CN103112946A - Culturing method of rare earth praseodymium modified aerobic granular sludge - Google Patents
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Abstract
The invention relates to a culturing method of rare earth praseodymium modified aerobic granular sludge. The method comprises the following steps of: (1) inputting a sequencing batch reactor (SBR) after active sludge are stuffed, wherein the addictive amount of the active sludge is 20-40 percent of the volume of a reaction column of the SBR; (2) performing circulating repeated domestication for 6-8 days by utilizing sewage containing 5-15mg/L of Pr<3+> metal concentration to prepare domestication sludge; (3) performing the circulating repeated domestication for 17-22 days on the domestication sludge by utilizing sewage containing 5-15mg/L of Pr<3+> metal concentration to prepare modified sludge; and (4) performing the circulating repeated granulation for 7-9 days on the modified sludge to prepare the modified aerobic granular sludge. According to the culturing method, by utilizing a low-promotion high-inhibition function of rare earth praseodymium on the microbial activity, a complicated requirement of an aerobic granular sludge system on an outside appropriate operating condition is improved, the defect of instability is overcome, and the preparation of the sludge is increased to form stable particles, so that the aerobic granular sludge is rapidly cultured.
Description
Technical field
The present invention relates to praseodymium (Pr
3+) cultural method of modification aerobic particle mud, belong to technical field of sewage.
Background technology
Aerobic particle mud is under the hydraulic shear effect, and microorganism is realized the self-protection of microorganism by a kind of special microbial film that self-cohesion action forms.1997, there is the scholar to form aerobic particle mud by self coagulation in intermittent type SBR (Sequencing Batch Reactor) reactor, since then, the research of aerobic particle mud is at home and abroad generally carried out.
Zhu built the flourish concept that takes the lead in proposing aerobic particle mud that waits in 1999, pointed out under the aerobic aeration condition, and turn out aerobic particle mud in the anaerobic-aerobic Alternating System, these particles are take bacterium as main, and particle diameter is 0.5～1.5mm, and proportion is 1.007t/m
3, water ratio is 97%～98%, and the clearance of COD, TP is all reached more than 90%.
Yang Qi etc. adopt the simulated domestic wastewater of artificial preparation, by the regulation and control to operational conditions, turn out high performance aerobic particle mud in the sbr reactor device, more than sludge quality concentration reaches 4.5g/L.
The utilizations such as Liu have the sbr reactor device of intermittent operation characteristic, confirmed to reduce aeration rate in the endogenous respiration phase of microorganism, except the profile of aerobic particle mud changes, do not affect the activity of aerobic particle mud, compare with the aeration of endogenous respiration phase, in the high aeration speed of microorganism increased logarithmic phase, the stability of aerobic particle mud is had prior meaning.
Zhang Donghua etc. pass through supporting well the research of Characteristics of Granular Sludge in sequencing batch reactor, the difference that sums up operational condition causes the difference of granule sludge structural form, settling time is the principal element of Granular sludge formation, and organic loading has certain influence to the structure of granule sludge.
This shows, the formation condition of aerobic particle mud is the focus place of each scholar's research.
China's municipal effluent is take the active sludge aerobic biological treatment as main, and its structure and settling property are the keys that guarantees treatment effect.The cultivation of research granular sludge and the application in various sewage disposals are conducive to the promotion and application of Aerobic Granular Sludge Technology.
China is the abundant country of a rare earth resources, and the rare earth total reserves occupies prostatitis, the world, and rare earth resources mainly is distributed in the west areas such as the Inner Mongol, Sichuan, Guangxi, and basic substance has been laid in the application for rare earth in every profession and trade.Rare earth is all obtaining good application aspect metallurgy, chemical industry, medical and health.Great mass of data shows, the rare earth element of suitable concentration has certain promoter action to the growth of living organism, surpasses a certain limit and produces restraining effect, and this biological effect is called as the Hormesis phenomenon.
Praseodymium, chemical symbol Pr, ordination number 59, nucleidic mass 140.90765, atom outermost electron track is 6s
24f
3, one of lanthanon.Praseodymium is a kind of as rare earth element, and effect and other rare earth element that living organism is produced have certain similarity.Have the scholar to think, praseodymium can alleviate cadmium to the injury of root system, and praseodymium has alleviates the effect and raising improving activity of root system, increase proline content, reduction MDA content and cell leakage that cadmium is coerced; Suitably the praseodymium of dosage can promote the accumulation of the effect of russule mycelial growth and meta-bolites.
But praseodymium has no report to the effect of modification aerobic particle mud.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of praseodymium (Pr is provided
3+) cultural method of modification aerobic particle mud.
