CN104891651A - Method for operating anaerobic ammoxidation reactor capable of rapidly restarting heavy metal pollution - Google Patents
Method for operating anaerobic ammoxidation reactor capable of rapidly restarting heavy metal pollution Download PDFInfo
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- CN104891651A CN104891651A CN201510233127.2A CN201510233127A CN104891651A CN 104891651 A CN104891651 A CN 104891651A CN 201510233127 A CN201510233127 A CN 201510233127A CN 104891651 A CN104891651 A CN 104891651A
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Abstract
The invention discloses a method for operating an anaerobic ammoxidation reactor capable of rapidly restarting the heavy metal pollution. According to the invention, a chelating cleaning solution is added in the anaerobic ammoxidation sludge subjected to heavy metal contamination, and then the obtained product is oscillated and washed in a shaking bath. The obtained supernatant is removed, and the low-storied sludge is oscillated and washed in an inorganic salt solution. The washed sludge is inoculated into a reactor, and simulated wastewater is pumped into the reactor, wherein the substrate initial concentration in the simulated wastewater is 50-70 mg/L. When the heavy metal concentration in the effluent water of the reactor is smaller than the heavy metal concentration in the inflowing water of the reactor, a growth activator is added into the inflowing water of the reactor. When the nitrate nitrogen concentration in the effluent water of the reactor is smaller than 10 mg/L and the three-day mean variation of the nitrate nitrogen concentration in the effluent water of the reactor is smaller than 15%, the substrate concentration in the simulated wastewater is gradually increased. When the total nitrogen removal rate is larger than 80% and the molar reaction stoichiometric ratio of the substrate is stable, the growth activator is no longer added into the inflowing water of the reactor. In this way, the restarting function is successfully realized. According to the invention, heavy metals remaining in the sludge can be efficiently removed. Meanwhile, the nitrogen removal performance of the reactor and the particle characteristics of the anaerobic ammoxidation sludge can be rapidly recovered.
Description
(1) technical field
The present invention relates to a kind of operation method restarting anaerobic ammonia oxidation reactor, be specifically related to a kind of operation method restarting the anaerobic ammonia oxidation reactor of heavy metal contamination fast.
(2) background technology
Nitrogen is indispensable bioelement, and it is self-evident to the importance of survival and development of mankind.But the excessive emissions of nitrogenous compound, causes a series of serious harms such as body eutrophication in recent years.In water, nitrogen often exists with the form of ammonia nitrogen, realizes high ammonia nitrogen, a difficult problem that the efficient low-consume process of low ratio of carbon to ammonium waste water is field of environment engineering always.
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 biological denitrification process.This technique reaches its maturity in process municipal sludge liquid field at present, and the heavy metal ion contained in livestock culture waste water, percolate, leather-making waste water, the contour nitrogenous effluent of metal etch processing waste water is (as Cu
2+, Zn
2+, Cd
2+, Pb
2+and Ni
2+) be the obstacle that restriction Anammox denitride technology is applied further always.These heavy metals are the trace element that microorganism is indispensable when lower concentration, also be the important component of many key enzymes or coenzyme, but excessive heavy metal can suppress even to poison microorganism with the functional group of cell interaction and the structure and function of degrade proteins.When long-term disposal high loading contains the waste water of heavy metal, heavy metal can because the materialization effects such as absorption, precipitation be accumulated in anaerobic ammonium oxidation sludge, and the operating performance affecting reactor even causes the collapse of reactor.In addition in actual motion due to variation water quality can hardly be avoided, heavy metal can be caused to impact to reactor.And lack pointed method of redress and recovery (or restarting) strategy at present.
For these problems, the present invention proposes a kind of operation method restarting the anaerobic ammonia oxidation reactor of heavy metal contamination fast.Efficiently can remove mud in reactor and hold the heavy metal stayed, the fast nitrogen removal performance of quick-recovery reactor and the particle characteristics of anaerobic ammonium oxidation sludge.
(3) summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of operation method restarting the anaerobic ammonia oxidation reactor of heavy metal contamination is fast provided.
