CN104150724A - Method for prolonging service life of active zeolite covering layer - Google Patents

Method for prolonging service life of active zeolite covering layer Download PDF

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CN104150724A
CN104150724A CN201410314108.8A CN201410314108A CN104150724A CN 104150724 A CN104150724 A CN 104150724A CN 201410314108 A CN201410314108 A CN 201410314108A CN 104150724 A CN104150724 A CN 104150724A
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zeolite
biofilm
nitrobacteria
bacterium
modification
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CN104150724B (en
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徐金兰
王威
黄福娣
张森森
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Xian University of Architecture and Technology
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Xian University of Architecture and Technology
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Abstract

The invention provides a method for prolonging the service life of an active zeolite covering layer. The method comprises the following steps: placing natural zeolite into a container, adding a cation solution, keeping a system temperature at 28 DEG C, regulating the pH value of the system to 9, modifying on a constant-temperature water bath shaker at a rotation speed of 120r/minute, and continuously reacting for 24 hours; pouring liquid supernatant, flushing with deionized water until the modified zeolite is clear, then, placing in a drying oven for drying to obtain the modified zeolite; and carrying out film-culturing activation onto the modified zeolite, so that the maximum regeneration rate of the modified film-cultured zeolite can reach 85.74% which is much higher than 69.12% of the modified zeolite and 54.29% of the unmodified zeolite. An in-situ regeneration rate for reusing the modified film-cultured zeolite by four times is over 95% which is much higher than 76% of the unmodified natural zeolite, and thus, the in-situ regeneration rate of the zeolite is further indicated to be greatly improved by virtue of the method of modifying and activating.

Description

A kind of method that extends the activated zeolite tectum life-span
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of method that extends the active tectum life-span, improve individual layer zeolite and cover the effect of repairing polluted bed mud, be specially adapted to the reparation of serious river, lake and Reservoir Sediment of endogenous nitrogen, phosphorus load.
Background technology
Suppressing polluted bed mud is the effective measure of 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 current countries in the world research, is sheltered by the physics of traditional thick, develops into thin active coating and covers.But, after active covering material is saturated to pollutent absorption by losing ability to function, the life-span is limited is the bottleneck that active coating soverlay technique is repaired serious pollution bed mud.At present mainly by increasing the cover thicknesss such as zeolite, calcite, increase the methods such as its loading capacity and increase the service life, although this forwarding method has certain effect, engineering cost increases substantially, and has limited its application in Practical Project.Therefore, exploitation method cheap, that extend efficiently the activated zeolite tectum life-span is significant for the reparation of serious pollution sediment in-situ, control body eutrophication.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to, provide a kind of and improve the quantity of adhering to nitrobacteria and denitrifying bacterium in zeolite by sodium modification and substep colonization method, increase substantially the in-situ regeneration rate of zeolite, extend the tectal life-span of zeolite.Adopt cation-modified zeolite, bacterial classification substep biofilm active zeolite, acting in conjunction improves zeolite in-situ regeneration rate, breaks through the technical bottleneck that the prior art mesolite tectum life-span is short, in-situ regeneration is difficult.
In order to realize above-mentioned task, the present invention adopts following technical scheme to be achieved:
Extend the method in activated zeolite tectum life-span, the method is carried out according to following steps:
Step 1, 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 cationic solution, and system temperature is 28 DEG C~50 DEG C, and regulation system pH value, in 4~11 scopes, is adsorbed exchange on water bath with thermostatic control shaking table, and successive reaction 24h, obtains modified zeolite;
Wherein, the cationic solution that the corresponding 200mL concentration of every 5g~15g natural zeolite is 1.0mol/L~2.0mol/L;
Step 1.2, outwells supernatant liquor, after using deionized water rinsing modified zeolite clean, is placed in drying in oven, obtains modified zeolite;
Step 2, carries out the activation of substep biofilm to the zeolite after step 1 modification, and concrete substep biofilm activation activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonas sp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonas sp.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, under 25~30 DEG C, 120rpm constant temperature, 2~3d is cultivated in vibration, obtains respectively enrichment nitrobacteria and denitrifying bacterium bacterium liquid;
Step 2.2: former water is carried out in High pressure steam sterilizer to sterilizing, sterilising conditions is 120~126 DEG C of temperature, pressure 0.10~0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 being obtained and denitrifying bacteria liquid are to add at 1: 9 to former water with former water according to volume ratio respectively, at 25~30 DEG C, 120rpm Water Under bath constant temperature oscillation 2~3d, former water becomes after muddiness, obtains respectively nitrobacteria biofilm bacterium liquid and denitrifying bacterium biofilm bacterium liquid that zeolite biofilm is used;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 being obtained is poured in the container that fills the modified zeolite that step 1.2 obtains, the ratio that adds 20mL~40mL according to every gram of zeolite adds, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, now in water, there is certain dissolved oxygen, hypoxemia is conducive to the growth of nitrobacteria, after 2d~3d, the ratio that the denitrifying bacterium biofilm bacterium liquid again 2.2 steps being obtained adds 20mL~40mL according to every gram of zeolite adds, now control anaerobic state, anaerobic is conducive to denitrifying bacterium growth, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, after 3d~4d, adopt solid stream of water to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
Preferably, cationic solution described above is for containing Na +, K +, Ca 2+or Mg 2+solion.
