CN110272890A - Complex microorganism carrier and preparation method and the application for having autotrophic denitrification function - Google Patents
Complex microorganism carrier and preparation method and the application for having autotrophic denitrification function Download PDFInfo
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Abstract
The present invention relates to a kind of complex microorganism carriers and the preparation method and application thereof for having autotrophic denitrification function, and the gel of aerobic activated sludge has been embedded at one layer of Anammox biofilm packing area load.Preparation method is to mix a certain amount of gel rubber material with water, after mixing, cooling, and the gel liquid with certain viscosity is made after a certain amount of activated sludge mixing sufficiently is added；A certain amount of filler for being attached to Anammox biomembrane is put into gel liquid obtained, is uniformly mixed；The area load filler of gel is taken out, a period of time is stood, removes extra gel under self gravitation effect；It is put into certain density crosslinked fluid and is crosslinked, take out filler later and extra crosslinked fluid is washed with water, obtain complex microorganism carrier.Invention utilizes Anammox technology of biological membrane and gel embedding technology, prepares a kind of complex microorganism carrier for having autotrophic denitrification function, can fast implement the synchronization short distance nitration anaerobic ammonium oxidation process of sanitary sewage.
Description
Technical field
The invention belongs to sewage treatment fields, are related to microorganism embedding techniques, especially one kind and have autotrophic denitrification function
Complex microorganism carrier preparation method and application, by Anammox biofilm carrier and activated sludge gel embedding
Method is fixed, and domestic sewage advanced denitrogenation is used for.
Background technique
Microorganism embedding techniques are one kind of immobilized microorganism technology, are limited intact cell using physics and chemical means
It makes or is positioned in certain space region, and it is made to keep certain biology catalytic activity, be current most widely used fixation
Change technology.Specific method is that gelatinous solid particle is made by crosslinked action in specific microorganism and embedding medium.The skill
The advantages of art is to make reactor biomass with higher and longer microorganism residence time, and gel has preferable object
Reason and chemical stability, safe growing environment can be provided for microorganism, has been widely used in sewage treatment, achieves very
Good effect.
In recent years, short distance nitration joint Anammox technology is generally considered as a kind of important of the following sewage treatment development
Technology, while also becoming the research hotspot in industry.But in current sanitary sewage disposal, due to C/N higher of intaking, water
The more low factor of temperature, realizes that the Anammox denitrification process of sanitary sewage is relatively difficult.Currently, there is related scholar to carry out one
A little correlative studys, patent CN108545830A pass through control on the basis of short distance nitration Anammox denitrification dephosphorization technique
The mode of sludge back flow quantity and long sludge age come promote sedimentation basin occur sludge fermentation, it is thin to ammoxidation using sludge fermentation object
The selectivity of bacterium and nitrite oxidizing bacteria strengthens the stability of short distance nitration.But the patent needs sludge reflux technique,
Energy consumption is increased to a certain extent, and this patent is not necessarily to sludge reflux.Patent CN106946352A is in integral anaerobic ammonia oxygen
Change in autotrophic denitrification biofilm reactor and set sponge filler, ammonia oxidation bacteria and anaerobic ammonia oxidizing bacteria are grown in the form of fixing film
In in Active biological filler, realizing synchronous short distance nitration Anammox, aeration quantity is reduced, making for additional carbon is reduced
Dosage saves operating cost, stable effluent quality can be made to reach country-level emission standard A.But the ammoxidation of the patent
Bacterium and anaerobic ammonia oxidizing bacteria biofilm mode are more traditional, are unable to accurately control the distribution of two kinds of microorganisms, and this patent utilizes gel
Embedding can carry out rapid biofilm, make two kinds of microbial profiles in different zones, do not interfere with each other, and cooperate with denitrogenation.
This patent and the method that the patent CN108285202A main distinction applied before me is gel load are different,
The method of gel layer thicknesses control is different.Plate membrane is to control gel layer thicknesses by control gel volume, and filler is
Gel layer thicknesses are controlled by control gel strength.