For achieving the above object, the present invention adopts following technical scheme:
Restart an operation method for the anaerobic ammonia oxidation reactor of heavy metal contamination fast, described method is carried out as follows:
(1) in the anaerobic ammonium oxidation sludge being subject to heavy metal contamination, chelation cleaning liquid is added, regulate pH to 7.40 ~ 7.60, after argon gas deoxygenation of exposing to the sun is airtight, be placed in shaking bath, at 30 ~ 35 DEG C, under 160 ~ 200rpm after vibration 12 ~ 24h, leave standstill, abandon upper strata scavenging solution, take off layer mud and use inorganic salt solution oscillation cleaning again 3 ~ 5 times, each 10 ~ 30min, obtains the mud after cleaning;
The volume ratio of described mud and chelation cleaning liquid is 1:8 ~ 12, and the concentration of described mud is 2.0 ~ 3.0gVSSL
-1; Described chelation cleaning liquid is made up of sequestrant and inorganic salt solution, and described sequestrant is EDETATE SODIUM or NTA, and the final concentration of described sequestrant in chelation cleaning liquid is 0.5 ~ 1mmol L
-1, the composition of described inorganic salt solution is: NaH
2pO
410mgL
-1, MgSO
47H
2o 58.6mg L
-1, CaCl
22H
2o 5.65mg L
-1, KHCO
31g L
-1, NH
4 +-N 50 ~ 70mgL
-1, NO
2-N 50 ~ 70mg L
-1, micro-I 1.25ml L
-1, micro-II 1.25ml L
-1, wherein said micro-I consists of: EDTA 5.00gL
-1, FeSO
49.14gL
-1, described micro-II consist 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;
(2) sludge seeding after being cleaned by step (1) gained, in reactor, under the lucifuge constant temperature of 30 ~ 35 DEG C, pumps into simulated wastewater, starting point concentration 50 ~ 70mg L separately of described simulated wastewater mesostroma ammonia nitrogen and nitrite nitrogen
-1, hydraulic detention time is 0.8 ~ 1.5h, moves to heavy metal concentration in water outlet and, lower than water inlet, then in water inlet, adds growth activating agent, and question response device water outlet nitrite nitrogen concentration is lower than 10mg L
-1and three per day deviations are less than 15%, with 14 ~ 28mg L
-1cloth width progressively improve simulated wastewater mesostroma ammonia nitrogen and nitrite nitrogen concentration, when nitrogen removal rate is greater than 80%, and the metering of matrix molar reactive is than stable, i.e. nitrite nitrogen/ammonia nitrogen and theoretical value 1.32, the T-test of nitre nitrogen/ammonia nitrogen and theoretical value 0.26 checks and all meets P<0.05, now stop the interpolation of growth activating agent, restart successfully;
Described simulated wastewater is identical with described inorganic salt solution; Described growth activating agent is for containing Ca
2+, Mg
2+, Fe
2+, Fe
3+, Zn
2+, Cu
2+in a kind of or two or more arbitrarily soluble salts, the addition of described growth activating agent is final concentration: Ca
2+0.5 ~ 2.5mmolL
-1, Mg
2+0.5 ~ 2.5mmolL
-1, Fe
2+0.01 ~ 0.1mmolL
-1, Fe
3+0.05 ~ 0.1mmolL
-1, Zn
2+0.01 ~ 0.025mmolL
-1or Cu
2+0.01 ~ 0.025mmolL
-1, and the growth activating agent added does not overlap with causing the heavy metal of sludge pollution.
The present invention restarts the operation method of the anaerobic ammonia oxidation reactor of heavy metal contamination fast, and wherein, described heavy metal is the one or two or more arbitrarily in Cu, Zn, Ni, Cr, Cd.
In step (1), the volume ratio of preferred described anaerobic ammonium oxidation sludge and chelation cleaning liquid is 1:8 ~ 12, and the concentration of described mud is 2.0 ~ 3.0gVSSL
-1.
In step (1), described mud is used in inorganic salt solution oscillation cleaning process again, and the volume ratio of preferred described mud and inorganic salt solution is 1:5 ~ 10.
In step (1), pH is regulated to recommend to adopt 2molL
-1hydrochloric acid and 2molL
-1naOH solution.
In step (2), reactor seed sludge concentration is generally 10 ~ 20gVSSL
-1.