The term explanation
Sewage: the present invention's sewage used refers to the COD value at 300～800mg/L, the C:N:P(mass ratio)=(95～105): (9～11): 1, Mg
2+Concentration is 4～6mg/L, Fe
3+Concentration is 4～6mg/L, Ga
2+Concentration is 75～85mg/L, Zn
2+, Co
2+, K
+, I
-Be 5～15mg/L etc. micro-total concn, pH is 6.5～7.5.
Praseodymium ion: the present invention's praseodymium ion used is trivalent praseodymium ion, is solubility salt praseodymium element compound praseodymium nitrate.
The cultural method of praseodymium modification aerobic particle mud, step is as follows:
(1) with active sludge is vexed exposed to the sun 45～50 hours after, put into sequencing batch reactor (SBR), the active sludge add-on be sequencing batch reactor the reaction column volume 20%～40%;
(2) be cycled to repeat domestication operation 6～8 days, each domestication operation steps is as follows, 4 hours used times: sewage water inlet 6min, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, and the COD of sewage value is 300～800mg/L, aeration 222min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 7min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make acclimation sludge;
(3) acclimation sludge that step (2) is made is cycled to repeat modification operation 17～22 days, and each modification operation steps is as follows, and 4 hours used times: the amount by 11.6mg/L～34.9mg/L adds solubility praseodymium salt in sewage, make into water to contain Pr
3+Concentration be the sewage 6min of 5～15mg/L, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, the COD of sewage value is 800mg/L, aeration 224min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 5min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make the modification aerobic particle mud;
(4) modified sewage sludge that step (3) is made continues to cultivate 7～9 days, and each operation steps is as follows, 4 hours used times: sewage water inlet 6min, and sewage water inlet water level reaches 3/4 place of sequencing batch reactor, and the COD of sewage value is 800mg/L, Pr in sewage
3+Concentration be 5-15mg/L, aeration 226min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 3min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make stable modification aerobic particle mud.
Preferred according to the present invention, the active sludge in described step (1) is taken from the active sludge of sewage work.
Preferred according to the present invention, the useful volume of the reaction column of the sequencing batch reactor (SBR) in described step (1) is 6.0L, internal diameter 10cm, and external diameter 11cm, height 100cm, volume of displacement is 60%.
Preferred according to the present invention, in described step (2), the domestication operation is the 1st～2 day, and the COD of sewage value is 300mg/L; Domestication operation the 3rd～5 day, the COD of sewage value is 500mg/L; Domestication operation the 6th～8 day, the COD of sewage value is 800mg/L.
Preferred according to the present invention, Pr in sewage in described step (3)
3+Concentration be 10mg/L.
Preferred according to the present invention, the solubility praseodymium salt in described step (3) is praseodymium nitrate.
Beneficial effect
The cultural method of praseodymium modification aerobic particle mud of the present invention, utilize Rare Earth Elements of Praseodymium to the low short high effect that presses down of microorganism active, improved the aerobic particle mud system to external world suitable operational conditions require complicated, instable shortcoming, accelerate sludge forms stable particle, thereby fast culture goes out aerobic particle mud.
Description of drawings
What Fig. 1 represented is the variation contrast of embodiment 1 and Comparative Examples 1 water outlet COD clearance;
What Fig. 2 represented is the variation contrast of sludge concentration in embodiment 1 and Comparative Examples 1;
Fig. 3 represents be embodiment 1 with Comparative Examples 1 extracellular polymeric in protein and the variation contrast of polysaccharide ratio.
Embodiment
The below is to being described further technical scheme of the present invention in conjunction with the embodiments, but institute of the present invention protection domain is not limited to this.
Active sludge in embodiment is taken from the active sludge in wide water utilities two plant aeration tanks in Jinan City;
Pr (NO
3)
3Available from Chemical Reagent Co., Ltd., Sinopharm Group;
The COD value is the waste water process of 300mg/L:
As carbon source, ammonium chloride is as nitrogenous source with sodium acetate, and potassium primary phosphate and dipotassium hydrogen phosphate are originated as phosphoric, preparation C:N:P(mass ratio)=100:10:1, COD is 300mg/L, NH3-N is 30mg/L, the P concentration of element is 3mg/L, adds simultaneously metal ion: Mg
2+Concentration is 5mg/L, Fe
3+Concentration is 5mg/L, Ga
2+Concentration is 80mg/L, and Zn
2+, Co
2+, K
+, I
-The microelement concentration sum is 10mg/L, regulates pH 7.
