CN104129894B - Cover the method that monolayer-modified biofilm zeolite in-situ continues to repair serious pollution bed mud - Google Patents
Cover the method that monolayer-modified biofilm zeolite in-situ continues to repair serious pollution bed mud Download PDFInfo
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Abstract
The invention provides and a kind ofly cover the method that monolayer-modified biofilm zeolite in-situ continues to repair serious pollution bed mud, natural zeolite is put into container, adds Na
+solion, system temperature is 28 DEG C, and regulation system pH value is 9, carries out modification, successive reaction 24h, obtain modified zeolite with the rotating speed of 120r/min on water bath with thermostatic control shaking table; To modified zeolite in confined conditions, adopt first inoculation nitrobacteria to carry out biofilm, inoculate the substep colonization method that denitrifying bacterium carries out biofilm, obtain modification biofilm zeolite.By modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 2kg/m
2~ 3kg/m
2, carry out continuing to repair to the pollutent in severe polluted bed mud.The persistence that method of the present invention repairs serious pollution bed mud is strong, and zeolite can in-situ regeneration; Employing individual layer is laid, and modification biofilm zeolite can fully be contacted with the dissolved oxygen in water, improves repairing effect; Good for low-oxygen environment adaptability.
Description
Technical field
The invention belongs to field of environment engineering, relate to in-situ immobilization pollutent, be specifically related to a kind ofly cover the method that single layer of zeolite original position continues to repair serious pollution bed mud.
Background technology
Polluted bed mud is suppressed to be the effective measure controlling body eutrophication to water body liberating nitrogen, phosphor contaminant, existing natural attenuation method has little effect to severe polluted bed mud, and Sediment Dredging exists drawbacks such as quantities is large, secondary pollution, destruction water ecological setting.Cladding process is the focus of research at present, has the physics of traditional thick to shelter, and develops into thin active coating and covers.Thin layer activity covers Problems existing: when zeolite being covered serious pollution bed mud, ammonia nitrogen release strength is far longer than the adsorptive power of natural zeolite, and the ability improving zeolite adsorption ammonia nitrogen is most important; Secondly, fast for the saturated inefficacy of serious pollution bed mud zeolite, the time length is short, extends repair time and needs to be studied further; When it is worth mentioning that bed mud serious pollution, Dissolved Oxygen in Water concentration is lower, the multilayer disclosing a kind of polluted bed mud in prior art covers restorative procedure, although the method have employed biofilm zeolite, because upper strata is covered with fine sand, the transmittance process of oxygen can be limited, hinder the nitrification that mineralized nitrogen is nitre nitrogen, zeolite can not in-situ regeneration, and the zeolite life-span is shorter, and the serious pollution sediment in-situ that cannot realize low-oxygen environment continues to repair.Visible, exploitation serious pollution bed mud continues restorative procedure and has great importance.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to, a kind of low-oxygen environment that adapts to is provided to cover the method that single layer of zeolite original position continues to repair serious pollution bed mud, cation-modified zeolite is adopted to improve the ability of zeolite adsorption ammonia nitrogen, inoculated bacteria substep cultivates biofilm active zeolite, acting in conjunction improves zeolite in-situ regeneration rate, break through the technical bottleneck that existing low-oxygen environment zeolite in-situ regeneration rate is low, the original position being further used for improving serious pollution bed mud continues repairing effect, controls body eutrophication.
In order to realize above-mentioned task, the present invention adopts following technical scheme to be achieved:
Cover the method that single layer of zeolite original position continues to repair the dirt of serious pollution bed mud, the method is carried out according to following steps:
Step one, carries out modification to natural zeolite, and concrete method of modifying carries out according to following steps:
Step 1.1, puts into container by natural zeolite, adds Na
+solion, system temperature is 28 DEG C, and regulation system pH value is 9, carries out modification, successive reaction 24h with the rotating speed of 120r/min on water bath with thermostatic control shaking table;
Wherein, the corresponding 200mL concentration of every 10g natural zeolite is the Na of 1.0mol/L
+solion;
Step 1.2, outwells supernatant liquor, after clean with deionized water rinsing modified zeolite, be placed in drying in oven, obtain modified zeolite;
Step 2, the zeolite after modified to step carries out the activation of substep biofilm, and concrete colonization method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonassp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonassp.HY1), deposit number CCTCCNO:M209180;
Step 2.1: above-mentioned nitrobacteria and denitrifying bacterium are inoculated in respectively in nitrobacteria liquid nutrient medium and denitrifying bacterium liquid nutrient medium, 25 ~ 30 DEG C, vibrate under 120rpm constant temperature cultivation 2 ~ 3d, obtains enrichment nitrobacteria and denitrifying bacterium bacterium liquid respectively;
Step 2.2: former water is carried out sterilizing in High pressure steam sterilizer, sterilising conditions is temperature 120 ~ 126 DEG C, pressure 0.10 ~ 0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 obtained and denitrifying bacteria liquid are add in former water at 1: 9 with former water according to volume ratio respectively, at 25 ~ 30 DEG C, 120rpm Water Under bath constant temperature oscillation 2 ~ 3d, after former water becomes muddiness, obtain nitrobacteria biofilm bacterium liquid and the denitrifying bacterium biofilm bacterium liquid of zeolite biofilm use respectively;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 obtained is poured in the container filling the modified zeolite that step 1.2 obtains, the ratio adding 20mL ~ 40mL according to every gram of zeolite adds, at 20 DEG C ~ 40 DEG C, biofilm is carried out under air tight condition, now there is certain dissolved oxygen in water, be conducive to the growth of nitrobacteria, oxygen in water approach exhaustion after 2d ~ 3d, the ratio that the denitrifying bacterium biofilm bacterium liquid 2.2 steps obtained again adds 20mL ~ 40mL according to every gram of zeolite adds, now present anaerobic state in water, be conducive to denitrifying bacterium growth, at 20 DEG C ~ 40 DEG C, biofilm is carried out under air tight condition, after 3d ~ 4d, solid stream of water is adopted to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
Step 3, adopt the modified zeolite in-situ of step 2 to continue to repair the pollutent in bed mud, concrete restorative procedure carries out according to following steps:
By modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 2kg/m
2~ 3kg/m
2, carry out continuing to repair to severe polluted bed mud.