Advantage of the present invention is mainly reflected in: efficiently can remove mud in reactor and hold the heavy metal stayed, the fast nitrogen removal performance of quick-recovery reactor and the particle characteristics of anaerobic ammonium oxidation sludge.
(4) accompanying drawing explanation
Fig. 1 is for restarting each stage reactors Inlet and outlet water Different Nitrogen Concentration and nitrogen removal rate;
Fig. 2 is for restarting each stage reactors Anammox stoichiometry;
Fig. 3 is the particle characteristics restarting each stage mud.
(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
A kind of operation method restarting the anaerobic ammonia oxidation reactor of heavy metal contamination fast of the present invention, test mud take from stand cupric ion suppress bimestrial upflow anaerobic sludge blanket reactor (concentration 5,8,10,12mg Cu L
-1time respectively run two weeks).
Restart operation as follows:
(1) 500ml anaerobic ammonium oxidation sludge etc. is dispensed in the band plug Erlenmeyer flask of 10 1000ml, adds chelation cleaning liquid 500ml respectively, use 2molL
-1dilute hydrochloric acid and 2molL
-1naOH solution regulates pH to 7.50.After pouring argon gas deoxygenation 10min, cover tightly stopper and be placed in shaking bath, at 35 DEG C, vibrate under 180rpm 12h, and mud mixture leaves standstill, and abandons upper strata scavenging solution, take off layer mud and use inorganic salt solution (volume ratio 1:10) oscillation cleaning 3 times again, each 30min, obtain the mud after cleaning.
(2) be then in the upflow anaerobic sludge blanket reactor of 0.5L to effective volume by the sludge seeding after cleaning, be placed in the lucifuge thermostatic chamber of 35 ± 1 DEG C, pump into simulated wastewater, the starting point concentration of described simulated wastewater mesostroma ammonia nitrogen and nitrite nitrogen is 70mg L separately
-1, hydraulic detention time is 1.2h.Water outlet Cu from 20d
2+concentration starts lower than water inlet (0.08mgL
-1).So add growth activating agent Ca in water inlet
2+(CaCl
2), Ca in intaking
2+concentration is increased to 2.05mmolL
-1, question response device water outlet nitrite nitrogen concentration is lower than 10mg L
-1and when deviation was less than 15% on 3rd, with 28mg L
-1stride progressively improve simulated wastewater substrate concn.From 60d, reactor nitrogen removal rate is stabilized in more than 80%, and the metering of matrix molar reactive is than (i.e. nitrite nitrogen/ammonia nitrogen and the theoretical value 1.32 that tend towards stability, the T-test of nitre nitrogen/ammonia nitrogen and theoretical value 0.26 checks P<0.05), now stop the interpolation of growth activating agent, restart successfully.
After this, reactor performance is steadily increasing, returns to original level during 96d.Reactor operating performance is as Fig. 1 and Fig. 2.The particle characteristics of mud is as protoheme (Heme c) content, dehydrogenase activity (TTC-DHA), be shown in Fig. 3 than anaerobic ammoxidation activity (SAA).
Above-mentionedly restart in process, described chelation cleaning liquid is by sequestrant (Na
2eDTA 1mmolL
-1) and inorganic salt solution composition.
Described inorganic salt solution consist of NaH
2pO
410mg L
-1, MgSO
47H
2o 58.6mg L
-1, CaCl
22H
2o5.65mg L
-1, KHCO
31g L
-1, NH
4 +-N 50mg L
-1, NO
2-N 50mg L
-1, micro-I 1.25ml L
-1, micro-II 1.25ml L
-1; Wherein, the consisting of of described micro-I: EDTA 5.00gL
-1, FeSO
49.14gL
-1, 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.
Described simulated wastewater consist of NaH
2pO
410mg L
-1, MgSO
47H
2o 58.6mg L
-1, CaCl
22H
2o 5.65mg L
-1, KHCO
31g L
-1, NH
4 +-N 70mg L
-1, NO
2-N 70mg L
-1, micro-I 1.25ml L
-1, micro-II 1.25ml L
-1; Wherein, the consisting of of described micro-I: EDTA 5.00gL
-1, FeSO
49.14gL
-1, 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.