Summary of the invention
This patent synthesizes a kind of carrier for loading aerobic activated sludge and anaerobic ammonia oxidizing bacteria using microorganism embedding techniques,
One layer of gel for having embedded aerobic activated sludge is loaded again in the filler surface for having formed Anammox biomembrane.Due to making
With gel embedding, external nutrition substance is affected to inner transmission matter, needs type and concentration by controlling gel rubber material, guarantees
Internal anaerobic bacteria can touch the nitrite nitrogen of activated sludge generation and be perforated through the ammonia nitrogen come from outside.
The present invention solves its technical problem and is achieved through the following technical solutions:
A kind of complex microorganism carrier having autotrophic denitrification function, in Anammox biofilm packing area load one
Layer has embedded the gel of aerobic activated sludge.
Moreover, the preparation method of the complex microorganism carrier for having autotrophic denitrification function, steps are as follows:
(1) a certain amount of gel rubber material is mixed with water, after mixing at 80~100 DEG C, is cooled to 25~35 DEG C, adds
The gel liquid with certain viscosity is made after entering a certain amount of activated sludge mixing sufficiently；
(2) a certain amount of filler for being attached to Anammox biomembrane is put into gel liquid made from step (1),
It is uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) it is put into certain density crosslinked fluid and is crosslinked, take out filler later and extra crosslinked fluid is washed with water, obtain
To complex microorganism carrier.
Moreover, gel rubber material described in step (1) is the mixing of 2-7wt% polyvinyl alcohol and 0.5-2wt% sodium alginate
Object.
Moreover, the mass percentage of step (1) activated sludge is 4-10wt%.
Moreover, the filler biological amount that step (2) is attached to Anammox biomembrane is 5~10gTSS/L.
Moreover, crosslinked fluid component and mass percentage described in step (4) are as follows: sodium nitrate 20-50wt%；Calcium chloride 1-
2wt%；Surplus is water.
Moreover, step (4) carries out 10~15h of crosslinking for 3~6 DEG C in crosslinked fluid.
Moreover, the ratio of step (4) gel volume and crosslinked fluid volume is 1:5.
Application of the complex microorganism carrier in sewage treatment a kind of described in.
The advantages and benefits of the present invention are:
The invention can be realized rapid biofilm, shorten the starting time of reactor；The ammonia oxidizing bacteria of oxygen is needed to be distributed
In outer layer, the anaerobic ammonia oxidizing bacteria of anaerobism is distributed in inside, and two kinds of denitrification process do not interfere with each other, cooperate with denitrogenation, in sanitary sewage
The COD of high concentration is decomposed by external aerobic sludge, reduces its inhibition to anaerobic ammonia oxidizing bacteria；It can be by controlling gel
Concentration and dosage realize that the ratio control of two kinds of microorganisms is realized according to the amount of the aerobic sludge of water inlet C/N ratio allotment embedding
The accuracy controlling of denitrification process.
Detailed description of the invention
Fig. 1 is the picture of different gel embedding filtrates；
Fig. 2 is the ammonia nitrogen diffusion coefficient comparison diagram of different gel embedding filtrates；
Fig. 3 be different gel embedding filter material aeratings fall off after 24 hours quality versus figure；
Fig. 4 is that ammonium nitrogen and nitrate nitrogen change with time in suspended active sludge and Anammox biofilm system
Figure；
Fig. 5 is that ammonium nitrogen and nitrate nitrogen be at any time in the Anammox biofilm system for embed the load of activated sludge gel
Variation diagram.
Specific embodiment
The R&D process of patent to facilitate the understanding of the present invention, spy enumerates 2 embodiments and 5 comparative examples to this hair herein
Explanation is described in bright method and other methods.
Embodiment 1 (7wt% polyvinyl alcohol gel embeds filtrate-without microorganism)
Steps are as follows for a kind of preparation method of gel load filler:
(1) sodium alginate of the polyvinyl alcohol of 7wt% and 2wt% are mixed with 100mL water, after mixing at 90 DEG C,
It is cooled to 30 DEG C and the gel liquid with certain viscosity is made；
(2) 50 particulate filler beads are put into gel liquid made from step (1), are uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) 4 DEG C of fixed crosslinking 12h of progress chemistry, gel in the crosslinked fluid of 50wt% sodium nitrate and 2wt% calcium chloride are put into
The ratio of volume and crosslinked fluid volume is 1:5, takes out filler later and extra crosslinked fluid is washed with water, obtain complex carrier.