Preferably, a kind of method that extends the zeolite tectum life-span, the method is carried out according to following steps:
Step 1, 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 cationic solution, and 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 cationic solution that the corresponding 200mL concentration of every 10g natural zeolite is 1.0mol/L;
Described cationic solution is for containing Na +, K +, Ca 2+or Mg 2+solion;
Step 1.2, outwells supernatant liquor, after using deionized water rinsing modified zeolite clean, is placed in drying in oven, obtains modified zeolite;
Step 2, carries out biofilm activation to the zeolite after step 1 modification, and concrete activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonas sp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonas sp.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, under 25~30 DEG C, 120rpm constant temperature, 2~3d is cultivated in vibration, obtains respectively enrichment nitrobacteria and denitrifying bacterium bacterium liquid;
Step 2.2: former water is carried out in High pressure steam sterilizer to sterilizing, sterilising conditions is 120~126 DEG C of temperature, pressure 0.10~0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 being obtained and denitrifying bacteria liquid are to add at 1: 9 to former water with former water according to volume ratio respectively, at 25~30 DEG C, 120rpm Water Under bath constant temperature oscillation 2~3d, former water becomes after muddiness, obtains respectively nitrobacteria biofilm bacterium liquid and denitrifying bacterium biofilm bacterium liquid that zeolite biofilm is used;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 being obtained is poured in the container that fills the modified zeolite that step 1.2 obtains, the ratio that adds 20mL~40mL according to every gram of zeolite adds, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, now in water, there is certain dissolved oxygen, low oxygen concentration is conducive to the growth of nitrobacteria, oxygen in water approach exhaustion after 2d~3d, the ratio that the denitrifying bacterium biofilm bacterium liquid again 2.2 steps being obtained adds 20mL~40mL according to every gram of zeolite adds, now control anaerobic state, anaerobic is conducive to denitrifying bacterium growth, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, after 3d~4d, adopt solid stream of water to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
Preferably, described cationic solution is Na +solion.
Preferably, the rotating speed of the water bath with thermostatic control shaking table described in step 1.1 is 120r/min.
Preferably, in described cationic solution: Na +solion adopts NaCl preparation, K +solion adopts KCl preparation, Ca 2+solion adopts CaCl 2preparation, Mg 2+solion adopts Mg Cl 2preparation.
Compared with prior art, useful technique effect is in the present invention:
The present invention adopts Na +the method of the airtight biofilm activation of modification associating substep improves the nitrobacteria that adheres in zeolite and the quantity of denitrifying bacterium, increases substantially the in-situ regeneration ability of zeolite, extends the tectal life-span of activated zeolite, passes through Na +modification increases the ability of zeolite adsorption ammonia nitrogen, strengthen the fecundity of predominant bacteria in zeolite, airtight substep biofilm, under hypoxia condition, inoculate nitrobacteria and carry out biofilm, under oxygen free condition, inoculate denitrifying bacterium and carry out biofilm, make two kinds of bacteriums growth and breeding in adapt circumstance separately respectively, after modification, nitrobacteria quantity increases 100 times compared with before modification, denitrifying bacterium quantity has increased 200 times, without continuous aeration, method is simple, can increase substantially zeolite in-situ regeneration rate, extends the tectal life-span of activated zeolite.The in-situ regeneration rate of biofilm modified zeolite can reach 85.74%, far away higher than 54.29% of 69.12% and unmodified zeolite of modified zeolite.Four reusable in-situ regeneration rates of modification biofilm zeolite are all more than 95%, far above unmodified natural zeolite 76%, the method that further illustrates modification and substep biofilm activation has increased substantially the in-situ regeneration rate of zeolite, extends activated zeolite tectal work-ing life.
Brief description of the drawings
Fig. 1 is the adsorptive capacity of the zeolite F1 of different inorganic salt after cation-modified to ammonia nitrogen.
Fig. 2 is different modified solution Na +concentration is on adsorbing the impact of rear ammonia nitrogen mass concentration and ammonia nitrogen removal frank.
Fig. 3 is the impact of different zeolites dosage on ammonia nitrogen absorption amount.
Fig. 4 is the impact of differing temps on ammonia nitrogen absorption amount.
Fig. 5 is the impacts of different pH values on ammonia nitrogen absorption amount.
Fig. 6 is the adsorptive capacity of the zeolite F2 of different inorganic salt after cation-modified to ammonia nitrogen.
Fig. 7 is biofilm zeolite total plate count curve over time
Fig. 8 is biofilm zeolite nitrifier quantity curve over time
Fig. 9 is the change curve of biofilm zeolite denitrifying bacteria quantity along with the time
Figure 10 is Na +the adsorptive capacity of zeolite F3 after ion modification to ammonia nitrogen.
Figure 11 is that embodiment 1 adsorbs zeolite in-situ regeneration rate curve over time with the ammonium of comparative example 1, comparative example 2.
Ammonia nitrogen quality change curve in overlying water when Figure 12 is embodiment 1 with the ammonium absorption zeolite in-situ regeneration of comparative example 1, comparative example 2.
