CN103013973A - Method for preparing aerobiotic nitrifier immobilizing vector - Google Patents
Method for preparing aerobiotic nitrifier immobilizing vector Download PDFInfo
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- CN103013973A CN103013973A CN201210544859XA CN201210544859A CN103013973A CN 103013973 A CN103013973 A CN 103013973A CN 201210544859X A CN201210544859X A CN 201210544859XA CN 201210544859 A CN201210544859 A CN 201210544859A CN 103013973 A CN103013973 A CN 103013973A
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Abstract
The invention discloses a method for preparing an aerobiotic nitrifier immobilizing vector, and belongs to the field of water treatment. The method comprises the steps of: firstly, carrying out acid washing on thermally modified attapulgite; adsorbing the nitrifier using the nanometer grade attapulgite; carrying out rapid inclusion by using the mixture gel of polyvinyl alcohol (PVA) and sodium alginate (SA); dropping the mixture into a crosslinking agent to soak for 24 hours using a granulator to obtain an immobilized nitrifier pellet; and finally, repeatedly washing the immobilized nitrifier pellet for three times using normal saline to obtain a vector particle. By taking advantage of pretty large specific surface area and pretty strong adsorption performance of the modified attapulgite, an adsorption vector which is conductive to the growth and reproduction of the aerobiotic nitrifier is prepared; the modified attapulgite is capable of ammonia and nitrogen adsorption, and can increase the ammonia and nitrogen removal rate in water; the carrier particle composited from the modified attapulgite and a macromolecular material can improve the activity and ammonia and nitrogen removal capacity of denitrification microorganisms; and the repeated use rate of the carrier is high.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of method for preparing aerobic nitrifier fixation support.
Background technology
Quickening along with Urbanization in China, the day by day raising of people's living standard, requirement to urban environment around it is more and more higher, city inland river is as resources and environment carrier important in the urban development, be related to the sound development in city, restricting urban development, is the important factor that affects Urban style and beautifying urban environment.At present, pollution source of water body can not get control, and trade effluent, the in line phenomenon of sanitary sewage are serious, and the urban river blackening is fouled, and the algae reproduction phenomenon is on the rise, according to investigations nearly 50% pollution that is subject in various degree of China's city river.Take Taihu Lake basin as example, make a general survey of the quality of water environment of main cities, water quality condition allows of no optimist, and total nitrogen, ammonia nitrogen, total phosphorus, COD are primary pollutant, and wherein polluted by nitrogen is the most serious.The river denitrogenation has become one of emphasis of Urban Water Environment comprehensive improvement.
In water body nitrogen cycle process, biological nitrogen fixation, ammonification, the peculiar environmental functional that nitrated, denitrification is microorganism, microorganism is the ammonia nitrogen in the water body, nitrous acid nitrogen and nitrate transformation nitrogen by ammonification, nitrification, denitrification, thereby the ammonia nitrogen in the reduction water body, nitroso-group nitrogen and nitrate have played the effect that prevents algal bloom.As seen, microorganism plays an important role in the river denitrogenation.But in the ecological management in river, directly add thalline and easily cause outflowing with water of thalline, must take immobilized effective means.Compare with traditional bio-denitrification technology, microbial immobilized technology has become one of the most popular research direction, wherein, entrapping method be study the most extensive and use one of best technology the earliest, embedding techniques not only can stop poky microorganism to leak out, but also alleviate ammonia nitrogen loading and the impact of other toxic pollutants on microorganism, such as patent of invention CN101497880A(novel method of improving the PVA immobilized microorganism).But the immobilized microorganism that entrapping method makes has certain impact to mass transfer, and the fixation support less stable, and work-ing life is short, and therefore, the over-all properties of fixed microorganism carrier has much room for improvement.