Comparative example 1 (5wt% polyvinyl alcohol gel embeds filtrate-without microorganism)
Steps are as follows for a kind of preparation method of gel load filler:
(1) sodium alginate of the polyvinyl alcohol of 5wt% and 2wt% are mixed with 100mL water, after mixing at 90 DEG C,
It is cooled to 30 DEG C and the gel liquid with certain viscosity is made；
(2) 50 particulate filler beads are put into gel liquid made from step (1), are uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) 4 DEG C of fixed crosslinking 12h of progress chemistry, gel in the crosslinked fluid of 50wt% sodium nitrate and 2wt% calcium chloride are put into
The ratio of volume and crosslinked fluid volume is 1:5, takes out filler later and extra crosslinked fluid is washed with water, obtain complex carrier.
Comparative example 2 (2wt% polyvinyl alcohol gel embeds filtrate-without microorganism)
Steps are as follows for a kind of preparation method of gel load filler:
(1) sodium alginate of the polyvinyl alcohol of 2wt% and 2wt% are mixed with 100mL water, after mixing at 90 DEG C,
It is cooled to 30 DEG C and the gel liquid with certain viscosity is made；
(2) 50 particulate filler beads are put into gel liquid made from step (1), are uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) 4 DEG C of fixed crosslinking 12h of progress chemistry, gel in the crosslinked fluid of 50wt% sodium nitrate and 2wt% calcium chloride are put into
The ratio of volume and crosslinked fluid volume is 1:5, takes out filler later and extra crosslinked fluid is washed with water, obtain complex carrier.
Comparative example 3 (polyacrylamide gel embeds filtrate-without microorganism)
Steps are as follows for a kind of preparation method of gel load filler:
(1) by after 12wt% acrylamide monomer stirring and dissolving, the N of 1.2wt%, N '-methylene-bisacrylamide is added
With the N of 1.5v/v%, N, N', N'- methyl ethylenediamine then adds the sodium alginate of 2wt%, is mixed with 100mL water
Gel liquid with certain viscosity；
(2) 50 particulate filler beads are put into gel liquid made from step (1), are uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) it is put into the crosslinked fluid of the sodium hydrogensulfite of the calcium chloride of 2wt%, 0.3wt% ATS (Ammonium thiosulphate) and 0.3wt%
The ratio of 4 DEG C of fixed crosslinking 12h of progress chemistry, gel volume and crosslinked fluid volume is 1:5, and taking-up filler is washed with water more later
Remaining crosslinked fluid, obtains complex carrier.
Comparative example 4 (polyethylene glycol gel embeds filtrate-without microorganism)
Steps are as follows for a kind of preparation method of gel load filler:
(1) sodium alginate of the Macrogol 6000 of 7wt% and 2wt% are mixed with 100mL water, being made has certain glue
The gel liquid of degree；
(2) 50 particulate filler beads are put into gel liquid made from step (1), are uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) 4 DEG C of fixed crosslinking 12h of progress chemistry in the calcium chloride of 4wt% and the aluminium citrate crosslinked fluid of 2wt% are put, are coagulated
The long-pending ratio with crosslinked fluid volume of colloid is 1:5, takes out filler later and extra crosslinked fluid is washed with water, obtain complex carrier.
Embodiment 2 (7wt% polyvinyl alcohol gel embeds filtrate-and contains microorganism)
A kind of complex microorganism carrier having autotrophic denitrification function, steps are as follows for preparation method:
(1) sodium alginate of the polyvinyl alcohol of 7wt% and 2wt% are mixed with 100mL water, after mixing at 90 DEG C,
It is cooled to room temperature, the concentration activated sludge after the 6000rpm centrifugation 10min of 4wt% is added, being made after mixing sufficiently has centainly
The gel liquid of viscosity；
(2) the filler bead (biomass 7gTSS/L) that 50 are attached to Anammox biomembrane is put into step (1)
In gel liquid obtained, it is uniformly mixed；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra coagulate under self gravitation effect
Glue；
(4) 4 DEG C of fixed crosslinking 12h of progress chemistry, gel in the crosslinked fluid of 50wt% sodium nitrate and 2wt% calcium chloride are put into
The ratio of volume and crosslinked fluid volume is 1:5, takes out filler later and extra crosslinked fluid is washed with water, and obtains complex microorganism load
Body.