The COD value is the waste water process of 500mg/L:
As carbon source, ammonium chloride is as nitrogenous source with sodium acetate, and potassium primary phosphate and dipotassium hydrogen phosphate are originated as phosphoric, preparation C:N:P(mass ratio)=100:10:1, COD is 500mg/L, NH3-N is 50mg/L, the P concentration of element is 5mg/L, adds simultaneously metal ion: Mg
2+Concentration is 5mg/L, Fe
3+Concentration is 5mg/L, Ga
2+Concentration is 80mg/L, and Zn
2+, Co
2+, K
+, I
-The microelement concentration sum is 10mg/L, regulates pH 7.
The COD value is the waste water process of 800mg/L:
As carbon source, ammonium chloride is as nitrogenous source with sodium acetate, and potassium primary phosphate and dipotassium hydrogen phosphate are originated as phosphoric, preparation C:N:P(mass ratio)=100:10:1, COD is 800mg/L, NH3-N is 80mg/L, the P concentration of element is 8mg/L, adds simultaneously metal ion: Mg
2+Concentration is 5mg/L, Fe
3+Concentration is 5mg/L, Ga
2+Concentration is 80mg/L, and Zn
2+, Co
2+, K
+, I
-The microelement concentration sum is 10mg/L, regulates pH 7.
The useful volume of the reaction column of sequencing batch reactor (SBR) is 6.0L, internal diameter 10cm, and external diameter 11cm, height 100cm, volume of displacement is 50%.
Embodiment 1
The cultural method of praseodymium modification aerobic particle mud, step is as follows:
(1) with active sludge is vexed exposed to the sun 48 hours after, put into sequencing batch reactor (SBR), the active sludge add-on be sequencing batch reactor the reaction column volume 1/3;
(2) be cycled to repeat domestication operation 7 days, each domestication operation steps is as follows, 4 hours used times: sewage water inlet 6min, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, and the COD of sewage value is 800mg/L, aeration 222min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 7min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2; Wherein the domestication operation is the 1st～2 day, and the COD of sewage value is 300mg/L; Domestication operation the 3rd～5 day, the COD of sewage value is 500mg/L; Domestication operation the 6th～7 day, the COD of sewage value is 800mg/L.
Make acclimation sludge;
(3) acclimation sludge that step (2) is made is cycled to repeat modification operation 18 days, and each modification operation steps is as follows, 4 hours used times: add 23.2mg Pr (NO in every liter of sewage
3)
3Preparation Pr
3+Concentration be the sewage of 10mg/L, then with the speed of 0.5L/min water inlet 6min, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, the COD of sewage value is 800mg/L, aeration 224min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 5min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make the modification aerobic particle mud;
(4) modified sewage sludge that step (3) is made continues cultivation and was cycled to repeat stable operation 8 days, and each operation steps is as follows, 4 hours used times: pass into Pr
3+Concentration is the sewage 6min of 10mg/L, makes sewage water inlet water level reach 3/4 place of sequencing batch reactor, and the COD of sewage value is 800mg/L, aeration 226min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 3min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2.
Make stable modification aerobic particle mud.
Comparative Examples 1
Cultural method as described in Example 1, difference is, does not add Pr (NO in the sewage of step (3) (4)
3)
3
Interpretation of result
For the result of the protein in water outlet COD clearance, sludge concentration and the extracellular polymeric of embodiment 1 and Comparative Examples 1 and polysaccharide ratio as shown in Fig. 1～3.
Step (2) domestication operation analysis:
The effect in this stage is to make the cotton-shaped active sludge of inoculation adapt to gradually new growing environment and stable propagation.After inoculation of activated-sludge, record that in reactor, sludge concentration is about 2489mg/L.When active sludge was in the adaptive phase, DO was controlled at 5mg/L, and influent COD is controlled at the 300mg/L left and right, and the rising according to sludge concentration later on strengthens the COD load, increases to the 500mg/L left and right, finally looks the mud stable case COD is transferred to the 800mg/L left and right.The ascending gas surface velocity is 0.0132m/s.By the mud growth mechanism, the initial period fungi accounts for leading primary, forms the thread fungus ball and rests in reactor, and the bacterium that granularity is less and floating flco are discharged with water outlet.When the poor flco of settling property was discharged, well behaved active sludge had been retained in reactor.This stage is when proceeding to the 7th day, the small-particle that has occurred yellow-white in reactor, because reactor is constantly discharged flco, add the growth of mud self, sludge concentration is compared with seed sludge and is changed not quite, but obvious enhancing of the removal effect of COD rises to 90% left and right by 55% left and right, this shows, it is stable that mud in reactor progressively tends to, and activity constantly strengthens, and also tends to gradually self-solidifying.