Summary of the invention
The object of the invention is to: a kind of method for preparing aerobic nitrifier fixation support is provided, the method adopts modified natural attapulgite sorbing material and macromolecular material polyvinyl alcohol and the fixing aerobic nitrifier of sodium alginate utilization absorption embedding techniques to prepare the carrier granule that hole is fine and close evenly, mass-transfer performance is good, to improve ammonia nitrogen removal frank.
Technical solution of the present invention is: first pickling heat modification attapulgite, utilize nano level attapulgite absorption nitrobacteria, recycling polyvinyl alcohol (PVA) and sodium alginate (SA) mixed gel carry out Rapid embedding, and with nodulizer mixture is splashed into and to soak 24h in the linking agent, being fixed thalline bead; At last, use again the physiological saline repeated washing three times; Namely get carrier granule.
A kind of method for preparing aerobic nitrifier fixation support of the present invention, carry out according to following step:
(1) modified attapulgite: after the pulverizing of attapulgite raw ore, cross 200 mesh sieves, under 80 ℃ of conditions, be immersed in 2-4h in the hydrochloric acid soln of 1-6mol/L according to solid-to-liquid ratio 1:10, and stir once per half an hour, filtering and washing is to neutral after the pickling, place it in again in the muffle furnace in 200-250 ℃ of high-temperature calcination 2h, after the cooling, grind;
(2) domestication aerobic nitrification bacterium: the high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, changed water once in two days, upper strata liquid is removed in clarification again before changing water, adds isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d;
(3) preparation of embedding gel: under 90 ℃ bath temperature, polyvinyl alcohol and sodium alginate are dissolved in respectively in the distilled water, constantly stir 2-3h, leave standstill, after the bubble in colloid is overflowed fully with the two stirring and evenly mixing; Be cooled to 25-30 ℃ for subsequent use, wherein the content of polyvinyl alcohol is 70-80g/L, the content of sodium alginate is 20-30g/L;
(4) immobilization particle preparation process: the aerobic nitrification bacterium that will tame is that 10:1 (ml:g) adding holds in the Erlenmeyer flask of modified attapulgite according to liquid-solid ratio, be placed in the shaking table, in 28-30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains the attapulgite throw out; Then will mix the embedding gel by volume 2-3:1 join in the modified attapulgite throw out stirring and evenly mixing; And freely vertically splash into nodulizer and to contain massfraction 3-5%CaCI
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use, can obtain aerobic nitrification bacteria immobilization carrier.
Wherein the nitrifier enrichment culture liquid described in the step (2) is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH.
The invention has the advantages that:
1, utilizes the attapulgite of modification to have larger specific surface area and stronger absorption property, prepare the absorption carrier that is fit to the breeding of aerobic nitrification bacteria growing.
2, the attapulgite after the modification itself has the ability of absorption ammonia nitrogen, can improve the clearance of ammonia nitrogen in the water body;
3, modified attapulgite can change the mass-transfer performance of PVA and SA gel, is conducive to the exchange of product conveying and gas;
4, utilize the compound carrier granule of preparing of modified attapulgite and macromolecular material, the ability that can improve the active of denitrification microorganism and remove ammonia nitrogen; And repeat usage is also very high.
Embodiment
Embodiment 1
To originate from the attapulgite ore of Xuyi after the fast-crushing machine is pulverized, cross 200 mesh sieves, getting the 5g concave and convex rod stone powder is placed in the 50ml hydrochloric acid soln (concentration 1mol/L), under 70 ℃ of conditions, soak 2h, then use the distilled water filtering and washing to neutral, be placed on 200 ℃ of high-temperature calcination 2h in the muffle furnace, cooling is ground for subsequent use;
The high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, change water once in two days, and changed the front clarification of water and remove again upper strata liquid, add isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d, for subsequent use; Nitrifier enrichment culture liquid is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH;
Get aerobic nitrification bacterium that 10ml tamed and add and hold in the Erlenmeyer flask of 1g modified attapulgite, in 30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains attapulgite throw out 5ml; Then 10ml embedding gel is joined wherein stirring and evenly mixing; And freely vertically splash into nodulizer and to contain 3%CaCl
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use.The bead for preparing is placed in the autogamy ammonia nitrogen waste water, and through behind 7 days Air Exposures, ammonia nitrogen removal frank is up to 83 ~ 85%, and bead physical strength and denitrification ability that still the keeper is higher.