The present invention also has following technical characteristic:
Described Na
+solion adopts NaCl preparation.
Compared with prior art, useful technique effect is in the present invention:
Method of the present invention adopts Na
+the zeolite of modification and substep biofilm repairs contaminated bed mud, and persistence is strong, can in-situ regeneration; The bio-film colonization mode that method of the present invention adopts airtight biofilm and bacterium substep to add, makes fact of modified zeolite continue repairing effect and strengthens, for the bed mud of lasting reparation serious pollution; Employing individual layer is laid, and not only construction is simple, and modification biofilm zeolite can fully be contacted with the dissolved oxygen in water, improves repairing effect; Method of the present invention DO=3.5 ± 0.5mg/L in low DO concentration situation only repairs the nitrogen removal rate that 12 days can reach 72%, good for low-oxygen environment adaptability.In addition, result shows that the clearance of modification biofilm zeolite to ammonia nitrogen is the highest, and the first round can reach 96%, second takes turns and can reach 85%, and 75% ammonia nitrogen is converted into nitrogen and removes, and the in-situ regeneration rate of zeolite is up to 89%, show the ammonia nitrogen can removing sediment release continuously, realize continuing to repair bed mud.And unmodified natural zeolite, second clearance of taking turns ammonia nitrogen in test significantly drops to 58% and 79% from 70%, 92% of the first round, the in-situ regeneration rate of zeolite is lower, comparatively modified zeolite is poor for the ability of lasting reparation bed mud, showing that the method that modification adds biofilm improves zeolite in-situ regenerative power, is a kind of in-situ remediation method of lasting abatement bed mud ammonia nitrogen.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 different zeolites repairs total nitrogen mass-change curve in the overlying water of bed mud.
Fig. 2 is that embodiment 1 different zeolites repairs ammonia nitrogen mass-change curve in the overlying water of bed mud.
Fig. 3 is that embodiment 1 different zeolites repairs nitre nitrogen mass-change curve in the overlying water of bed mud.
Fig. 4 is that embodiment 1 different zeolites repairs nitrite nitrogen mass-change curve in the overlying water of bed mud.
Fig. 5 is that embodiment 2 Cover treatment density repairs total nitrogen mass-change curve in the overlying water of bed mud.
Fig. 6 is that embodiment 2 Cover treatment density repairs ammonia nitrogen mass-change curve in the overlying water of bed mud.
Fig. 7 is that embodiment 2 Cover treatment density repairs nitre nitrogen mass-change curve in the overlying water of bed mud.
Fig. 8 is that embodiment 2 Cover treatment density repairs nitrite nitrogen mass-change curve in the overlying water of bed mud.
Fig. 9 is embodiment 3 dissolved oxygen is ammonia nitrogen mass-change curve in the overlying water of 3.5mg/L.
Figure 10 is embodiment 3 dissolved oxygen is ammonia nitrogen mass-change curve in the overlying water of 5.5mg/L.
Figure 11 is embodiment 3 dissolved oxygen is ammonia nitrogen mass-change curve in the overlying water of 8.5mg/L.
Figure 12 is that embodiment 4 to change before and after bed mud ammonia nitrogen change curve in overlying water.
Figure 13 is that embodiment 4 to change before and after bed mud nitrite nitrogen change curve in overlying water.
Figure 14 is that embodiment 4 to change before and after bed mud nitre nitrogen change curve in overlying water.
Figure 15,16 is that embodiment 5 Zeolite modifying temperature is on the impact of in-situ regeneration.
