convenient to cultivate the superior microorganism population simultaneously, improve the stability for the treatment of processes, reduce or eliminate the embedding immobilization method for anaerobic ammoxidation mixed culture of the generation of side reaction.
In order to achieve the above object, the present invention realizes by following scheme:
A kind of embedding immobilization method for anaerobic ammoxidation mixed culture, in may further comprise the steps and processing condition:
(1) obtaining of embedding medium:, weighing polyvinyl alcohol and sodium alginate are made solution, according to the mass percent meter, the concentration 6%～10wt% of polyvinyl alcohol, the concentration of sodium alginate is 1%～2wt%, stirs, and makes the mixing embedding medium;
(2) embedding medium mixes with mud: it is centrifugal that Anammox mud is through pH that 6～8 phosphoric acid buffer cleans the back, mixes with embedding medium; In mass fraction, the blending ratio of embedding medium and mud is 1～2: 1;
(3) obtaining of immobilization Anammox bead: the mixed solution of mud and embedding medium is dropwise added 4 excessive～6wt%CaCl
2Solution can being fixed Anammox bead after crosslinked 8～24 hours under the sealing freezing conditions; It is standby to clean back refrigeration;
(4) activation of immobilization Anammox bead: before disposing of sewage, immobilized spherule needs activation culture 5～8 days earlier.
Described immobilization Anammox bead particle diameter is 3～5mm.
Described immobilized spherule activation culture is meant in 25～35 ℃ of temperature ranges, adopts target waste water to criticize formula and cultivates 5～10 days, makes the activity of immobilized microorganism fully be recovered and tame.
The present invention prepares the mixing solutions of polyvinyl alcohol (PVA) and sodium alginate (SA) as embedding medium with concentration according to a certain percentage, it is centrifugal that Anammox mud is cleaned the back through phosphoric acid buffer, make it to mix with embedding medium, with peristaltic pump mixed solution is dropwise added cross-linking agent solution, under given conditions crosslinked being fixed Anammox bead.It is standby that immobilized spherule cleans back refrigeration.Before disposing of sewage, immobilized spherule needs 1 all left and right sides time of activation culture earlier.Nitrite concentration must not be higher than 280mg/L in the handled sewage, otherwise inhibited to the anaerobic ammoxidation mixed culture thing.
Action principle of the present invention is: PVA and SA have high strength, good stability and to advantage such as biological nontoxic is harmless, it is one of embedded material that is most widely used, but PVA is the poorest to the balling-up effect that ANAMMOX mixes the embedded immobilization of training thing, has very serious adhesion phenomenon.A large amount of wetting ability hydroxyl in the PVA molecule, has certain water-swelling, crosslinked insufficient, these have all influenced the intensity of PVA bead, in the PVA system, introduce a spot of SA, some hydrophilic hydroxyl groups wherein and the combination of SA molecule, water-swelling and the adhesion phenomenon of PVA have been reduced, in addition, the hydroxyl in the PVA molecule has automatic cohesion tendency, thereby the PVA viscosity in aqueous solution can change along with the time, after the cooling of PVA solution, and after first room temperature lower seal deposits 24h, mix with microorganism again and splash into cross-linking agent solution, the refrigeration after the shaping particles can further improve the particulate performance.Microorganism live in these two kinds of macromolecular carriers formed mesh-structured in, can not only effectively prevent to run off, and the local strictly anaerobic environment of easier formation, favourable and the growth of anaerobic ammoxidation mixed culture thing have guaranteed the bio-denitrifying sewage efficient of stability and high efficiency.
The present invention compared with prior art, have following advantage and effect: technology is simple, easy and simple to handle, cheap, embedded immobilization ANAMMOX mixes the success of training thing, can flexible design go out to act on single-minded anaerobic ammonia oxidation reactor efficiently, with the biological denitrification system of preposition nitrosation reaction device composition efficient stable, be suitable for suitability for industrialized production, can obtain good economy, environmental benefit.The immobilization Anammox bead that obtains does not have marked inflation, feels like jelly in strong acid and strong base and high salinity solution, disintegration, has good physical stability and physical strength.
Embodiment
Below in conjunction with embodiment the present invention is done further concrete description, but embodiments of the present invention are not limited thereto.
Embodiment 1:
Utilize immobilization anaerobic ammoxidation mixed culture thing, under batch formula condition, handle nitrogenous effluent.Detailed process is: the mixing solutions of preparation 8wt% polyvinyl alcohol (PVA) and 2wt% sodium alginate (SA) is as embedding medium, again with Anammox mud according to 2: 1 ratio mixings (it is centrifugal that Anammox mud is through pH that 7.0 phosphoric acid buffer cleans the back), above-mentioned mixed solution is added drop-wise to the CaCl of 4wt% through No. 9 injection needless with peristaltic pump
2Solution (CaCl
2Liquor capacity is more than 3 times of embedding medium and mud mixed volume) as linking agent, the rapid moulding of bead, the bead particle diameter is between 3～5mm, and bead was collected in the sealing triangular flask, guarantees in the bottle anaerobic environment fully, in 4 ℃ of refrigerators crosslinked 12 hours.Crosslinking time helps embedding medium and linking agent full cross-linked fully, improves the stability and the physical strength (change stirrer 1500 and stir the breakage rate of 8 hours beads less than 2%) of bead.After crosslinked the finishing, clean bead three times with clear water, 4 ℃ of refrigerations are standby.Must get an amount of immobilized spherule through activation culture before using, add target waste water, in 30 ℃ of shaking tables, cultivate about 1 week, help the recovery of microorganism active in the bead, during progressively shorten hydraulic detention time (foreshortening to 36 hours) from 72 hours.