Figure 13 be embodiment 1 with comparative example 1, comparative example 2 be ammonium absorption zeolite in-situ regeneration time overlying water in nitre nitrogen quality change curve.
Figure 14 be embodiment 1 with comparative example 1, comparative example 2 be ammonium absorption zeolite in-situ regeneration time overlying water in nitrite nitrogen quality change curve.
Figure 15 is the change curve of biofilm time to zeolite ammonia nitrogen absorption.
Figure 16 is bacterium liquid and the change curve of zeolite throwing amount solid-to-liquid ratio to zeolite ammonia nitrogen absorption.
Figure 17, the 18th, the impact of Zeolite modifying temperature on in-situ regeneration.
Figure 19 is the impact of biofilm temperature on natural zeolite in-situ regeneration.
Figure 20 is the impact of biofilm temperature on modified zeolite in-situ regeneration.
Figure 21 is that the total nitrogen concentration of different biofilm modes changes.
Figure 22 is that the ammonia nitrogen concentration of different biofilm modes changes.
Figure 23 is that the nitre nitrogen concentration of different biofilm modes changes.
Figure 24 is the nitrite nitrogen change in concentration of different biofilm modes.
Figure 25 is the rate of the subduing change curve of total nitrogen in overlying water.
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Embodiment
The present invention relates to the high-efficiency strain of screening for screening and obtain nitrobacteria SY1 (pseudomonas SY1) and denitrifying bacterium HY1 (pseudomonas HY1) from Heihe Reservoir bed mud, this two bacterial classification is preserved in Chinese Typical Representative culture collection center on August 24th, 2009, be called for short CCTCC, and register on the books, this biological inoculum was preserved 30 years in 24 days Augusts in 2009.Wherein nitrobacteria pseudomonas SY1 (Pseudomonas sp.SY1), preserving number is: CCTCCNO:M209181; Denitrifying bacterium pseudomonas HY1 (Pseudomonas sp.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 growth or react positive)
Nitrobacteria substratum: sodium acetate 0.3g/L, K 2hPO 40.02g/L, MgCl 20.05g/L, NH 4cl 0.1g/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 preparation: EDTA50g, ZnSO 42.2g, CaCl 25.5g, MnCl 24H 2o 5.06g, FeSO 47H 2o 5.0g, ammonium molybdate 1.1g, CuSO 45H 2o 1.57g, CoCl 26H 2o 1.61g, joins in 1000mL deionized water, then uses 1molL -1hCl and 1molL -1naOH regulates pH=7.
The preparation of buffered soln: 10.86g K 2hPO 4and 13.97gKH 2pO 4constant volume, to 500mL volumetric flask, adds aqua sterilisa to carry out constant volume.
Bacteria culture fluid: take respectively CH 3cOONa 1.61g/L, MgC1 20.10g/L, CaCl 20.10g/L, Na 2hPO 40.20g/L, NaNO 30.20g/L is dissolved in 1000mL and is made into the nutrient solution of 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 of doing on present techniques scheme basis all fall into protection scope of the present invention.
Embodiment 1: inorganic cation modification
Its physical property of natural zeolite F1 described in embodiment 1 to 7 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.
Accurately take 1 part of 10g and handle natural zeolite F1 for subsequent use well and be labeled as 1. number, be put in the tool plug Erlenmeyer flask of 250mL, adding respectively 200mL concentration is the Na of 1.0mol/L +solution (preparing with NaCl), at 28 DEG C, vibrate in water bath with thermostatic control shaking table and remove and cover solution after 24h with the rotating speed of 120r/min, cleans modified zeolite with deionized water, is then placed in baking oven and dries under the condition of 105 DEG C.The good zeolite of taking-up modification is put into moisture eliminator and is cooled to room temperature sealing preservation.
Embodiment 2: inorganic cation modification
Accurately take 1 part of 10g and handle natural zeolite F1 for subsequent use well and be labeled as 2. number, be put in the tool plug Erlenmeyer flask of 250mL, adding respectively 200mL concentration is the K of 1.0mol/L +solution (preparing with KCl), at 28 DEG C, vibrate in water bath with thermostatic control shaking table and remove and cover solution after 24h with the rotating speed of 120r/min, cleans modified zeolite with deionized water, is then placed in baking oven and dries under the condition of 105 DEG C.The good zeolite of taking-up modification is put into moisture eliminator and is cooled to room temperature sealing preservation.
Embodiment 3: inorganic cation modification
Accurately take 1 part of 10g and handle natural zeolite F1 for subsequent use well and be labeled as 3. number, be put in the tool plug Erlenmeyer flask of 250mL, adding respectively 200mL concentration is the Ca of 1.0mol/L 2+solution (is used CaCl 2preparation), at 28 DEG C, vibrate in water bath with thermostatic control shaking table and remove and cover solution after 24h with the rotating speed of 120r/min, modified zeolite is cleaned with deionized water, be then placed in that baking oven is interior dries under the condition of 105 DEG C.The good zeolite of taking-up modification is put into moisture eliminator and is cooled to room temperature sealing preservation.