Figure 17 is that embodiment 6 biofilm temperature is on the impact of natural zeolite in-situ regeneration.
Figure 18 is that embodiment 6 biofilm temperature is on the impact of modified zeolite in-situ regeneration.
Figure 19 is the total nitrogen concentration change of the different biofilm mode of embodiment 7.
Figure 20 is the ammonia nitrogen concentration change of the different biofilm mode of embodiment 7.
Figure 21 is the nitre nitrogen concentration change of the different biofilm mode of embodiment 7.
Figure 22 is the nitrite nitrogen change in concentration of the different biofilm mode of embodiment 7.
Figure 23 is that embodiment 8 multilayer covers and covering individual layer repairing effect compares
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Embodiment
The high-efficiency strain that the present invention relates to screening obtains nitrobacteria SY1 (pseudomonas SY1) and denitrifying bacterium HY1 (pseudomonas HY1) for screening from Heihe Reservoir bed mud, this two bacterial classification is preserved in China typical culture collection center on August 24th, 2009, be called for short CCTCC, and register on the books, the preservation 30 years in 24 days Augusts in 2009 of this biological inoculum.Wherein nitrobacteria pseudomonas SY1 (Pseudomonassp.SY1), preserving number is: CCTCCNO:M209181; Denitrifying bacterium pseudomonas HY1 (Pseudomonassp.HY1) preserving number is: CCTCCNO:M209180.
Wherein nitrobacteria SY1 and denitrifying bacterium HY1 bacterial strain all belong to Rhodopseudomonas, and it has following feature separately:
Table I colony morphology characteristic and morphological features
Table II major physiological, biochemical character
(note: √ expresses support for ,+represent that growth or reaction are for positive)
Nitrobacteria substratum: sodium acetate 0.3g/L, K
2hPO
40.02g/L, MgCl
20.05g/L, NH
4cl0.1g/L. liquid microelement 2ml/L, activation culture time 3d.
Denitrifying bacterium substratum: sodium acetate 0.3g/L, K
2hPO
40.02g/L, MgCl
20.05g/L, NaNO
30.06g/L, liquid microelement 2ml/L, activation culture time 3d.
Liquid microelement is prepared: EDTA50g, ZnSO
42.2g, CaCl
25.5g, MnCl
24H
2o5.06g, FeSO
47H
2o5.0g, ammonium molybdate 1.1g, CuSO
45H
2o1.57g, CoCl
26H
2o1.61g, joins in 1000mL deionized water, then uses 1molL
-1hCl and 1molL
-1naOH regulates pH=7.
The preparation of buffered soln: 10.86gK
2hPO
4and 13.97gKH
2pO
4constant volume, to 500mL volumetric flask, adds aqua sterilisa and carries out constant volume.
Bacteria culture fluid: take CH respectively
3cOONa1.61g/L, MgC1
20.10g/L, CaCl
2: 0.10g/L, Na
2hPO
40.20g/L, NaNO
30.20g/L is dissolved in the nutrient solution that 1000mL is made into C:N=6:1.
Defer to technique scheme, below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Its physical property of natural zeolite F1 is as follows: particle diameter is 1.0 ~ 2.0mm; Density is 2.3 × 10
3kg/m
3; Tap density is 9.0 × 10
2kg/m
3; Mohs' hardness is 3 ~ 4; Color is crimson look, purchased from folder Tianjin, Henan Gongyi City Kou Hai space filler factory.
Its physical property of natural zeolite F2 is as follows: particle diameter is 1.0 ~ 2.0mm; Density is 2.24 × 10
3kg/m
3; Tap density is 10.1 × 10
2kg/m
3; Mohs' hardness is 3 ~ 4; Specific surface area is 42.31m
2/ g, color is grey, purchased from folder Tianjin, Henan Gongyi City Kou Hai space filler factory.
Its physical property of natural zeolite F3 is as follows: particle diameter is 2.0 ~ 3.0mm; Density is 2.4 × 10
3kg/m
3; Tap density is 13.1 × 10
2kg/m
3; Mohs' hardness is 3 ~ 4; Specific surface area is 34.31m
2/ g, color is pink, purchased from folder Tianjin, Henan Gongyi City Kou Hai space filler factory.
Present invention employs above-mentioned three kinds of natural zeolites as experiment natural zeolite, following examples are all using natural zeolite F1 as experiment natural zeolite.