Above-mentioned activation bead is added target waste water, and the formula of criticizing under the anaerobic environment is cultivated.Wherein sewage ammonia nitrogen load and nitrite load are respectively 0.15kg/m
3.d with 0.19 kg/m
3.d, the reaction times is between 35 hours, sedimentation time 30 minutes.Water outlet monitoring result: chemical oxygen demand COD
CrClearance reaches 98.2%; Ammonia nitrogen NH
3-N is at 2.2mg/L, and its clearance reaches 97.6%, nitrite nitrogen NO
2-N is below 0.53mg/L, and its clearance reaches 99%.Has extraordinary application prospect.
Embodiment 2:
Utilize immobilization anaerobic ammoxidation mixed culture thing, under the cultured continuously condition, handle nitrogenous effluent.Detailed process is: the mixing solutions of preparation 10wt%PVA and 2wt%SA is as embedding medium, according to 7: 1 ratio mixings, again with Anammox mud according to 1: 1 ratio mixing (it is centrifugal that Anammox mud is through pH that 6.0 phosphoric acid buffer cleans the back), be added drop-wise to the CaCl of 6wt%
2Solution (CaCl
2Liquor capacity is more than 3 times of embedding medium and mud mixed volume) as linking agent, the rapid moulding of bead, the bead particle diameter is between 3～5mm, and bead was collected in the sealing triangular flask, guarantees in the bottle anaerobic environment fully, in 4 ℃ of refrigerators crosslinked 8 hours.Crosslinking time helps embedding medium and linking agent full cross-linked fully, improves the stability and the physical strength (change stirrer 1500 and stir the breakage rate of 8 hours beads less than 2%) of bead.After crosslinked the finishing, clean bead three times with clear water, 4 ℃ of refrigerations are standby.Must get an amount of immobilized spherule through activation culture before using, add target waste water, in 30 ℃ of shaking tables, cultivate 8 days, help the recovery of microorganism active in the bead, during progressively shorten hydraulic detention time (foreshortening to 10 hours) from 36 hours.
Above-mentioned activation bead is added target waste water, carry out cultured continuously under the anaerobic environment.Wherein sewage ammonia nitrogen load and nitrite load are respectively 0.20kg/m
3.d with 0.26 kg/m
3.d, hydraulic detention time is between 10 hours.In experiment, change simultaneously processing condition such as pH, temperature, load, the processing condition of Anammox reaction after the test immobilization.The water outlet monitoring result: chemical oxygen demand COD Cr clearance reaches 84.6%; Ammonia nitrogen NH
3-N clearance reaches 90.1%, nitrite nitrogen NO
2-N reaches 94.7% at clearance.Has extraordinary Nitrogen removal effect.Experiment of process conditions shows, immobilized anaerobic ammonium oxidation process and not immobilization compare, have tangible anti-load impact ability, simultaneously to the tolerance range increase of pH (6～8.5) and temperature (15～37).Demonstrate good prospects for application.
Embodiment 3
Utilize immobilization anaerobic ammoxidation mixed culture thing, under batch formula condition, handle nitrogenous effluent.Detailed process is: the mixing solutions of preparation 8wt%PVA and 1wt%SA is as embedding medium, again with Anammox mud according to 1.2: 1 ratio mixings (it is centrifugal that Anammox mud is through pH that 8.0 phosphoric acid buffer cleans the back), above-mentioned mixed solution is added drop-wise to the CaCl of 5wt% through No. 9 injection needless with peristaltic pump
2Solution (volume is more than 3 times of embedding medium and mud mixed volume) is as linking agent, the rapid moulding of bead, and the bead particle diameter is between 3～5mm, and bead was collected in the sealing triangular flask, guarantees in the bottle anaerobic environment fully, in 4 ℃ of refrigerators crosslinked 24 hours.Crosslinking time helps embedding medium and linking agent full cross-linked fully, improves the stability and the physical strength (change stirrer 1500 and stir the breakage rate of 8 hours beads less than 2%) of bead.After crosslinked the finishing, clean bead three times with clear water, 4 ℃ of refrigerations are standby.Must get an amount of immobilized spherule through activation culture before using, add target waste water, in 30 ℃ of shaking tables, cultivate 7 days, help the recovery of microorganism active in the bead, during progressively shorten hydraulic detention time (foreshortening to 24 hours) from 72 hours.