Na +the condition of modified optimization ammonia nitrogen absorption performance:
Embodiment 4: under different N a+ concentration conditions, prepare modified zeolite
Accurately take several parts of 10g and handle zeolite raw material for subsequent use well, be put in the tool plug Erlenmeyer flask of 250mL, add respectively that 200mL molar mass concentration is 0.2,0.5,1.0,1.5, the Na of 2.0mol/L +solution, respectively at 28 DEG C, with the rotating speed of the 120r/min 24h that vibrates in water bath with thermostatic control shaking table, cation zeolites modification completes.In removal, cover modified solution, modified zeolite is cleaned with deionized water, clean three times, then with stand-by in drying under the condition of 105 DEG C in baking oven.
Embodiment 5: different solid, than under condition, is prepared modified zeolite
The zeolite raw material for subsequent use of accurately take 5,10,12,15,17,20,25,30g handling well, be put in 250mL tool plug Erlenmeyer flask in, all add the Na that 200mL molar mass concentration is 1.0mol/L +solution, respectively at 28 DEG C, with the rotating speed of the 120r/min 24h that vibrates in water bath with thermostatic control shaking table, cation zeolites modification completes.In removal, cover modified solution, modified zeolite is cleaned with deionized water, clean three times, then with stand-by in drying under the condition of 105 DEG C in baking oven.
Embodiment 6: under condition of different temperatures, prepare modified zeolite
Accurately take several parts of 15g and handle zeolite raw material mark for subsequent use well, be put in respectively in the tool plug Erlenmeyer flask of 250mL, unification adds the Na that 200mL molar mass concentration is 1.0mol/L +solution, respectively at 28,35,40,50 DEG C, with the rotating speed of the 120r/min 24h that vibrates in water bath with thermostatic control shaking table, make modified zeolite.After modified zeolite is rinsed well with deionized water, the drying in oven that is placed in 105 DEG C is stand-by.
Embodiment 7: under condition of different pH, prepare modified zeolite:
Accurately take several parts of 15g and handle zeolite raw material for subsequent use well, be put in respectively in the tool plug Erlenmeyer flask of 250mL, adding respectively 200mL concentration is the Na of 1.0mol/L +solution, regulates pH value to be respectively 4,5,7,9,11, and pH value regulates and adopts respectively hydrochloric acid soln and sodium hydroxide solution, and during due to adjusting pH value, the consumption of sodium hydroxide solution is little, therefore can be to Na +concentration impact.Respectively at 28 DEG C, with the rotating speed of the 120r/min 24h that vibrates in water bath with thermostatic control shaking table, cation zeolites modification completes.In removal, cover modified solution, modified zeolite is cleaned with deionized water, clean three times, then with stand-by in drying under the condition of 105 DEG C in baking oven.
Embodiment 8 to 11:
Its physical property of natural zeolite F2 described in embodiment 8 to 11 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.
Embodiment 8 is identical with the modifying process of embodiment 1, and difference is only to have changed natural zeolite into F2 by F1; Embodiment 9 is identical with the modifying process of embodiment 2, and difference is only to have changed natural zeolite into F2 by F1; Embodiment 10 is identical with the modifying process of embodiment 3, and difference is only to have changed natural zeolite into F2 by F1; Embodiment 11 is identical with the modifying process of embodiment 1, and difference is only to have changed natural zeolite into F2 by F1, the Na that is 1.0mol/L by 200mL concentration +solution (preparing with NaCl) becomes the Mg that 200mL concentration is 1.0mol/L 2+solution (is used MgCl 2preparation).
Embodiment 12:
Its physical property of natural zeolite F3 described in embodiment 12 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.
Embodiment 12 is identical with the modifying process of embodiment 1, and difference is only to have changed natural zeolite into F3 by F1.
Embodiment 13:Na +modification biofilm zeolite
The present embodiment provides a kind of method that extends the zeolite tectum life-span by modification and biofilm, it is characterized in that: the method is carried out according to following steps:
Step 1, 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 (preparing with NaCl), system temperature is 28 DEG C, 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 cationic solution that the corresponding 200mL concentration of every 10g natural zeolite is 1.0mol/L;
Step 1.2, outwells supernatant liquor, after using deionized water rinsing modified zeolite clean, is placed in drying in oven, obtains modified zeolite;
Step 2, carries out the activation of substep biofilm to the zeolite after step 1 modification, and concrete colonization method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonas sp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonas sp.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, under 25~30 DEG C, 120rpm constant temperature, 2~3d is cultivated in vibration, obtains respectively enrichment nitrobacteria and denitrifying bacterium bacterium liquid;
Step 2.2: former water is carried out in High pressure steam sterilizer to sterilizing, sterilising conditions is 120~126 DEG C of temperature, pressure 0.10~0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 being obtained and denitrifying bacteria liquid are to add at 1: 9 to former water with former water according to volume ratio respectively, at 25~30 DEG C, 120rpm Water Under bath constant temperature oscillation 2~3d, former water becomes after muddiness, obtains respectively nitrobacteria biofilm bacterium liquid and denitrifying bacterium biofilm bacterium liquid that zeolite biofilm is used;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 being obtained is poured in the container that fills the modified zeolite that step 1.2 obtains, the ratio that adds 20mL~40mL according to every gram of zeolite adds, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, now in water, there is certain dissolved oxygen, hypoxemia is conducive to the growth of nitrobacteria, after 2d~3d, the ratio that the denitrifying bacterium biofilm bacterium liquid again 2.2 steps being obtained adds 20mL~40mL according to every gram of zeolite adds, now control anaerobic state, anaerobic is conducive to denitrifying bacterium growth, at 20 DEG C~40 DEG C, under air tight condition, carry out biofilm, after 3d~4d, adopt solid stream of water to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
Embodiment 14 to 16:
Embodiment 14 is identical with the modification biofilm process of embodiment 13, the Na that it is 1.0mol/L that difference is only the 200mL concentration in step 1.1 +solution (preparing with NaCl) replaces with the K that 200mL concentration is 1.0mol/L +solution (preparing with KCl).Embodiment 15 is identical with the modification biofilm process of embodiment 13, the Na that it is 1.0mol/L that difference is only the 200mL concentration in step 1.1 +solution (preparing with NaCl) replaces with the Ca that 200mL concentration is 1.0mol/L 2+solution (is used CaCl 2preparation).Embodiment 16 is identical with the modification biofilm process of embodiment 13, the Na that it is 1.0mol/L that difference is only the 200mL concentration in step 1.1 +solution (preparing with NaCl) replaces with the Mg that 200mL concentration is 1.0mol/L 2+solution (is used MgCl 2preparation).