Embodiment 1:(different zeolites is on the impact of remedying sludge)
The present embodiment provides a kind of method adopting modification biofilm zeolite in-situ to continue to repair pollutants in sediments, and the method is carried out according to following steps:
Step one, carries out modification to natural zeolite, and concrete method of modifying carries out according to following steps:
Step 1.1, puts into container by natural zeolite, adds Na
+solion (NaCl preparation), system temperature is 28 DEG C, and regulation system pH value is 9, carries out modification, successive reaction 24h with the rotating speed of 120r/min on water bath with thermostatic control shaking table;
Wherein, the corresponding 200mL concentration of every 10g natural zeolite is the Na of 1.0mol/L
+solion;
Step 1.2, outwells supernatant liquor, after clean with deionized water rinsing modified zeolite, be placed in drying in oven, obtain modified zeolite;
Step 2, the zeolite after modified to step carries out biofilm activation, and concrete activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonassp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonassp.HY1), deposit number CCTCCNO:M209180;
Step 2.1: above-mentioned nitrobacteria and denitrifying bacterium are inoculated in respectively in nitrobacteria liquid nutrient medium and denitrifying bacterium liquid nutrient medium, 25 ~ 30 DEG C, vibrate under 120rpm constant temperature cultivation 2 ~ 3d, obtains enrichment nitrobacteria and denitrifying bacterium bacterium liquid respectively;
Step 2.2: former water is carried out sterilizing in High pressure steam sterilizer, sterilising conditions is temperature 120 ~ 126 DEG C, pressure 0.10 ~ 0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 obtained and denitrifying bacteria liquid are add in former water at 1: 9 with former water according to volume ratio respectively, at 25 ~ 30 DEG C, 120rpm Water Under bath constant temperature oscillation 2 ~ 3d, after former water becomes muddiness, obtain nitrobacteria biofilm bacterium liquid and the denitrifying bacterium biofilm bacterium liquid of zeolite biofilm use respectively;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 obtained is poured in the container filling the modified zeolite that step 1.2 obtains, the ratio adding 20mL ~ 40mL according to every gram of zeolite adds, at 20 DEG C ~ 40 DEG C, biofilm is carried out under air tight condition, now there is certain dissolved oxygen in water, be conducive to the growth of nitrobacteria, oxygen in water approach exhaustion after 2d ~ 3d, the ratio that the denitrifying bacterium biofilm bacterium liquid 2.2 steps obtained again adds 20mL ~ 40mL according to every gram of zeolite adds, now present anaerobic state in water, be conducive to denitrifying bacterium growth, at 20 DEG C ~ 40 DEG C, biofilm is carried out under air tight condition, after 3d ~ 4d, solid stream of water is adopted to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
Step 3, adopt the modified zeolite in-situ of step 2 to continue to repair the pollutent in bed mud, concrete restorative procedure carries out according to following steps:
By modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 2.09kg/m
2, carry out continuing to repair to the pollutent in bed mud, Grand Canal in Yangzhou bed mud, source water TN concentration (total nitrogen concentration) above bed mud is 3.5mg/L.
Comparative example 1: bed mud
This comparative example adopts Grand Canal in Yangzhou bed mud, and the source water TN concentration above bed mud is that 3.5mg/L tests as blank.
Comparative example 2: bed mud repaired by natural zeolite
Other conditions of comparative example 2 are all identical with embodiment 1, and it is cation-modified that difference is only that zeolite had not both adopted, and also do not adopt the substep biofilm of embodiment 1 to activate.
Comparative example 3: modified zeolite repairs bed mud
Other conditions of comparative example 3 are all identical with embodiment 1, and difference is only that zeolite only adopts Na
+solion modification, does not adopt the substep biofilm of embodiment 1 to activate.
The test result of embodiment 1, comparative example 1 to 3: Fig. 1, for adding total nitrogen concentration curve over time after zeolite, from figure, adds the total nitrogen concentration after zeolite and declines to some extent.Modification biofilm zeolite overlying water remains total nitrogen concentration will much smaller than other two groups, the abatement rate of modification biofilm zeolite to total nitrogen reaches as high as 84.5% (see table 1), the abatement rate of total nitrogen is the highest, and the abatement rate of unmodified zeolite to total nitrogen reaches as high as 62.9% (see table 1), prove that modification improves the ability of zeolite abatement total nitrogen.This may increase the adsorption potential quantity of zeolite due to modification, accelerates biological self reproducing process.
Ammonia nitrogen mass concentration, nitre nitrogen concentration and nitrite nitrogen mass concentration change curve in overlying water when Fig. 2, Fig. 3 and Fig. 4 are ammonium adsorbent zeolite in-situ regenerations.As can be seen from Fig., initial 10d, because bed mud is constantly to overlying water release ammonia nitrogen, in water, ammonia nitrogen concentration rises to 6.89mg/L by initial 4.02mg/L.10d is to 16d, and ammonia nitrogen concentration starts to decline, and nitrite nitrogen concentration and nitre nitrogen concentration rise rapidly simultaneously, show that zeolite in-situ regenerates.Modification biofilm zeolite, modified zeolite and the clearance of natural zeolite to ammonia nitrogen are respectively 87.1%, 54.2% and 50%, and show that method that modification adds activation accelerates the removal of ammonia nitrogen, the clearance of corresponding nitre nitrogen and nitrite nitrogen is also higher.
