CN104445846A - Method for fast activating activity of heavy metal contaminated anaerobic ammonia oxidation sludge - Google Patents
Method for fast activating activity of heavy metal contaminated anaerobic ammonia oxidation sludge Download PDFInfo
- Publication number
- CN104445846A CN104445846A CN201410608179.9A CN201410608179A CN104445846A CN 104445846 A CN104445846 A CN 104445846A CN 201410608179 A CN201410608179 A CN 201410608179A CN 104445846 A CN104445846 A CN 104445846A
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- heavy metal
- sludge
- oxidation sludge
- anaerobic ammonium
- ammonium oxidation
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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
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for fast activating the activity of heavy metal contaminated anaerobic ammonia oxidation sludge. The method comprises the following steps: cleaning the heavy metal contaminated anaerobic ammonia oxidation sludge by using distilled water, adding the washed sludge to a closed container, adding a cleaning solution with the pH value of 7.40-7.60, introducing argon, deoxidizing, and then closing; carrying out ultrasonic processing on the closed container under the condition that the rated frequency is 28 kHz and the ultrasonic intensity is 0.6-0.8 w.cm<-2>, then placing into a shaking table at the constant temperature of 30-35 DEG C, and oscillating away from light at 150-200 rpm; finally centrifugalizing an oscillated sludge water mixture, and taking a precipitation, namely the activated anaerobic ammonia oxidation sludge. The method disclosed by the invention can be used for effectively remitting the inhibition effect of heavy metals on the anaerobic ammonia oxidation sludge, efficiently removing the heavy metals adsorbed on a sludge surface and fast activating the denitrification activity of the anaerobic ammonia oxidation bacteria.
Description
(1) technical field
The present invention relates to the method for a kind of active sludge activation, the method for the anaerobic ammonium oxidation sludge activity of particularly a kind of quick active heavy metal contamination.
(2) background technology
Anaerobic ammonia oxidation process because of its without the need to additional organic carbon source, denitrifying load is high, working cost is low, take up an area the advantages such as space is little becomes one of most economical at present Process of Biological Nitrogen Removal.But due to actual waste water complicated component, the normal inhibition containing anaerobic ammonia oxidizing bacteria, limits the large-scale application of anaerobic ammonia oxidation process in Practical Project.
And heavy metal is exactly common are one of malicious pollutent in multiple nitrogenous effluent, the heavy metal ion contained in livestock culture waste water, percolate, the contour nitrogenous effluent of process hides is (as Cu
2+, Zn
2+) be the obstacle that this technology of restriction is applied further always.These heavy metal-containing waste water short-terms can produce acute Toxicity Influence to microorganism, and some heavy metal is as Cu
2+also can be accumulated in microorganism for a long time, destroy cytolemma, suppress its enzyme to be lived.
For these problems, the present invention proposes a kind of quick active suppresses anaerobic ammonium oxidation sludge activity method by heavy metal.EDTA as synthetic organic sequestering agent can within the scope of very wide pH with most of heavy metal particularly transition heavy metal form stable mixture, can desorb by the metal adsorbed.Utilizing the chelation evoked heavy metal of EDTA to increase its deliquescent method is the new approaches that anaerobic ammonium oxidation sludge is repaired.
In addition, low intensity ultrasound radiation can produce significant stimulation effect to bio-reaction system.Ultrasonic radiation can cause the generation of cavitation phenomenon and with a large amount of fault offset, cause organism in reactor to produce physics or chemical property change, cavitation phenomenon can increase cell walls permeability, promotes microorganism active.For this reason, the present invention proposes EDTA chelating coupling low intensity ultrasound radioactivation suppresses anaerobic ammonium oxidation sludge activity novel method by heavy metal.It is active that the present invention effectively can activate suppressed anaerobic ammonium oxidation sludge, and the efficient heavy metal removing Sludge Surface and inner absorption, realizes the fast quick-recovery of anaerobic ammonia oxidation reactor function and restart.
(3) summary of the invention
The object of the invention is to provide a kind of method of anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination.