The natural zeolite that embodiment 13 to embodiment 21 and comparative example 1 and 2 adopt be above-mentioned natural zeolite F1, F2 and F3 all can, following embodiment is only taking natural zeolite F1 as example explanation.
Comparative example 1: natural zeolite
The zeolite of comparative example 1 had not both adopted cation-modified, did not adopt the actication of culture of embodiment 13 yet, was the natural zeolite of biofilm not.
Comparative example 2: modified zeolite
Other conditions of comparative example 2 are all identical with embodiment 13, and it is cation-modified that difference is only that zeolite only adopts, and do not adopt the actication of culture of embodiment 13, the modified zeolite that embodiment 1 obtains.
Comparative example 3: natural biofilm zeolite
Other conditions of comparative example 3 are all identical with embodiment 13, and difference is not adopt cation-modifiedly, directly adopts the method for embodiment 13 to carry out actication of culture, obtains biofilm natural zeolite.
Testing method: after natural zeolite modification biofilm, measure modification biofilm zeolite and remove ability and the bacterial number of ammonia nitrogen: accurately take the zeolite after a certain amount of modification biofilm, put into respectively the tool plug Erlenmeyer flask of 250mL, adding 200mL mass concentration is the ammonia nitrogen solution of 100mg/L, at 28 DEG C of temperature, rotating speed with 120r/min vibrates on water bath with thermostatic control shaking table, simulation repairing test, after certain interval of time, getting supernatant liquor 0.45 μ m millipore filtration filters, measure ammonia nitrogen, nitre nitrogen and nitrite nitrogen concentration, measuring method is with reference to " water and effluent monitoring analytical procedure ", and adopt MPN method to measure total plate count, nitrifier and denitrifying bacteria quantity.
Comparative example 1, comparative example 2, comparative example 3 contrast with the performance test results of embodiment 13:
Fig. 8, Fig. 9, Figure 10 are the number change of total plate count, nitrifier and denitrifying bacteria in repairing test process, can find out after Zeolite modifying that total bacterium, nitrifier, denitrifying bacteria quantity are all higher than natural unmodified zeolite, after 18d, modification biofilm zeolite total count is 8.5 × 10 6individual/gram zeolite, and natural biofilm system of zeolites total count is 1.1 × 10 6individual/gram zeolite, has improved 8 times, after the modification of nitrifier quantity from 7.1 × 10 4individual/gram zeolite increases to 1.4 × 10 6individual/gram zeolite, has approximately increased 100 times, after the modification of denitrifying bacteria quantity from 1.1 × 10 4individual/gram zeolite is increased to 1.8 × 10 6individual/gram zeolite, has approximately increased 200 times.Visible, after Zeolite modifying, be conducive to the apposition growth of nitrifier and denitrifying bacteria, create strong condition for extending the activated zeolite tectum life-span.
Figure 11 is zeolite in-situ regeneration rate curve over time, and from scheming, in-situ regeneration all exists again in four groups of experiments, but in-situ regeneration speed is not identical.The in-situ regeneration rate that biofilm modified zeolite is one group always, higher than other three groups, shows after Zeolite modifying, and zeolite in-situ regeneration rate obviously increases, the cause increasing mainly due to the nitrifier adhering in zeolite after modification and denitrifying bacteria quantity.The in-situ regeneration rate of biofilm modified zeolite can reach 85.74%, far away higher than the in-situ regeneration rate (49%) of unmodified natural zeolite, also higher than the modified zeolite (69.12%) and the unmodified natural zeolite (54.29%) that are biofilm.