The repairing effect of table 1 modification biofilm zeolite
The impact of embodiment 2:(Cover treatment density)
The present embodiment is identical with other steps of embodiment 1, and difference is only in step 3, and by modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 3.14kg/m
2, carry out continuing to repair to the pollutent in bed mud.
Comparative example 4:
The present embodiment is identical with other steps of embodiment 2, and difference is only in step 3, and by modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 1.05kg/m
2, carry out continuing to repair to the pollutent in bed mud.
The test result of embodiment 1, embodiment 2, comparative example 1 and comparative example 4: Fig. 5 is the variation diagram of the total nitrogen concentration of overlying water under different zeolites coverage density condition, and as can be seen from the figure, coverage density is larger, and the clearance of total nitrogen is higher.When covering modification biofilm zeolite, density is 1.05kg/m
2, 2.09kg/m
2, 3.14kg/m
2the abatement rate of total nitrogen is 61.48%, 82.52%, 87.63% (see table 2) respectively.As can be seen from the above data, increase the abatement rate that zeolite coverage density can improve total nitrogen, optimum coverage density should be greater than 2.09kg/m
2, for cost consideration, preferably 2 ~ 3kg/m
2.
From ammonia nitrogen, nitrite nitrogen, nitre concentration profile of nitrogen that Fig. 6, Fig. 7, Fig. 8 are different zeolites coverage density condition in overlying water.Can find out, first 12 days, (modification biofilm zeolite 1.05kg/m under three kinds of coverage density conditions
2, 2.09kg/m
2, 3.14kg/m
2) ammonia nitrogen concentration is all on a declining curve, and coverage density is larger, decline faster, final ammonia nitrogen removal frank is respectively 55%, 75% and 95%.
Table 2 coverage density continues the impact of repairing polluted bed mud to modification biofilm zeolite
Embodiment 3:(modification biofilm zeolite is to the adaptability of oxygen concn)
Test design: the test in embodiment 3 is main it is considered that dissolved oxygen continues the impact of repairing on modification biofilm zeolite.Adopt natural zeolite (comparative example 2), modified zeolite (comparative example 3), modification biofilm zeolite (embodiment 1).By three kinds of zeolite uniform spreadings on bed mud, coverage density is 3.14kg/m
2slowly add source water (total nitrogen concentration is 3.5mg/L), totally 9 reactors, wherein the Dissolved Oxygen concentration Control of 1#, 2#, 3# reactor is 3.5mg/L, the Dissolved Oxygen concentration Control of 4#, 5#, 6# reactor is 5.5mg/L, 7#, the Dissolved Oxygen concentration Control of 8#, 9# reactor is 8.5mg/L.
The performance test results: Fig. 9, Figure 10, Figure 11 are dissolved oxygen DO is under the condition of 3.5mg/L, 5.5mg/L, 8.5mg/L, overlying water ammonia nitrogen concentration change curve, as can be seen from Figure 9, during DO=3.5 ± 0.5mg/L, after covering modification biofilm zeolite 12d, it is that after 1.12mg/L, 12d, nitrogen removal rate is 72% that total nitrogen residual concentration reaches minimum value, far above modified zeolite (30%) and unmodified zeolite (28%) (see table 3).Visible, the method that modification adds biofilm activation significantly improves the ability of cutting down total nitrogen.
As can be seen from Figure 10, during DO=5.5 ± 0.5mg/L, after covering modification biofilm zeolite, 12d total nitrogen residual concentration reaches minimum value 0.56mg/L, and nitrogen removal rate is up to 86%; And covering the system of modified zeolite and natural zeolite, total nitrogen residual concentration is higher, is respectively 1.8mg/L and 2.3mg/L, and nitrogen removal rate is only 55% and 43% (see table 3).
As can be seen from Figure 11, during DO=8.5 ± 0.5mg/L, after covering modification biofilm zeolite 12d, the ammonia nitrogen concentration of overlying water is cut down to minimum value (0.42mg/L), speed is greater than the repairing effect (1.5mg/L and 1.8mg/L) of other two kinds of zeolites, the clearance of total nitrogen is up to 90%, far above modified zeolite (63%) and unmodified zeolite (55%) (see table 3), further illustrate the quantity that modification increases adsorption potential, increase substantially the ability removing total nitrogen.
In sum, as can be seen from Fig. 9 to Figure 11 and in table 3, along with the reduction of dissolved oxygen concentration, although 12d nitrogen removal rate has reduction, but it is minimum that modification biofilm zeolite reduces amplitude, the nitrogen removal rate of 12 days 72% is also had in low DO concentration situation, good for low-oxygen environment adaptability.
Table 3 dissolved oxygen concentration continues the impact of repairing polluted bed mud to modification biofilm zeolite
Comparative example 5: natural biofilm zeolite repairs bed mud
Other conditions of comparative example 5 are all identical with embodiment 2, and difference is only that zeolite only adopts bacterial classification biofilm, does not adopt the Na of embodiment 1
+solion modification.