Embodiment 2
To originate from the attapulgite ore of Xuyi after the fast-crushing machine is pulverized, cross 200 mesh sieves, getting the 5g concave and convex rod stone powder is placed in the 50ml hydrochloric acid soln (concentration 6mol/L), under 70 ℃ of conditions, soak 4h, then use the distilled water filtering and washing to neutral, be placed on 250 ℃ of high-temperature calcination 2h in the muffle furnace, cooling is ground for subsequent use;
The high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, change water once in two days, and changed the front clarification of water and remove again upper strata liquid, add isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d, for subsequent use; Nitrifier enrichment culture liquid is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH;
Get aerobic nitrification bacterium that 20ml tamed and add and hold in the Erlenmeyer flask of 2g modified attapulgite, in 30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains attapulgite throw out 12ml; Then 24ml embedding gel is joined wherein stirring and evenly mixing; And freely vertically splash into nodulizer and to contain 5%CaCl
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use.The bead for preparing is placed in the autogamy ammonia nitrogen waste water, and through behind 7 days Air Exposures, ammonia nitrogen removal frank is up to 83 ~ 85%, and bead physical strength and denitrification ability that still the keeper is higher.
Embodiment 3
To originate from the attapulgite ore of Xuyi after the fast-crushing machine is pulverized, cross 200 mesh sieves, getting the 5g concave and convex rod stone powder is placed in the 50ml hydrochloric acid soln (concentration 2mol/L), under 70 ℃ of conditions, soak 4h, then use the distilled water filtering and washing to neutral, be placed on 250 ℃ of high-temperature calcination 2h in the muffle furnace, cooling is ground for subsequent use;
The high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, change water once in two days, and changed the front clarification of water and remove again upper strata liquid, add isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d, for subsequent use; Nitrifier enrichment culture liquid is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH;
Get aerobic nitrification bacterium that 30ml tamed and add and hold in the Erlenmeyer flask of 3g modified attapulgite, in 30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains attapulgite throw out 15ml; Then 30ml embedding gel is joined wherein stirring and evenly mixing; And freely vertically splash into nodulizer and to contain 4%CaCl
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use.The bead for preparing is placed in the autogamy ammonia nitrogen waste water, and through behind 7 days Air Exposures, ammonia nitrogen removal frank is up to 83 ~ 85%, and bead physical strength and denitrification ability that still the keeper is higher.
Embodiment 4
To originate from the attapulgite ore of Xuyi after the fast-crushing machine is pulverized, cross 200 mesh sieves, getting the 5g concave and convex rod stone powder is placed in the 50ml hydrochloric acid soln (concentration 4mol/L), under 70 ℃ of conditions, soak 4h, then use the distilled water filtering and washing to neutral, be placed on 250 ℃ of high-temperature calcination 2h in the muffle furnace, cooling is ground for subsequent use;
The high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, change water once in two days, and changed the front clarification of water and remove again upper strata liquid, add isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d, for subsequent use; Nitrifier enrichment culture liquid is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH;
Get aerobic nitrification bacterium that 10ml tamed and add and hold in the Erlenmeyer flask of 1g modified attapulgite, in 30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains attapulgite throw out 5ml; Then 15ml embedding gel is joined wherein stirring and evenly mixing; And freely vertically splash into nodulizer and to contain in the saturated boric acid solution of 5%CaCl2, and constantly to stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use.The bead for preparing is placed in the autogamy ammonia nitrogen waste water, and through behind 7 days Air Exposures, ammonia nitrogen removal frank is up to 83 ~ 85%, and bead physical strength and denitrification ability that still the keeper is higher.