The technical solution used in the present invention is:
The invention provides a kind of method of anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination, described method is: (1) gets the anaerobic ammonium oxidation sludge of heavy metal contamination, with washed with de-ionized water (preferably cleaning 5-8 time), mud after washing is added in encloses container, add the scavenging solution that pH value is 7.40 ~ 7.60, airtight after passing into argon gas deoxygenation; (2) by encloses container rated frequency be 28kHz, ultrasound intensity is 0.6 ~ 0.8wcm
-2condition under carry out supersound process (preferred supersound process 1.9 ~ 2.1min), and then put into 30 ~ 35 DEG C of constant-temperature tables, lucifuge vibration under 150 ~ 200rpm, form the mud mixture of supernatant liquid, lower floor's mud, vibration to lower floor's Heavy Metals in Sludge clearance is greater than 80%, and in supernatant liquid, the gaining rate of concentration of heavy metal ion in 1h is less than 5%; Finally by centrifugal for the mud mixture after vibration, get the anaerobic ammonium oxidation sludge that precipitation is activation;
Described scavenging solution is the nutrient solution containing final concentration 0.1 ~ 2mM EDETATE SODIUM, and described nutrient solution consists of: 50 ~ 100mgL
-1matrix NH
4 +-N, 50 ~ 100mgL
-1nO
2 --N, matrix NH
4 +-N and matrix NO
2 --N concentration ratio is 1:1, inorganic salt concentrated solution 50mlL
-1, micro-I 1.25mlL
-1with micro-II 1.25mlL
-1, solvent is distilled water;
Described micro-I consists of: EDTA 5.00gL
-1, FeSO
49.14gL
-1, solvent is distilled water;
Described micro-II consists of: EDTA 15.0gL
-1, ZnSO
47H
2o 0.430gL
-1, CoCl
26H
2o 0.240gL
-1, MnCl
24H
2o 0.990gL
-1, CuSO
45H
2o 0.250gL
-1, NaMoO
42H
2o 0.220gL
-1, NiCl
26H
2o 0.210gL
-1, H
3bO
40.014gL
-1, solvent is distilled water;
Described inorganic salt concentrated solution composition is: NaH
2pO
40.2gL
-1, MgSO
47H
2o 1.172gL
-1, CaCl
20.113gL
-1, NaHCO
316.8gL
-1, solvent is distilled water.
Further, described scavenging solution uses 2M dilute hydrochloric acid and the 1M NaOH aqueous solution by pH regulator to 7.40 ~ 7.60.
Further, the anaerobic ammonium oxidation sludge of described heavy metal contamination and scavenging solution volume ratio are 1:5 ~ 15 (preferred 1:10 ~ 11), and sludge concentration is 2.0 ~ 3.0gVSSL
-1(i.e. in the mixed solution of anaerobic ammonium oxidation sludge and scavenging solution, sludge concentration is 2.0 ~ 3.0gVSSL
-1).
Further, in the anaerobic ammonium oxidation sludge of described heavy metal contamination, heavy metal final concentration is 0.01 ~ 0.5mmol/gSS.
Further, described heavy metal comprises Cu, Zn, Ni, Cr and Cd, preferred Cu.
Further, preferred described mud mixture centrifugal 30 ~ 40min under 1600 ~ 2000g, obtains the anaerobic ammonium oxidation sludge activated.
The anaerobic ammonium oxidation sludge of heavy metal contamination of the present invention refers to long-term anaerobic ammonium oxidation sludge of coercing lower operation in high density heavy metal ion (5 ~ 12mg/L).
Advantage of the present invention is mainly reflected in: the inventive method effectively can alleviate the restraining effect of heavy metal to anaerobic ammonium oxidation sludge, the efficient heavy metal removing Sludge Surface absorption, the denitrification activity of quick active anaerobic ammonium oxidizing bacteria.
(4) accompanying drawing explanation
Fig. 1 is the schema of the inventive method.
Fig. 2 is cupric ion clearance graphic representation over time under different concns EDTA.
Fig. 3 is sludge anaerobic ammoxidation activity (SAA) column diagram after different concns EDTA cleans.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
With reference to the flow process shown in Fig. 1, carry out the test of the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination.
Test mud: take from long-term upflow anaerobic sludge blanket reactor (the effective volume 1.0L run in 35 DEG C of thermostatic chambers, sludge concentration 20gVSS/L), cupric ion final concentration respectively at 5mg/L, 8mg/L, 10mg/L, 12mg/L time respectively run two weeks, final TN removel rate (NRR) is 0.05kgNm
-3d
-1.