Embodiment 4:(modification biofilm zeolite is to the in-situ regeneration persistence of remedying sludge)
Test design: this experiment is two-wheeled altogether, be divided into five reactors, be respectively 1# blank (comparative example 1), 2# natural zeolite (comparative example 2), 3# modified zeolite (comparative example 3), the natural biofilm zeolite of 4# (comparative example 5), 5# modification biofilm zeolite (embodiment 1).
Above-mentioned zeolite is repaired bed mud in the following manner:
The first round: by zeolite uniform spreading on bed mud, coverage density is 2.09kg/m
2, slowly add source water (ammonia nitrogen concentration is about 3mg/L), dissolved oxygen variation range is 3mg/L ~ 8mg/L, and the variation range of pH value is 7.41 ~ 7.70, and test temperature is 20 ~ 30 DEG C.
Second takes turns: by whole for overlying water in bottle sucking-off, change and discharge bed mud completely, separated by zeolite for subsequent use.In bottle, again add fresh bed mud, by zeolite uniform spreading on bed mud, slowly add source water (ammonia nitrogen concentration is about 3mg/L), investigate the effect that zeolite continues to repair bed mud.
Test-results: Figure 12 is the change in concentration figure that different zeolites covers that bed mud continues the ammonia nitrogen repaired.As can be seen from the data of Figure 12 and table 4, the clearance of modification biofilm zeolite to ammonia nitrogen is the highest, and the first round can reach 96%, second takes turns and can reach 85%, the in-situ regeneration rate of zeolite, up to 89%, shows the ammonia nitrogen can removing sediment release continuously, realizes continuing to repair bed mud.And unmodified natural zeolite and natural biofilm zeolite, second clearance of taking turns ammonia nitrogen in test significantly drops to 58% and 79% from 70%, 92% of the first round, the in-situ regeneration rate of zeolite is lower, comparatively modified zeolite is poor to continue to repair the ability of bed mud, shows that the method that modification adds biofilm improves the ability that zeolite continues abatement bed mud ammonia nitrogen.
Figure 13 is the change in concentration figure that different zeolites covers that bed mud continues the nitrite nitrogen repaired.As can be seen from the data of Figure 13 and table 4, in modification biofilm zeolite and natural biofilm system of zeolites, the nitrite nitrogen residual concentration of two-wheeled test is all minimum, up to more than 97%, there is not accumulation, illustrate that ammonia nitrogen is further converted to nitrogen under the effect of biology in clearance.
Figure 14 is the change in concentration figure that different zeolites covers that bed mud continues the nitre nitrogen repaired.As can be seen from the data of Figure 14 and table 4, in modification biofilm system of zeolites, the clearance best result of nitre nitrogen is not 75% and 87%, shows that the mineralized nitrogen of 75% and 87% is that nitrogen is removed, can realize continuing to repair.
Table 4 modification biofilm zeolite continues to repair bed mud result
Embodiment 5: modification temperature is on the impact of modification biofilm zeolite
Test design: take natural zeolite (A), modified zeolite (B), modification biofilm zeolite (C), natural biofilm zeolite (D) 10g respectively in the Erlenmeyer flask of 200mL, first group of modified zeolite temperature is 30 DEG C, and second group of modified zeolite temperature is 50 DEG C.Measure respectively mass concentration be the ammonium chloride solution 200mL of 0mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L in the Erlenmeyer flask weighing up zeolite, leave standstill 20 days upon adsorption stable after, measure Na in overlying water
+burst size and NH
4 +the residual volume of-N.
Described natural biofilm zeolite refers to natural zeolite and directly carries out according to the step 2 of embodiment 1 zeolite that biofilm obtains.
Testing method: after natural zeolite modification biofilm, measure modification biofilm zeolite to the adsorptive power of ammonia nitrogen: accurately take the zeolite after a certain amount of modification biofilm, put into the tool plug Erlenmeyer flask of 250mL respectively, add the ammonia nitrogen solution that 200mL mass concentration is 100mg/L, at 28 DEG C of temperature, to vibrate on water bath with thermostatic control shaking table 24h with the rotating speed of 120r/min, get supernatant liquor 0.45 μm of millipore filtration afterwards and filter, remove the suspended matter in solution, reduce the unnecessary impact on experiment.Measure the absorbancy of water sample with DR5000 high precision ultraviolet spectrophotometer, its principle is Berthelot spectrophotometry.Ammonia nitrogen concentration is calculated, the clearance (η) of ammonia nitrogen by typical curve:
η＝(C
0-C)/C
0×100％
In formula: C
0---initial ammonia nitrogen concentration; C---final ammonia nitrogen concentration.