Claims (5)
1. restart an operation method for the anaerobic ammonia oxidation reactor of heavy metal contamination fast, it is characterized in that, described method is carried out as follows:
(1) in the anaerobic ammonium oxidation sludge being subject to heavy metal contamination, chelation cleaning liquid is added, regulate pH to 7.40 ~ 7.60, after argon gas deoxygenation of exposing to the sun is airtight, be placed in shaking bath, at 30 ~ 35 DEG C, under 160 ~ 200rpm after vibration 12 ~ 24h, leave standstill, abandon upper strata scavenging solution, take off layer mud and use inorganic salt solution oscillation cleaning again 3 ~ 5 times, each 10 ~ 30min, obtains the mud after cleaning;
The volume ratio of described mud and chelation cleaning liquid is 1:8 ~ 12, and the concentration of described mud is 2.0 ~ 3.0gVSSL
-1; Described chelation cleaning liquid is made up of sequestrant and inorganic salt solution, and described sequestrant is EDETATE SODIUM or NTA, and the final concentration of described sequestrant in chelation cleaning liquid is 0.5 ~ 1mmol L
-1, the composition of described inorganic salt solution is: NaH
2pO
410mg L
-1, MgSO
47H
2o 58.6mg L
-1, CaCl
22H
2o 5.65mg L
-1, KHCO
31g L
-1, NH
4 +-N 50 ~ 70mg L
-1, NO
2-N50 ~ 70mg L
-1, micro-I 1.25ml L
-1, micro-II 1.25ml L
-1, wherein said micro-I consists of: EDTA 5.00gL
-1, FeSO
49.14gL
-1, described micro-II consists of: EDTA 15.0gL
-1, ZnSO
47H
2o0.430gL
-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;
(2) sludge seeding after being cleaned by step (1) gained, in reactor, under the lucifuge constant temperature of 30 ~ 35 DEG C, pumps into simulated wastewater, starting point concentration 50 ~ 70mg L separately of described simulated wastewater mesostroma ammonia nitrogen and nitrite nitrogen
-1, hydraulic detention time is 0.8 ~ 1.5h, moves to heavy metal concentration in water outlet and, lower than water inlet, then in water inlet, adds growth activating agent, and question response device water outlet nitrite nitrogen concentration is lower than 10mg L
-1and three per day deviations are less than 15%, with 14 ~ 28mg L
-1cloth width progressively improve simulated wastewater mesostroma ammonia nitrogen and nitrite nitrogen concentration, when nitrogen removal rate is greater than 80%, and the metering of matrix molar reactive is than stable, i.e. nitrite nitrogen/ammonia nitrogen and theoretical value 1.32, the T-test of nitre nitrogen/ammonia nitrogen and theoretical value 0.26 checks and all meets P<0.05, now stop the interpolation of growth activating agent, restart successfully;
Described simulated wastewater is identical with described inorganic salt solution; Described growth activating agent is for containing Ca
2+, Mg
2+, Fe
2+, Fe
3+, Zn
2+, Cu
2+in a kind of or two or more arbitrarily soluble salts, the addition of described growth activating agent is final concentration: Ca
2+0.5 ~ 2.5mmolL
-1, Mg
2+0.5 ~ 2.5mmolL
-1, Fe
2+0.01 ~ 0.1mmolL
-1, Fe
3+0.05 ~ 0.1mmolL
-1, Zn
2+0.01 ~ 0.025mmolL
-1or Cu
2+0.01 ~ 0.025mmolL
-1, and the growth activating agent added does not overlap with causing the heavy metal of sludge pollution.
2. operation method as claimed in claim 1, it is characterized in that, described heavy metal is the one or two or more arbitrarily in Cu, Zn, Ni, Cr, Cd.
3. operation method as claimed in claim 1, it is characterized in that, in step (1), described mud is used in inorganic salt solution oscillation cleaning process again, and the volume ratio of described mud and inorganic salt solution is 1:5 ~ 10.
4. operation method as claimed in claim 1, is characterized in that, in step (1), regulates pH to adopt 2molL
-1hydrochloric acid and 2molL
-1naOH solution.
5. operation method as claimed in claim 1, it is characterized in that, in step (2), reactor seed sludge concentration is 10 ~ 20gVSSL
-1.
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