Get mud washed with de-ionized water 5 times, add in band plug serum bottle with the mud (content of copper ion is 15.7gCu/gSS) after graduated cylinder measures 10ml washing, add scavenging solution 110ml, regulate pH to 7.40 ~ 7.60 with 2M dilute hydrochloric acid and the 1M NaOH aqueous solution.Airtight be filled with argon gas deoxygenation 10min in serum bottle after, put into the ultrasonic 1.9min of ultrasonic cleaning instrument that rated frequency is 28kHz, ultrasound intensity is 0.7wcm
-2then 35 DEG C of constant-temperature tables are put into, lucifuge vibration 240min under 180rpm, form the mud mixture of supernatant liquid, lower floor's mud, front 30min gets supernatant liquid once every 10min syringe, after 30min every 30min sampling once, and every sub-sampling 3ml, water sample 4 DEG C preservation, adopts atomic absorption spectrophotometer to measure content of copper ion.Vibration to lower floor's Heavy Metals in Sludge clearance is greater than 80%, and the gaining rate of concentration of heavy metal ion in 1h is less than 5% in supernatant liquid, mud mixture centrifugal 30min under 1600g after vibration is terminated, after removing supernatant liquid, namely mud for determination of activity (when being determined at 35 DEG C, the anaerobic ammonia oxidizing bacteria total nitrogen wear rate of unit mass).
Ratio according to copper content total in Determined Copper in Aqueous Solution content and initial mud is cupric ion clearance.As shown in Figure 2, the anaerobic ammonium oxidation sludge activity after strengthening cleaning as shown in Figure 3 for the time dependent data of cupric ion clearance.Known when EDETATE SODIUM concentration is in 0.1 ~ 2mM from Fig. 2-3, the anaerobic ammoxidation activity energy fast lifting after ultrasound-enhanced cleaning, when after oscillation cleaning 210 ~ 240min, the clearance of cupric ion no longer obviously increases.Illustrate that the inventive method effectively can alleviate the restraining effect of heavy metal to anaerobic ammonium oxidation sludge, the efficient heavy metal removing Sludge Surface absorption, the denitrification activity of quick active anaerobic ammonium oxidizing bacteria.
Described scavenging solution is the nutrient solution containing final concentration 0.1mM sequestrant EDETATE SODIUM, and described nutrient solution consists of: 100mgL
-1matrix NH
4 +-N, 100mgL
-1matrix NO
2 --N, matrix NH
4 +-N and matrix NO
2 --N concentration ratio is 1:1, inorganic salt concentrated solution 50mlL
-1, micro-I 1.25mlL
-1with micro-II 1.25mlL
-1, solvent is distilled water.
Described micro-I consists of: EDTA 5.00gL
-1, FeSO
49.14gL
-1, solvent is distilled water;
Described micro-II consists of: EDTA 15.0gL
-1, ZnSO
47H
2o 0.430gL
-1, CoCl
26H
2o 0.240gL
-1, MnCl
24H
2o 0.990gL
-1, CuSO
45H
2o 0.250gL
-1, NaMoO
42H
2o 0.220gL
-1, NiCl
26H
2o 0.210gL
-1, H
3bO
40.014gL
-1, solvent is distilled water.
Described inorganic salt concentrated solution composition is NaH
2pO
40.2gL
-1, MgSO
47H
2o 1.172gL
-1, CaCl
20.113gL
-1, NaHCO
316.8gL
-1, solvent is distilled water.
The final concentration of EDETATE SODIUM in nutrient solution is changed into 0.5mM, 1mM, 2mM, 5mM, 10mM, 20mM, with 0mM EDETATE SODIUM in contrast under similarity condition.
Claims (6)
1. the method for the anaerobic ammonium oxidation sludge activity of a quick active heavy metal contamination, it is characterized in that described method is: (1) gets the anaerobic ammonium oxidation sludge of heavy metal contamination, clean with distilled water, mud after washing is added in encloses container, add the scavenging solution that pH value is 7.40 ~ 7.60, airtight after passing into argon gas deoxygenation; (2) by encloses container rated frequency be 28kHz, ultrasound intensity is 0.6 ~ 0.8wcm
-2condition under carry out supersound process, and then put into 30 ~ 35 DEG C of constant-temperature tables, lucifuge vibration under 150 ~ 200rpm, form the mud mixture of supernatant liquid, lower floor's mud, vibration to lower floor's Heavy Metals in Sludge clearance is greater than 80%, and the gaining rate of concentration of heavy metal ion in 1h is less than 5% in supernatant liquid, finally by centrifugal for the mud mixture after vibration, get the anaerobic ammonium oxidation sludge that precipitation is activation;
Described scavenging solution is the nutrient solution containing final concentration 0.1 ~ 2mM EDETATE SODIUM, and described nutrient solution consists of: 50 ~ 100mgL
-1matrix NH
4 +-N, 50 ~ 100mgL
-1matrix NO
2 --N, matrix NH
4 +-N and matrix NO
2 --N concentration ratio is 1:1, inorganic salt concentrated solution 50mlL
-1, micro-I 1.25mlL
-1with micro-II 1.25mlL
-1, solvent is distilled water;
Described micro-I consists of: EDTA 5.00gL
-1, FeSO
49.14gL
-1, solvent is distilled water;
Described micro-II consists of: EDTA 15.0gL
-1, ZnSO
47H
2o 0.430gL
-1, CoCl
26H
2o 0.240gL
-1, MnCl
24H
2o 0.990gL
-1, CuSO
45H
2o 0.250gL
-1, NaMoO
42H
2o 0.220gL
-1, NiCl
26H
2o 0.210gL
-1, H
3bO
40.014gL
-1, solvent is distilled water;
Described inorganic salt concentrated solution consists of: NaH
2pO
40.2gL
-1, MgSO
47H
2o1.172gL
-1, CaCl
20.113gL
-1, NaHCO
316.8gL
-1, solvent is distilled water.