Interpretation of result: Figure 15 is Zeolite modifying temperature is 30 DEG C of impacts on in-situ regeneration, when can find out that ammonia nitrogen absorption tends towards stability, the clearance of ammonia nitrogen is up to more than 98%, when initial ammonia nitrogen concentration is 200mg/L, the in-situ regeneration amount of natural biofilm zeolite, natural zeolite, modified zeolite and modification biofilm zeolite is respectively 0.153mmol/L, 0.142mmol/L, 0.111mmol/L and 0.126mmol/L (see table 5).This shows that the in-situ regeneration ability of biofilm zeolite is better than non-biofilm zeolite.
Figure 16 is modification temperature is 50 DEG C of impacts on in-situ regeneration.When ammonia nitrogen absorption tends towards stability, the clearance of ammonia nitrogen is up to more than 97%, when initial ammonia nitrogen concentration is 200mg/L, the in-situ regeneration amount of natural biofilm zeolite, natural zeolite, modified zeolite and modification biofilm zeolite is respectively 0.09mmol/L, 0.07mmol/L, 0.02mmol/L, 0.01mmol/L (see table 5); This shows little compared with 30 DEG C of modification biofilm zeolites of the in-situ regeneration ability of 50 DEG C of modification biofilm zeolites.Visible, be in-situ regeneration optimum condition when modification temperature is 30 DEG C.
Embodiment 6: the impact of biofilm temperature
Test design: each 5g of modified zeolite taking natural zeolite and embodiment 1 preparation respectively, be placed in 250mL Erlenmeyer flask, 20mL nitrated biofilm bacterium liquid and denitrification biofilm bacterium liquid is added respectively according to every gram of zeolite, biofilm temperature controls, in 20 DEG C (room temperature states), 30 DEG C (constant temperature water bath heating), 40 DEG C (constant temperature water bath heating), to carry out airtight biofilm according to the step 2.3 of embodiment 13 respectively.Then adding 200mL mass concentration is that the ammonium chloride solution of 50mg/L carries out adsorption test, measures NH in overlying water
4 +the residual volume of-N.
Interpretation of result: Figure 17 is the impact that biofilm temperature regenerates zeolite in-situ.When biofilm temperature is 40 DEG C, in-situ regeneration maximum is 9.94mg/L (see table 6).When biofilm temperature is 30 DEG C, in-situ regeneration maximum is 5.35mg/L.But when biofilm temperature is 20 DEG C, zeolite does not have in-situ regeneration.
As can be seen from Figure 18, when biofilm temperature is 30 DEG C, it is 5.48mg/L that in-situ regeneration reached maximum the 4th day time.When biofilm temperature be 20 DEG C and 40 DEG C time, zeolite does not have in-situ regeneration.Visible, the temperature that biofilm is suitable is 30 DEG C ~ 40 DEG C.
Embodiment 7: biofilm mode is on the impact of modification biofilm zeolite
Test design: take the modified zeolite 70g of 3 parts of embodiments 1 preparations respectively in the vial of 5L, the nitrated biofilm bacterium liquid that the step 2.2 all adding embodiment 13 obtains and each 1400mL of denitrification biofilm bacterium liquid, carry out zeolite continuous aeration biofilm, not aeration respectively according to the step 2.3 of embodiment 1 namely leave standstill uncovered biofilm and leave standstill airtight biofilm, cultivate after 8 days, outwell bacterium liquid, rinse 2 times gently with distilled water, obtain modification biofilm zeolite.
Evenly rendered to by bed mud highly at the bottom of the synthetic glass post of 1.2m, DN300mm, bed mud thickness is about 50cm (quality is about 55kg), and by above-mentioned modification biofilm zeolite uniform fold on bed mud, coverage strength is 2kg/m
2, more former for Guyue Library water is slowly injected, making overlying water is deeply about 50cm (volume is about 35L), carries out the test that modification biofilm zeolite repairs bed mud.
Interpretation of result: Figure 19 gives overlying water total nitrogen concentration changing conditions in remedying sludge process, after can finding out that the system covering airtight biofilm zeolite repairs 60d, total nitrogen concentration is reduced to 2.76mg/L rapidly, nitrogen removal rate is 77%, and continuous aeration biofilm system of zeolites total nitrogen residual concentration is up to 11.07mg/L, nitrogen removal rate is 7.7%, repairing effect is the poorest, aeration biofilm system is not between therebetween (nitrogen removal rate 71%), shows that airtight biofilm mode is optimum mode.In repair process, residual ammonia nitrogen, nitre nitrogen and nitrite nitrogen concentration are shown in Figure 20,21,22.After repairing 53d, airtight biofilm, not aeration biofilm, continuous aeration biofilm three individual system remain ammonia nitrogen concentration and are respectively 0.73mg/L, 1.77mg/L, 8.83mg/L, the ability the strongest (see Figure 20) of airtight biofilm zeolite adsorption ammonia nitrogen is described, ammonia nitrogen can also be further converted to nitre nitrogen (see Figure 21), in-situ regeneration occurs.In addition, the nitrite nitrogen concentration of three individual system is all lower, does not occur nitrite nitrogen accumulation (see Figure 22).