Above-mentioned activation bead is added target waste water, carry out sequence batch (under the anaerobic environment and cultivate.Wherein sewage ammonia nitrogen load and nitrite load are respectively 0.16kg/m
3.d and 0.21kg/m
3.d, hydraulic detention time is between 24 hours.In experiment, change simultaneously substrate concn, the test substrate concn to immobilization after the influence of Anammox reaction.The water outlet monitoring result: chemical oxygen demand COD Cr clearance reaches 97.6%; Ammonia nitrogen NH
3-N clearance reaches 99.1%, nitrite nitrogen NO
2-N reaches 98.7% at clearance.Has extraordinary Nitrogen removal effect.The substrate concn test shows ammonia nitrogen NH
3-N and nitrite nitrogen NO
2The ratio of-N is best at 1: 1.30 left and right sides reaction effect, simultaneously, and nitrite nitrogen NO
2The concentration of-N surpasses 280mg/L, otherwise inhibited reaction normally carries out.
Embodiment 4
Utilize immobilization anaerobic ammoxidation mixed culture thing, under batch formula condition, handle nitrogenous effluent.Detailed process is: the mixing solutions of preparation 6wt%PVA and 2wt%SA is as embedding medium, again with Anammox mud according to 1.5: 1 ratio mixings (it is centrifugal that Anammox mud is through pH that 7.0 phosphoric acid buffer cleans the back), above-mentioned mixed solution is added drop-wise to 6% CaCl with peristaltic pump through No. 9 injection needless
2Solution (CaCl
2Liquor capacity is more than 3 times of embedding medium and mud mixed volume) as linking agent, the rapid moulding of bead, the bead particle diameter is between 3～5mm, and bead was collected in the sealing triangular flask, guarantees in the bottle anaerobic environment fully, in 4 ℃ of refrigerators crosslinked 10 hours.Crosslinking time helps embedding medium and linking agent full cross-linked fully, improves the stability and the physical strength (change stirrer 1500 and stir the breakage rate of 8 hours beads less than 2%) of bead.After crosslinked the finishing, clean bead three times with clear water, 4 ℃ of refrigerations are standby.Must get an amount of immobilized spherule through activation culture before using, add target waste water, in 30 ℃ of shaking tables, cultivate 10 days, help the recovery of microorganism active in the bead, during progressively shorten hydraulic detention time (foreshortening to 12 hours) from 72 hours.
Above-mentioned activation bead is added target waste water, carry out sequence batch (under the anaerobic environment and cultivate.Wherein sewage ammonia nitrogen load and nitrite load are respectively 0.10kg/m
3.d and 0.13kg/m
3.d, hydraulic detention time is between 12 hours.Simultaneously in experiment, change pH, temperature, the processing condition of immobilization Anammox reaction under the test batch formula condition.The water outlet monitoring result: chemical oxygen demand COD Cr clearance reaches 93.6%; Ammonia nitrogen NH
3-N clearance reaches 97.1%, nitrite nitrogen NO
2-N reaches 98.8% at clearance.Has extraordinary Nitrogen removal effect.Experiment of process conditions shows, not immobilized Anammox mud optimum process condition is between pH (6.5～7.5) and temperature (25～30), and immobilized anaerobic ammoxidation mixed culture thing is under pH (6～8.5) and temperature (20～37) condition, the reaction efficiency influence is little, and tolerance range obviously increases.Demonstrate good prospects for application.
Claims (3)
1. embedding immobilization method for anaerobic ammoxidation mixed culture is characterized in that may further comprise the steps and processing condition:
(1) obtaining of embedding medium: weighing polyvinyl alcohol and sodium alginate, make solution, according to the mass percent meter, the concentration 6%～10wt% of polyvinyl alcohol, the concentration of sodium alginate is 1%～2wt%, stirs, and makes the mixing embedding medium;
(2) embedding medium mixes with mud: it is centrifugal that Anammox mud is through pH that 6～8 phosphoric acid buffer cleans the back, mixes with embedding medium; In mass fraction, the blending ratio of embedding medium and mud is 1～2: 1;
(3) obtaining of immobilization Anammox bead: the mixed solution of mud and embedding medium is dropwise added 4 excessive～6wt%CaCl
2Solution can being fixed Anammox bead after crosslinked 8～24 hours under the sealing freezing conditions; It is standby to clean back refrigeration;
(4) activation of immobilization Anammox bead: before disposing of sewage, immobilized spherule needs activation culture 5～8 days earlier.
2. embedding immobilization method for anaerobic ammoxidation mixed culture according to claim 1 is characterized in that described immobilization Anammox bead particle diameter is 3～5mm.
3. embedding immobilization method for anaerobic ammoxidation mixed culture according to claim 1, it is characterized in that described immobilized spherule activation culture is meant in 25～35 ℃ of temperature ranges, adopt target waste water to criticize formula and cultivated 5～10 days, make the activity of immobilized microorganism fully be recovered and tame.
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