Step (3) modification operation analysis:
In this stage, the COD load maintains 800mg/L always, suitably increases the gas surface velocity and increases the water conservancy shearing force to 0.0172m/s.Add Pr (NO in embodiment 1 water inlet
3)
3Reagent makes into water Pr
3+Ion content 10mg/L.At this moment, in embodiment 1, owing to having added rare earth ion, mud can't adapt at short notice, and all relative Comparative Examples 1 is relatively poor so MLSS is with the COD clearance.Through the adaptive phase in a few days, the mud in embodiment 1 takes a turn for the better to some extent.When culturing sludge to the after 14 days the sludge concentration in Comparative Examples and embodiment 1 reach respectively 3527mg/L and 3890mg/L, more yellow particle has appearred, the grain diameter of diameter in 1.4～1.8mm(embodiment 1 is greater than Comparative Examples 1), quality is comparatively loose, but has had settleability preferably.Along with the growth of incubation time, sludge activity strengthens, COD, NH
3-N treatment effect is obvious, due to the inhomogeneous reason of reactor aeration this moment, in Comparative Examples 1 clearance of COD at short notice clearance descend to some extent, but the clearance of embodiment 1 is more stable, remain on more than 90%, in embodiment 1, granule sludge is than consolidation comparatively in Comparative Examples 1, and effluent quality is more clear.After this, adjust the gas surface velocity, keep oxygen delivery capacity, continue to observe the variation of sludge settling property and effluent index.Culturing process was by the 24th day, and the mud each side tends towards stability, and the domestication stage finishes.
Measurement result shows, this stage active sludge stable growth adds the mud of praseodymium, more is conducive to keep the stability of mud, makes that in mud, microbic activity maintains higher level.
Step (4) stable operation analysis:
This operation is shortened the settling time mainly according to Sludge Settling Characteristics, is adjusted into 3min, and the better mud granule of settling property is remained, and removes the slightly poor mud of settling property, observes the variation that the granular sludge process occurs.In this stage, in mud granule, organic concentration rolls up, and mud granule grows into certain ripening degree.The index of mud each side all tends towards stability, and more than in Comparative Examples 1, MLSS reaches 4400mg/L, and in continuous steady growth, more than in embodiment 1, MLSS reached 4700mg/L, higher than Comparative Examples 1, the intensity of particle strengthened gradually, and it is even that particle diameter also is tending towards.The COD clearance of two reactors has also reached respectively 90% and 94%.Each index tends towards stability, and aerobic particle mud is ripe.
After the cultivation of 35 days, the median size of the aerobic particle mud of turning out in Comparative Examples 1 is 1.8mm, and particle sludge intensity is (the mud integrity coefficient IC after shaking) 76.3%, and sludge concentration is that 4875mg/L:SVI is 54.1mL/g; The median size of the aerobic particle mud of turning out in embodiment 1 is 2.5mm, and particle sludge intensity is 87.2%, and sludge concentration is that 5224mg/L:SVI is 44.3mL/g;
In sum, so reach a conclusion, add 10mg/L Pr
3+The particle that forms in SBR of active sludge do not add the particle of formation of rare earth faster, more stable, and effluent quality is better.
The cultural method of praseodymium modification aerobic particle mud as described in Example 1, difference are, are cycled to repeat domestication operation 7 days, are cycled to repeat modification operation 17 days, are cycled to repeat granulation operation 8 days, add in modification operation and stable operation and contain Pr
3+Concentration be the sewage of 5mg/L, add 22.6mg Pr (NO in every liter of sewage
3)
3
Comparative Examples 2
Cultural method as described in Example 2, difference is, does not add Pr (NO in the sewage of step (3) (4)
3)
3
Interpretation of result
The mud starting point concentration of test is 3125mg/L, detects the COD of embodiment 2 and Comparative Examples 2, MLSS, and granularity, three nitrogen change, extracellular polymeric:
Cultivate after 32 days, the median size of the aerobic particle mud of turning out in Comparative Examples 2 is 1.9mm, and particle sludge intensity is 77.5%, and sludge concentration is that 5003mg/L:SVI is 55.1mL/g; The median size of the aerobic particle mud of turning out in embodiment 2 is 2.1, and particle sludge intensity is 85.1%, and sludge concentration is that 5437mg/L:SVI is 45.7mL/g;
In sum, so reach a conclusion, add 5mg/L Pr
3+The aerobic sludge granular that forms in SBR of active sludge do not add rare earth the formation particle comparatively fast, more stable, and effluent quality is slightly good.