Ammonia nitrogen quality change curve in overlying water when Figure 12 is zeolite in-situ regeneration.As can be seen from the figure, in initial 1 week, because ammonia nitrogen concentration in the release overlying water of bed mud is in rising trend, natural zeolite, modified zeolite, natural biofilm zeolite, biofilm modified zeolite group, maximum ammonia nitrogen quality is respectively 0.72mg, 0.51mg, 0.68mg, 0.28mg, wherein adopt the ammonia nitrogen concentration of biofilm modified zeolite minimum, the effect that shows this system removal ammonia nitrogen is the strongest, after 2 weeks, the ammonia nitrogen quality of biofilm modified zeolite group is 0.08mg, far below natural biofilm zeolite (0.3mg), natural zeolite (0.42mg) and modified zeolite (0.31mg), the method that this explanation modification adds biofilm activation has increased the microbe population that zeolite surface adheres to, can subdue fast the ammonia nitrogen of overlying water.
Nitre nitrogen quality change curve in overlying water when Figure 13 is zeolite in-situ regeneration.From scheming, after 6 days, four groups of nitre nitrogen quality are dense all rises, and the microorganism in this explanation zeolite can be nitre nitrogen by mineralized nitrogen, and obvious nitrification has occurred.After 12 days, the nitre nitrogen of biofilm modified zeolite group overlying water is almost nil, illustrates that microorganism can be further converted to nitre nitrogen nitrogen and remove.And the nitre nitrogen concentration of overlying water is always higher in other three kinds of system of zeolites.
Nitrite nitrogen quality change curve in overlying water when Figure 14 is zeolite in-situ regeneration.From scheming, there is not nitrite nitrogen accumulation in biofilm modified zeolite group in whole experimentation, and this is to remove because biofilm zeolite can be converted into nitrite nitrogen nitrogen.And other three kinds of zeolites nitrite nitrogen after 6 days starts accumulation, within the 15th day, reach maximum.This method that further illustrates that modification adds substep biofilm activation can be that nitrogen is removed fast by mineralized nitrogen, extends the tectal life-span of zeolite.
Embodiment 17: the impact of biofilm time
Test design: take respectively modified zeolite 5g prepared by 3 parts of embodiment 1 in the tool plug Erlenmeyer flask of 250mL, the biofilm bacterium liquid 100mL that all adds the step 2.2 of embodiment 13 to obtain, cultivate after 4,8 and 16 days according to the respectively airtight biofilm of the step 2.3 of embodiment 13, outwell bacterium liquid, rinse gently 2 times with distilled water, 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 12 is the impact of biofilm time on biofilm modified zeolite characterization of adsorption, and table 1 has provided corresponding ammonia nitrogen removal frank.Can find out that 16 days adsorption rate of biofilm are the fastest, incubation time is longer, initial stage adsorption rate is faster, but after reaction 4d, the ammonia nitrogen residual concentration of three groups approaches, biofilm 16d, 8d and 4d ammonia nitrogen residual concentration are respectively 2.96mg/L, 3.82mg/L and 3.68mg/L, ammonia nitrogen removal frank all reaches more than 90%, shows that the biofilm time is greater than 4d just passable.
Embodiment 18: the impact of inoculum size
Test design: take respectively modified zeolite 5g prepared by 3 parts of embodiment 1 in the tool plug Erlenmeyer flask of 250mL, the biofilm bacterium liquid 100mL and the 200mL that add respectively the step 2.2 of embodiment 13 to obtain, step 2.3 difference normal temperature (20 DEG C~23 DEG C) biofilm according to embodiment 13 was cultivated after 8 days, outwell bacterium liquid, rinse gently 2 times with distilled water, 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 13 and table 2 are inoculum size impacts on biofilm modified zeolite characterization of adsorption.When zeolite and biofilm bacterium liquid throwing amount solid-to-liquid ratio (quality: volume) are respectively 1:20 and 1:40, the ammonia-nitrogen content that covers liquid residue on reacting after three days is respectively 3.26mg/L and 1.25mg/L, and ammonia nitrogen removal frank is respectively 86.8% and 92.1%.But after four days, both residual ammonia nitrogen concentration difference is little, is respectively 0.22mg/L and 0.29mg/L, ammonia nitrogen removal frank all reaches more than 90%.Thus can, this shows, the biofilm bacterium liquid that inoculum size adds 20mL~40mL according to every gram of zeolite is just passable.
Embodiment 19: the impact of modification temperature
Test design: take respectively natural zeolite (A), modified zeolite (B), modification biofilm zeolite (C), natural biofilm zeolite (D) 10g 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 and be 0,50,100,150, the ammonium chloride solution 200mL of 200mg/L in weighing up the Erlenmeyer flask of 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 13 zeolite that biofilm obtains.
Interpretation of result: Figure 14 is that Zeolite modifying temperature is 30 DEG C of impacts on in-situ regeneration, can find out when ammonia nitrogen absorption tends towards stability, the clearance of ammonia nitrogen is up to more than 98%, when in the situation that 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 (in table 3).The in-situ regeneration ability that this shows biofilm zeolite is better than non-biofilm zeolite.
Figure 15 is that 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 in the situation that 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 (in table 3); The in-situ regeneration ability that this shows 50 DEG C of modification biofilm zeolites is little compared with 30 DEG C of modification biofilm zeolites.Visible, when modification temperature is 30 DEG C, be in-situ regeneration optimum condition.