The impact of table 5 modification temperature
The impact of table 6 biofilm temperature
Example 8: cover monolayer-modified biofilm zeolite and cover repairing effect with multilayer and compare
Test design: first add in 10L vial by the 2.5kg bed mud of weighing, 1# is blank's test, and 2# covers monolayer-modified biofilm zeolite, and zeolite coverage density is 2kg/m
2, 3# is that fine sand and biofilm zeolite multilayer cover system, and the coverage density of its mesolite and fine sand is 2kg/m
2, according to zeolite under, fine sand lays in upper mode, more slowly injected by former for Guyue Library water, making overlying water is deeply about 50cm (volume is about 35L), carries out the test of repairing bed mud.
Interpretation of result: carried out the reparation scheduling to last 54d, overlying water total nitrogen (TN) change in concentration as shown in Figure 23.As can be seen from the figure, after repairing 15d, cover the system of monolayer-modified zeolite, total nitrogen concentration reduces to 7.1mg/L from 21.9mg/L, TN clearance is 67.6%, repairing effect is obviously better than the system (56.6%) covering biofilm zeolite and fine sand, along with the prolongation of repair time, the TN concentration that modification biofilm zeolite covers individual layer system continues to reduce, after repairing 40d, 54d, TN concentration reduces to 5.3mg/L and 3.8mg/L, and TN clearance is 80% and 84%, shows that covering modification biofilm zeolite can carry out continuing to repair to severe polluted bed mud; And in multilayer covering system, TN concentration raises along with the prolongation of repair time, after repairing 40d, TN concentration is upgraded to 13.4mg/L, after extending to 54d, and TN concentration or 13.4mg/L, the fine sand that possible upper strata covers hinders the transmission of oxygen, and zeolite in-situ regenerative power reduces, and can not continue to repair.
Claims (2)
1. cover the method that monolayer-modified biofilm zeolite in-situ continues to repair serious pollution bed mud, it is characterized in that: the method is carried out according to following steps:
Step one, carries out modification to natural zeolite, and concrete method of modifying carries out according to following steps:
Step 1.1, puts into container by natural zeolite, adds Na
+solion, system temperature is 28 DEG C, and regulation system pH value is 9, carries out modification, successive reaction 24h with the rotating speed of 120r/min on water bath with thermostatic control shaking table;
Wherein, the corresponding 200mL concentration of every 10g natural zeolite is the Na of 1.0mol/L
+solion;
Step 1.2, outwells supernatant liquor, after clean with deionized water rinsing modified zeolite, be placed in drying in oven, obtain modified zeolite;
Step 2, the zeolite after modified to step carries out biofilm activation, and concrete activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonassp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonassp.HY1), deposit number CCTCCNO:M209180;
Step 2.1: above-mentioned nitrobacteria and denitrifying bacterium are inoculated in respectively in nitrobacteria liquid nutrient medium and denitrifying bacterium liquid nutrient medium, 25 ~ 30 DEG C, vibrate under 120rpm constant temperature cultivation 2 ~ 3d, obtains enrichment nitrobacteria bacterium liquid and denitrifying bacterium bacterium liquid respectively;
Step 2.2: former water is carried out sterilizing in High pressure steam sterilizer, sterilising conditions is temperature 120 ~ 126 DEG C, pressure 0.10 ~ 0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 obtained and denitrifying bacterium bacterium liquid are add in former water at 1: 9 with former water according to volume ratio respectively, at 25 ~ 30 DEG C, 120rpm Water Under bath constant temperature oscillation 2 ~ 3d, obtain nitrobacteria biofilm bacterium liquid and the denitrifying bacterium biofilm bacterium liquid of the use of zeolite biofilm respectively;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 obtained is poured in the container filling the modified zeolite that step 1.2 obtains, the ratio adding 20mL ~ 40mL according to every gram of zeolite adds, 20 DEG C ~ 40 DEG C, carry out biofilm under air tight condition, the ratio that denitrifying bacterium biofilm bacterium liquid step 2.2 obtained again after 2d ~ 3d adds 20mL ~ 40mL according to every gram of zeolite adds, 20 DEG C ~ 40 DEG C, carry out biofilm under air tight condition, after 3d ~ 4d, adopt solid stream of water to wash out the bacterium of filling surface absorption, obtain modification biofilm zeolite;
Step 3, adopt the modification biofilm zeolite in-situ of step 2 to continue to repair the pollutent in bed mud, concrete restorative procedure carries out according to following steps:
By modification biofilm zeolite individual layer uniform spreading on bed mud, coverage density is 2kg/m
2~ 3kg/m
2, carry out continuing to repair to the pollutent in bed mud.
2. the monolayer-modified biofilm zeolite in-situ of covering as claimed in claim 1 continues the method for repairing serious pollution bed mud, it is characterized in that: described Na
+solion adopts NaCl preparation.
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