Comparative example 5 (closes activated sludge and Anammox biology film filtering material-contains microorganism)
A kind of traditional synchronization short distance nitration-anaerobic ammoxidation reactor, by the filler of 50 Anammox biomembranes
Bead (biomass 7gTSS/L) is mixed with the activated sludge (sludge concentration 6gTSS/L) of 200mL.
1. the form comparison of different gel embedding filtrates
Fig. 1 is the photo of embodiment 1,2 and the gel embedding filtrate of comparative example 1-4, it can be seen that different gel rubber materials close
At filtrate it is different, without apparent gel layer outside the filtrate that comparative example 2 and comparative example 4 are formed, and embodiment 1 and right
For the filtrate of the processing of ratio 1 since gel strength is higher, also there are many gels, comparative example 3 and comparative example 1 and embodiment in outside
The filtrate of 1 processing is similar.Embodiment 2 is microorganism embedding gel filtrate, it can be seen that has embedded a large amount of micro- life inside filtrate
Object, and the external gas shearing force due to being aerated for a long time, substantially without microorganism.Pass through the form pair of different gel embedding filtrates
Than finding to get over consolidation with the increase of gel strength, embedding degree, opposite polyvinyl alcohol gel material, polyacrylamide gel
Material embeds degree more consolidation, and polyethylene glycol gel material embeds degree then loosely.
2. the ammonia nitrogen diffusion coefficient comparison of different gel embedding filtrates
Fig. 2 shows the comparing result of the ammonia nitrogen diffusion coefficient of different gel embedding filtrates, it can be found that embodiment 1 and right
The diffusion coefficient of ratio 3 is consistent, is 3.67 × 10-5cm2/ s, and the diffusion coefficient of comparative example 4 is slightly increased, reach 4.86 ×
10-5cm2/ s illustrates that polyethylene glycol is smaller than polyvinyl alcohol and polyacrylamide to the resistance to mass tranfer of ammonia nitrogen.In addition, comparative example 2
Diffusion coefficient it is maximum, be 8.08 × 10-5cm2/ s, with the raising of polyvinyl alcohol concentration, diffusion coefficient is gradually reduced, comparison
Example 2 and embodiment 1 are reduced to 5.89 × 10 respectively-5cm2/ s and 3.67 × 10-5cm2/ s illustrates that higher polyvinyl alcohol concentration increases
The big resistance to mass tranfer of ammonia nitrogen.The result shows that the material of polyvinyl alcohol is better than polyacrylamide and polyethylene glycol, gel strength is got over
Low, resistance to mass tranfer is smaller.
3. the binding force of different gel rubber materials and filtrate compares
After different gel embedding filter material aeratings 24 hours, the ratio that the quality to fall off accounts for gross mass is calculated, as a result such as Fig. 3
Shown, the gel that comparative example 4 falls off is most, illustrates that polyethylene glycol and filtrate binding force are most weak, followed by the polypropylene of comparative example 3
Amide material.On the contrary, the gel amount of falling off of embodiment 1 and comparative example 1,2 is smaller, especially embodiment 1 and comparative example 1, substantially
The gel not fallen off.Illustrate that the binding ability of polyvinyl alcohol and filtrate is most strong, and with the increase of gel strength, in conjunction with energy
Power is gradually increased, 5% polyvinyl alcohol concentration, although 7% polyvinyl alcohol binding force is stronger, the biography of nutriment
Defeated resistance increases (Fig. 2).
4. suspended active sludge and Anammox biomembrane be simply mixed after nitrogen removal performance
The activated sludge of suspension and Anammox biofilm packing are simply mixed comparative example 5, carry out sequence in beaker
Batch test, by temperature of reactor be set as 20 DEG C, dissolved oxygen concentration 2-3mg/L, influent ammonia nitrogen 50mg/L, water inlet sucrose it is dense
Degree is 25mg/L, measures ammonium nitrogen and nitrate nitrogen in water and changes with time trend, as a result as shown in Figure 4.