Embodiment 5
To originate from the attapulgite ore of Xuyi after the fast-crushing machine is pulverized, cross 200 mesh sieves, getting the 5g concave and convex rod stone powder is placed in the 50ml hydrochloric acid soln (concentration 4mol/L), under 70 ℃ of conditions, soak 4h, then use the distilled water filtering and washing to neutral, be placed on 200 ℃ of high-temperature calcination 2h in the muffle furnace, cooling is ground for subsequent use;
The high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, change water once in two days, and changed the front clarification of water and remove again upper strata liquid, add isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d, for subsequent use; Nitrifier enrichment culture liquid is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH;
Get aerobic nitrification bacterium that 20ml tamed and add and hold in the Erlenmeyer flask of 2g modified attapulgite, in 30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains attapulgite throw out 10ml; Then 30ml embedding gel is joined wherein stirring and evenly mixing; And freely vertically splash into nodulizer and to contain 4%CaCl
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use.The bead for preparing is placed in the autogamy ammonia nitrogen waste water, and through behind 7 days Air Exposures, ammonia nitrogen removal frank is up to 83 ~ 85%, and bead physical strength and denitrification ability that still the keeper is higher.
Claims (2)
1. method for preparing aerobic nitrifier fixation support is characterized in that carrying out according to following step:
(1) modified attapulgite: after the pulverizing of attapulgite raw ore, cross 200 mesh sieves, under 80 ℃ of conditions, be immersed in 2-4h in the hydrochloric acid soln of 1-6mol/L according to solid-to-liquid ratio 1:10 (g:ml), and stir once per half an hour, filtering and washing is to neutral after the pickling, place it in again in the muffle furnace in 200-250 ℃ of high-temperature calcination 2h, after the cooling, grind;
(2) domestication aerobic nitrification bacterium: the high-efficiency activated mud of taking from sewage work's biochemistry pool joins in the nitrifier enrichment culture liquid, at 28-30 ℃, pH is under the 7.0-8.0 condition, take the intermittent aeration mode, changed water once in two days, upper strata liquid is removed in clarification again before changing water, adds isopyknic nitrobacteria enrichment culture liquid, enrichment culture 28d;
(3) preparation of embedding gel: under 90 ℃ bath temperature, polyvinyl alcohol and sodium alginate are dissolved in respectively in the distilled water, constantly stir 2-3h, leave standstill, after the bubble in colloid is overflowed fully with the two stirring and evenly mixing; Be cooled to 25-30 ℃ for subsequent use, wherein the content of polyvinyl alcohol is 70-80g/L, the content of sodium alginate is 20-30g/L;
(4) immobilization particle preparation process: the aerobic nitrification bacterium that will tame is that 10:1 (ml:g) adding holds in the Erlenmeyer flask of modified attapulgite according to liquid-solid ratio, be placed in the shaking table, in 28-30 ℃, under the 130r/min condition, vibration absorption 120min, after the vibration, static 90min, low speed 600r.min
-1Centrifugal 2min under the condition pours out supernatant liquor and obtains the attapulgite throw out; Then will mix the embedding gel by volume 2-3:1 join in the modified attapulgite throw out stirring and evenly mixing; And freely vertically splash into nodulizer and to contain massfraction 3-5%CaCI
2In the saturated boric acid solution, and constantly stir, titration is placed on crosslinked fixedly 24h in the refrigerator after finishing, and uses at last 0.9% normal saline flushing three times, is placed in 4 ℃ of refrigerators and preserves, and is for subsequent use, can obtain aerobic nitrification bacteria immobilization carrier.
2. a kind of method for preparing aerobic nitrifier fixation support according to claim 1 is characterized in that wherein the nitrifier enrichment culture liquid described in the step (2) is glucose 14.1g/L, NH
4CI 1.34g/L, KH
2PO
40.7g/L, MgSO
40.5g/L, CaCI
20.5g/L 20min sterilizes under 7.5,121 ℃ of conditions of pH.
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