Embodiment 20: the impact of biofilm temperature
Test design: take respectively the each 5g of modified zeolite prepared by natural zeolite and embodiment 1, be placed in 250mL Erlenmeyer flask, add 20mL biofilm bacterium liquid according to every gram of zeolite, biofilm temperature is controlled at respectively 20 DEG C (room temperature states), 30 DEG C (constant temperature water bath heating), 40 DEG C (constant temperature water bath heating), carries out airtight biofilm according to the step 2.3 of embodiment 13.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 16 is the impact of biofilm temperature on zeolite in-situ regeneration.In the time that biofilm temperature is 40 DEG C, in-situ regeneration maximum is 9.94mg/L (in table 4).In the time that biofilm temperature is 30 DEG C, in-situ regeneration maximum is 5.35mg/L.But in the time that biofilm temperature is 20 DEG C, zeolite does not have in-situ regeneration.
As can be seen from Figure 17, in the time that biofilm temperature is 30 DEG C, it is 5.48mg/L that in-situ regeneration reached maximum in the time of the 4th day.In the time that biofilm temperature is 20 DEG C and 40 DEG C, zeolite does not have in-situ regeneration.Visible, the temperature that biofilm is suitable is 30 DEG C~40 DEG C.
Embodiment 21: the impact of biofilm mode
Test design: take respectively modified zeolite 70g prepared by 3 parts of embodiment 1 in the vial of 5L, the biofilm bacterium liquid 1400mL that all adds the step 2.2 of embodiment 13 to obtain, according to the step 2.3 of embodiment 13 carry out respectively zeolite continuous aeration biofilm, not aeration leave standstill uncovered biofilm and leave standstill airtight biofilm, cultivate after 8 days, outwell bacterium liquid, rinse gently 2 times with distilled water, obtain biofilm modified zeolite.
At the bottom of bed mud is evenly rendered to highly to the synthetic glass post for 1.2m, DN300mm, bed mud thickness is 50cm left and right (quality is about 55kg), and by above-mentioned biofilm modified zeolite uniform fold, on bed mud, coverage strength is 2kg/m 2, more former ancient canal water is slowly injected, making overlying water is 50cm left and right (volume is about 35L) deeply, carries out the test of biofilm modified zeolite reparation bed mud.
Interpretation of result: Figure 18 has provided overlying water total nitrogen concentration changing conditions in bed mud repair process, can find out after the system reparation 60d that covers airtight biofilm zeolite, total nitrogen concentration is reduced to rapidly 2.76mg/L, 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, between (nitrogen removal rate 71%) between the two, does not show that airtight biofilm mode is optimum mode.In repair process, residual ammonia nitrogen, nitre nitrogen and nitrite nitrogen concentration are shown in Figure 19,20,21.Repair after 53d, airtight biofilm, aeration biofilm, the residual ammonia nitrogen concentration of continuous aeration biofilm three individual system are not respectively 0.73mg/L, 1.77mg/L, 8.83mg/L, ability (the seeing Figure 19) the most by force of airtight biofilm zeolite adsorption ammonia nitrogen is described, ammonia nitrogen can also be further converted to nitre nitrogen (seeing Figure 20), in-situ regeneration occurs.In addition, the nitrite nitrogen concentration of three individual system is all lower, does not occur nitrite nitrogen accumulation (seeing Figure 21).
Embodiment 22: analyzing of applying effects
Take 5 parts of 200g Grand Canal in Yangzhou bed muds of bed mud, be laid in the glass jar of 5L, take respectively natural zeolite (1#), modified zeolite (2#), natural biofilm zeolite (3#), modification biofilm zeolite (4#) 70g, uniform spreading is on bed mud, slowly adding TN concentration is the source water of 3.13mg/L, carry out repairing test, establish one group of blank that does not add zeolite.In order to measure the tectal life cycle of zeolite, bed mud after stopping discharging takes out zeolite layer, is reentered into bed mud and carries out new round test, carries out altogether 4 and takes turns test.
Interpretation of result: Figure 25 is the rate of the subduing change curve of total nitrogen in overlying water, the strongest from scheming the ability that known modification biofilm zeolite tectum subdues TN, longest-lived, 1 to 4 takes turns the clearance of TN in test is respectively 88.28%, 85.87%, 83.58%, 80.40%, as shown in table 5, the ability of reusing post-modification biofilm zeolite tectum removal total nitrogen for 4 times is substantially constant, improved the quantity of adhering to nitrifier and denitrifying bacteria on zeolite mainly due to modification, in-situ regeneration rate is up to more than 90%, reuse rear TN clearance for 4 times still up to 80%, show that modification biofilm zeolite tectum can repair polluted bed mud long-term effectively.
But other three kinds of zeolite layer natural zeolites, day biofilm zeolite, modified zeolite use the clearance of TN after 4 times lower, difference 15%, 35% and 58%, part zeolite lost efficacy, and can not repair long-term effectively polluted bed mud.