From fig. 4, it can be seen that ammonium nitrogen concentration continues to decline, and nitrate nitrogen persistently increases, the change of the two in 7 hours
Always, total nitrogen is essentially unchanged for change amount, illustrates in suspended active sludge and Anammox biofilm system, nitrite-oxidizing bacterium
Activity is stronger, produces a large amount of nitrate nitrogen, without the accumulation of nitrite nitrogen, completely inhibits the life of anaerobic ammonia oxidizing bacteria
It is long.By calculating slope and measuring biomass, it is known that compare NH4 +- N removal rate is 9.56mg/ (gVSSd), and total nitrogen base
This is not degraded, happens is that complete nitrification acts on.
5. the filtrate nitrogen removal performance of loading microorganisms gel
It is for strengthened anaerobic ammoxidation biomembrane and activated sludge combining deamination effect, anaerobic ammonia oxidizing bacteria and activity is dirty
The above-mentioned gel embedding of mud, is prepared the composite filtering material in embodiment 2.Carry out sequence batch test in beaker, by reactor temperature
Degree be set as 20 DEG C, dissolved oxygen concentration 2-3mg/L, influent ammonia nitrogen 50mg/L, water inlet sucrose concentration be 25mg/L, measure water
Middle ammonium nitrogen and nitrate nitrogen change with time trend, as a result as shown in Figure 5.
As shown in Figure 5, the Anammox biofilm system of the activated sludge gel load after gel embedding is de-
Nitrogen better performances, not generating a large amount of nitrate nitrogen and nitrite nitrogen, (the former stablizes in 1mg/L or so, the latter's concentration after measured
Less than 2mg/L).In addition to this, ammonia nitrogen degradation rate is 32.08mg/ (gVSSd) than ammonium nitrogen removal rate quickly, and right
Ratio 5 is compared, and is non-entrapment systems more than 3 times than ammonium nitrogen removal rate.And due to there is no nitrate nitrogen and nitrite nitrogen
Generation, nitrogen removal rate is higher, and the ammonium nitrogen of consumption is completely reformed into N2。
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (9)
1. a kind of complex microorganism carrier for having autotrophic denitrification function, it is characterised in that: in Anammox biofilm packing
One layer of the area load gel for having embedded aerobic activated sludge.
2. the preparation method of the complex microorganism carrier according to claim 1 for having autotrophic denitrification function, feature exist
In: steps are as follows:
(1) a certain amount of gel rubber material is mixed with water, after mixing at 80~100 DEG C, is cooled to 25~35 DEG C, is added one
The gel liquid with certain viscosity is made after quantitative activated sludge mixing sufficiently；
(2) a certain amount of filler for being attached to Anammox biomembrane is put into gel liquid made from step (1), is mixed
Uniformly；
(3) the area load filler of gel is taken out, a period of time is stood, removes extra gel under self gravitation effect；
(4) it is put into certain density crosslinked fluid and is crosslinked, take out filler later and extra crosslinked fluid is washed with water, answered
Close microbe carrier.
3. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: gel rubber material described in step (1) is the mixture of 2-7wt% polyvinyl alcohol and 0.5-2wt% sodium alginate.
4. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: the mass percentage of step (1) activated sludge is 4-10wt%.
5. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: the biomass that step (2) is attached to the filler of Anammox biomembrane is 5~10gTSS/L.
6. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: crosslinked fluid component and mass percentage described in step (4) are as follows: sodium nitrate 20-50wt%；Calcium chloride 1-2wt%；Surplus
For water.
7. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: step (4) carries out 10~15h of crosslinking for 3~6 DEG C in crosslinked fluid.
8. the preparation method of the complex microorganism carrier according to claim 2 for having autotrophic denitrification function, feature exist
In: the ratio of step (4) gel volume and crosslinked fluid volume is 1:5.
9. application of the complex microorganism carrier in sewage treatment described in a kind of claim 1~8 any claim.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484134A (en) * | 2020-05-06 | 2020-08-04 | 北京工业大学 | Preparation and application of denitrification embedded biological annular active filler |
| CN111484135A (en) * | 2020-05-06 | 2020-08-04 | 北京工业大学 | Preparation and application of efficient anaerobic ammonium oxidation composite bacteria embedded bioactive filler |
| CN114380393A (en) * | 2022-01-25 | 2022-04-22 | 南京大学 | Ferrocene-loaded coupling denitrification biological filler and preparation method and application thereof |
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