2. the method for the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination as claimed in claim 1, is characterized in that described scavenging solution uses 2M dilute hydrochloric acid and the 1M NaOH aqueous solution by pH regulator to 7.40 ~ 7.60.
3. the method for the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination as claimed in claim 1, it is characterized in that the anaerobic ammonium oxidation sludge of described heavy metal contamination and scavenging solution volume ratio are 1:5 ~ 15, sludge concentration is 2.0 ~ 3.0gVSSL
-1.
4. the method for the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination as claimed in claim 1, is characterized in that in the anaerobic ammonium oxidation sludge of described heavy metal contamination, heavy metal final concentration is 0.01 ~ 0.5mmol/gSS.
5. the method for the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination as claimed in claim 1, is characterized in that described heavy metal comprises Cu, Zn, Ni, Cr and Cd.
6. the method for the anaerobic ammonium oxidation sludge activity of quick active heavy metal contamination as claimed in claim 1, is characterized in that described mud mixture centrifugal 30 ~ 40min under 1600 ~ 2000g, obtains the anaerobic ammonium oxidation sludge activated.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104829058A (en) * | 2015-05-08 | 2015-08-12 | 杭州师范大学 | Simultaneous nitrogen removal and heavy metal recovering process method for waste water and special system for process method |
CN104891651A (en) * | 2015-05-08 | 2015-09-09 | 杭州师范大学 | Method for operating anaerobic ammoxidation reactor capable of rapidly restarting heavy metal pollution |
CN105036324A (en) * | 2015-08-07 | 2015-11-11 | 杭州师范大学 | Running method for improving copper-containing wastewater denitrification processing performance of anaerobic ammonia oxidation reactor |
CN114956316A (en) * | 2022-06-17 | 2022-08-30 | 江西理工大学 | Method for improving heavy metal impact resistance of short-cut nitrified sludge |
CN115448451A (en) * | 2022-10-11 | 2022-12-09 | 西安建筑科技大学 | Rapid recovery method for inhibition of heavy metal by anaerobic ammonia oxidation |
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JPS60209297A (en) * | 1984-03-31 | 1985-10-21 | Kemikooto:Kk | Dissolving agent of water-insoluble calcium salt |
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CN103823005A (en) * | 2014-02-28 | 2014-05-28 | 东华大学 | Method of measuring contents of trace tetracycline, oxytetracycline and aureomycin in sludge |
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Cited By (8)
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CN104829058A (en) * | 2015-05-08 | 2015-08-12 | 杭州师范大学 | Simultaneous nitrogen removal and heavy metal recovering process method for waste water and special system for process method |
CN104891651A (en) * | 2015-05-08 | 2015-09-09 | 杭州师范大学 | Method for operating anaerobic ammoxidation reactor capable of rapidly restarting heavy metal pollution |
CN104891651B (en) * | 2015-05-08 | 2017-01-04 | 杭州师范大学 | Quickly restart the operation method of the anaerobic ammonia oxidation reactor of heavy metal pollution |
CN105036324A (en) * | 2015-08-07 | 2015-11-11 | 杭州师范大学 | Running method for improving copper-containing wastewater denitrification processing performance of anaerobic ammonia oxidation reactor |
CN105036324B (en) * | 2015-08-07 | 2018-04-10 | 杭州师范大学 | Lift the operation method of anaerobic ammonia oxidation reactor Treatment of Copper denitrogenation of waste water performance |
CN114956316A (en) * | 2022-06-17 | 2022-08-30 | 江西理工大学 | Method for improving heavy metal impact resistance of short-cut nitrified sludge |
CN114956316B (en) * | 2022-06-17 | 2023-12-08 | 江西理工大学 | Method for improving heavy metal impact resistance of short-cut nitrified sludge |
CN115448451A (en) * | 2022-10-11 | 2022-12-09 | 西安建筑科技大学 | Rapid recovery method for inhibition of heavy metal by anaerobic ammonia oxidation |
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