The impact of table 1 biofilm time
The impact of table 2 inoculum size
The impact of table 3 modification temperature
The impact of table 4 biofilm temperature
The in-situ regeneration situation of 4 recyclings of table 5 zeolite tectum

Claims (7)

1. a method that extends the activated zeolite tectum life-span, is characterized in that: the method is carried out according to following steps:
Step 1, 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 cationic solution, and system temperature is 28 DEG C~50 DEG C, and regulation system pH value, in 4~11 scopes, is adsorbed exchange on water bath with thermostatic control shaking table, and successive reaction 24h, obtains modified zeolite;
Wherein, the cationic solution that the corresponding 200mL concentration of every 5g~15g natural zeolite is 1.0mol/L~2.0mol/L;
Step 1.2, outwells supernatant liquor, after using deionized water rinsing modified zeolite clean, is placed in drying in oven, obtains modified zeolite;
Step 2, carries out the activation of substep biofilm to the zeolite after step 1 modification, and concrete substep biofilm activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonas sp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonas sp.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, under 25~30 DEG C, 120rpm constant temperature, 2~3d is cultivated in vibration, obtains respectively enrichment nitrobacteria and denitrifying bacterium bacterium liquid;
Step 2.2: former water is carried out in High pressure steam sterilizer to sterilizing, sterilising conditions is 120~126 DEG C of temperature, pressure 0.10~0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 being obtained and denitrifying bacteria liquid are to add at 1: 9 to former water with former water according to volume ratio respectively, at 25~30 DEG C, 120rpm Water Under bath constant temperature oscillation 2~3d, obtain respectively nitrobacteria biofilm bacterium liquid and denitrifying bacterium biofilm bacterium liquid that zeolite biofilm is used;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 being obtained is poured in the container that fills the modified zeolite that step 1.2 obtains, the ratio that adds 20mL~40mL according to every gram of zeolite adds, under 20 DEG C~40 DEG C, air tight condition, carry out biofilm, the ratio that the denitrifying bacterium biofilm bacterium liquid again 2.2 steps being obtained after 2d~3d adds 20mL~40mL according to every gram of zeolite adds, under 20 DEG C~40 DEG C, air tight condition, carry out biofilm, after 3d~4d, adopt solid stream of water to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
2. the method for claim 1, is characterized in that: the method is carried out according to following steps:
Step 1, 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 cationic solution, and system temperature is 28 DEG C, and regulation system pH value is 9, carries out modification, successive reaction 24h on water bath with thermostatic control shaking table;
Wherein, the cationic solution that the corresponding 200mL concentration of every 10g natural zeolite is 1.0mol/L;
Step 1.2, outwells supernatant liquor, after using deionized water rinsing modified zeolite clean, is placed in drying in oven, obtains modified zeolite;
Step 2, carries out biofilm activation to the zeolite after step 1 modification, and concrete activation method carries out according to following steps:
Nitrobacteria is pseudomonas SY1 (Pseudomonas sp.SY1), deposit number CCTCCNO:M209181; Denitrifying bacterium is pseudomonas HY1 (Pseudomonas sp.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, under 25~30 DEG C, 120rpm constant temperature, 2~3d is cultivated in vibration, obtains respectively enrichment nitrobacteria and denitrifying bacterium bacterium liquid;
Step 2.2: former water is carried out in High pressure steam sterilizer to sterilizing, sterilising conditions is 120~126 DEG C of temperature, pressure 0.10~0.14MPa, time 30min, then enrichment nitrobacteria bacterium liquid step 2.1 being obtained and denitrifying bacteria liquid are to add at 1: 9 to former water with former water according to volume ratio respectively, at 25~30 DEG C, 120rpm Water Under bath constant temperature oscillation 2~3d, obtain respectively nitrobacteria biofilm bacterium liquid and denitrifying bacterium biofilm bacterium liquid that zeolite biofilm is used;
Step 2.3: the nitrobacteria biofilm bacterium liquid first step 2.2 being obtained is poured in the container that fills the modified zeolite that step 1.2 obtains, the ratio that adds 20mL~40mL according to every gram of zeolite adds, under 20 DEG C~40 DEG C, air tight condition, carry out biofilm, the ratio that the denitrifying bacterium biofilm bacterium liquid again 2.2 steps being obtained after 2d~3d adds 20mL~40mL according to every gram of zeolite adds, under 20 DEG C~40 DEG C, air tight condition, carry out biofilm, after 3d~4d, adopt solid stream of water to wash out the bacterium of the absorption of filling surface, obtain modification biofilm zeolite.
3. the method as described in claim 1 and 2 arbitrary claims, is characterized in that: described cationic solution is for containing Na +, K +, Ca 2+or Mg 2+solion.
4. method as claimed in claim 3, is characterized in that: described cationic solution is Na +solion.
5. the method as described in claim 1 and 2 arbitrary claims, is characterized in that: the rotating speed of the water bath with thermostatic control shaking table described in step 1.1 is 120r/min.
6. method as claimed in claim 3, is characterized in that: in described cationic solution: Na +solion adopts NaCl preparation, K +solion adopts KCl preparation, Ca 2+solion adopts CaCl 2preparation, Mg 2+solion adopts MgCl 2preparation.
7. method as claimed in claim 4, is characterized in that: Na in described cationic solution +solion adopts NaCl preparation.
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