Embodiment 3
The cultural method of praseodymium modification aerobic particle mud as described in Example 1, difference are, are cycled to repeat domestication operation 7 days, are cycled to repeat modification operation 22 days, are cycled to repeat granulation operation 8 days, add in modification operation and stable operation and contain Pr
3+Concentration be the sewage of 15mg/L, add 34.9mg Pr (NO in every liter of sewage
3)
3
Comparative Examples 3
Cultural method as described in Example 3, difference is, does not add Pr (NO in the sewage of step (3) (4)
3)
3
Interpretation of result
The mud starting point concentration of test is 3125mg/L, detects the COD of embodiment 3 and Comparative Examples 3, MLSS, and granularity, three nitrogen change, extracellular polymeric:
Cultivate after 37 days, the median size of the aerobic particle mud of turning out in Comparative Examples 3 is 1.8mm, and particle sludge intensity is 79.4%, and sludge concentration is that 4978mg/L:SVI is 54.9mL/g; The median size of the aerobic particle mud of turning out in embodiment 3 is 2.3mm, and particle sludge intensity is 86.6%, and sludge concentration is that 5343mg/L:SVI is 46.2mL/g;
In sum, so reach a conclusion, add 15mg/L Pr
3+The aerobic sludge granular that forms in SBR of active sludge do not add the formation particle of rare earth faster, more stable, and effluent quality is better, the time that mud need to adapt at the modification initial stage is longer.
Claims (6)
1. the cultural method of praseodymium modification aerobic particle mud, is characterized in that, step is as follows:
(1) with active sludge is vexed exposed to the sun 45～50 hours after, put into sequencing batch reactor, the active sludge add-on be sequencing batch reactor the reaction column volume 20%～40%;
(2) be cycled to repeat domestication operation 6～8 days, each domestication operation steps is as follows, 4 hours used times: sewage water inlet 6min, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, and the COD of sewage value is 300～800mg/L, aeration 222min, dissolved oxygen (DO) is 4.5～5.5mg/L, precipitation 7min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make acclimation sludge;
(3) acclimation sludge that step (2) is made is cycled to repeat modification operation 17～22 days, and each modification operation steps is as follows, and 4 hours used times: the amount by 11.6mg/L～34.9mg/L adds solubility praseodymium salt in sewage, make into water to contain Pr
3+Concentration be the sewage 6min of 5～15mg/L, sewage water inlet water level reaches 3/4 place of sequencing batch reactor, the COD of sewage value is 800mg/L, aeration 224min, dissolved oxygen are 4.5～5.5mg/L, precipitation 5min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make modified sewage sludge;
(4) modified sewage sludge that step (3) is made is cycled to repeat granulation operation 7～9 days, each granulation operation steps is as follows, 4 hours used times: sewage water inlet 6min, and sewage water inlet water level reaches 3/4 place of sequencing batch reactor, the COD of sewage value is 800mg/L, Pr in sewage
3+Concentration be 5-15mg/L, aeration 226min, dissolved oxygen are 4.5～5.5mg/L, precipitation 3min, draining 5min, water displacement be water in sequencing batch reactor cumulative volume 1/2;
Make the modification aerobic particle mud.
2. cultural method as claimed in claim 1, is characterized in that, the active sludge in described step (1) is taken from the active sludge of sewage work.
3. cultural method as claimed in claim 1, is characterized in that, the useful volume of the reaction column of the sequencing batch reactor in described step (1) is 6.0L, internal diameter 10cm, and external diameter 11cm, height 100cm, volume of displacement is 50%.
4. cultural method as claimed in claim 1, is characterized in that, in described step (2), the domestication operation is the 1st～2 day, and the COD of sewage value is 300mg/L; Domestication operation the 3rd～5 day, the COD of sewage value is 500mg/L; Domestication operation the 6th～8 day, the COD of sewage value is 800mg/L.
5. cultural method as claimed in claim 1, is characterized in that, Pr in sewage in described step (3)
3+Concentration be 10mg/L.
6. cultural method as claimed in claim 1, is characterized in that, the solubility praseodymium salt in described step (3) is praseodymium nitrate.
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| CN106242045B (en) * | 2016-09-22 | 2018-01-16 | 湖南大学 | A kind of aerobic particle mud fast culture process |
| CN111995053A (en) * | 2020-08-24 | 2020-11-27 | 哈尔滨工业大学 | A/A/O system based on synchronous reinforced biochemical phosphorus removal of powdered lanthanum-based adsorbent |
| CN111995053B (en) * | 2020-08-24 | 2022-01-28 | 哈尔滨工业大学 | A/A/O system based on synchronous reinforced biochemical phosphorus removal of powdered lanthanum-based adsorbent |
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