CN114772732B - Device and method for removing antibiotics in marine product culture wastewater - Google Patents
Device and method for removing antibiotics in marine product culture wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 27
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 171
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000004098 Tetracycline Substances 0.000 claims abstract description 77
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 77
- 229960002180 tetracycline Drugs 0.000 claims abstract description 70
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- OJMMVQQUTAEWLP-KIDUDLJLSA-N lincomycin Chemical compound CN1C[C@H](CCC)C[C@H]1C(=O)N[C@H]([C@@H](C)O)[C@@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](SC)O1 OJMMVQQUTAEWLP-KIDUDLJLSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a device and a method for removing antibiotics in marine culture wastewater, and belongs to the technical field of wastewater treatment. The removal device comprises a reactor, wherein the reactor comprises a reaction column; the lower end of the reaction column is a closed end; the inner wall of the reaction column is connected with a baffle plate which divides the interior of the reaction column into a first reaction chamber and a second reaction chamber, and the two reaction chambers are communicated with each other at the upper end and the lower end of the reaction column; the position of the first reaction chamber, which is close to the closed end, is provided with a water inlet, the position of the second reaction chamber, which is close to the closed end, is connected with an aerator, and the middle part of the second reaction chamber is provided with a first water outlet. The removing device has simple structure and low cost, and can be popularized and applied in the aspect of removing antibiotics (such as tetracycline) in marine culture wastewater. The corresponding removal method is simple to operate, the process is easy to control, and tetracycline in the marine culture wastewater can be removed efficiently.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a device and a method for removing antibiotics in marine culture wastewater.
Background
Aquaculture is the fastest growing food production sector in the world for nearly 40 years, with marine aquaculture accounting for 1/3 of the whole. In order to prevent and treat diseases of fish and other marine animals, tetracycline, one of the most widespread antibiotics, is used in a large amount. It is counted that europe and the united states consume about 5500 tons of tetracycline each year. Unfortunately, antibiotics are not efficiently metabolized by animals, which results in the discharge of marine culture wastewater containing large amounts of antibiotics into receiving water bodies, thereby causing environmental pollution and ecological damage.
The circulating culture mode (RAS) is one of the modes of aquaculture with the highest industrialization degree, and can realize energy-saving and emission-reducing environment-friendly production and even zero-emission production modes through on-line sewage treatment. However, these treatment units often employ conventional aerobic biological treatment or biofilter technology, which is ineffective in removing nitrate nitrogen and accumulated antibiotics in the system.
It is reported that the removal effect of the conventional biological treatment process on typical antibiotics is general, for example, the average removal rate of lincomycin is only 42.1%, aureomycin is 58.8%, and sulfamethoxazole and tetracycline are about 66%.
Thus, there is a great need for a treatment route that allows for the economical and efficient removal of tetracyclines.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a device and a method for removing antibiotics in marine culture wastewater, so as to solve the technical problems.
The application can be realized as follows:
in a first aspect, the present application provides a device for removing antibiotics from seafood cultivation wastewater, comprising a reactor comprising a reaction column;
the lower end of the reaction column is a closed end;
the inside of the reaction column is provided with a baffle plate which is connected with the inner wall of the reaction column and vertically separates the inside of the reaction column into a first reaction chamber and a second reaction chamber, and the first reaction chamber and the second reaction chamber are communicated with each other at the upper end and the lower end of the reaction column, so that granular sludge in the reaction column and marine culture wastewater to be treated can circularly flow along the first reaction chamber to the second reaction chamber in the treatment process;
the position of the first reaction chamber, which is close to the closed end, is provided with a water inlet, the position of the second reaction chamber, which is close to the closed end, is connected with an aerator, and the middle part of the second reaction chamber is provided with a first water outlet.
In an alternative embodiment, the bottom of the reaction column is also provided with a controller for controlling the water inlet and outlet conditions.
In an alternative embodiment, the top of the reaction column is also sleeved with a protection cylinder (preventing abnormal system operation from overflowing), the upper end of the protection cylinder is open, the lower end of the protection cylinder is closed, and the side wall of the protection cylinder is provided with a second water outlet.
In a second aspect, the present application provides a method for removing tetracycline from seafood culture wastewater, comprising the steps of: the removal device of any of the preceding embodiments is used to remove antibiotics from the seafood wastewater to be treated.
In an alternative embodiment, the antibiotic is tetracycline.
In an alternative embodiment, the removal process comprises at least 1 treatment cycle, each treatment cycle comprising in sequence a water inlet phase, an anaerobic phase, an aerobic phase, a sedimentation phase, a water outlet phase and a rest phase;
the marine culture wastewater to be treated is introduced into a reaction column containing granular sludge through a water inlet in the water inlet stage; and then carrying out anaerobic stage treatment, introducing air into the reaction column through an aerator after entering an aerobic stage, settling granular sludge in a settling stage, and discharging treated marine culture wastewater through a first water outlet in a water outlet stage.
In an alternative embodiment, the volume of the seafood wastewater per replacement during the treatment is 1/2 of the volume of the reaction column.
In an alternative embodiment, the ratio of processing times for each stage is 10:50-70:130-160:5:10:10 in sequence.
In an alternative embodiment, each treatment cycle is 4 hours.
In an alternative embodiment, the addition amount of the granular sludge in the reaction column is 1300-2500mg/L, and the particle size of the granular sludge is 0.8-2.5mm in the removal process.
In an alternative embodiment, the hydraulic residence time in the reaction column is 8 hours throughout the removal process.
In an alternative embodiment, the dissolved oxygen level in the reaction column does not exceed 0.4mg/L during the anaerobic phase.
In an alternative embodiment, the dissolved oxygen level in the reaction column is not less than 4mg/L during the aerobic phase.
In an alternative embodiment, the water temperature during removal is 20-35 ℃.
The beneficial effects of this application include:
the removing device provided by the application can enable the granular sludge to generate better treatment effect on the antibody under the action of shearing force. Specifically, marine product aquaculture wastewater added from the water inlet is downwards collected in the first reaction chamber under the action of self gravity and flows into the second reaction chamber through the closed end at the lower end of the reaction column, then more and more wastewater is continuously introduced into the first reaction chamber, meanwhile, the amount of marine product aquaculture wastewater entering into the second reaction chamber is increased, the liquid level in the second reaction chamber is gradually increased until the marine product aquaculture wastewater flows back to the first reaction chamber again through the upper end of the reaction column, and impact force is generated on the wastewater in the first reaction chamber, which is close to the lower end of the reaction column, so that the wastewater in the reaction column can continuously flow along the anticlockwise direction to form stronger shearing force.
The device for removing the antibiotics in the marine culture wastewater has the advantages of simple structure and low cost, and can be popularized and applied in the aspect of removing the antibiotics (such as tetracycline) in the marine culture wastewater. The corresponding removal method is simple to operate, the process is easy to control, antibiotics in marine culture wastewater can be efficiently removed, COD, ammonia nitrogen and total nitrogen contained in the wastewater are stably treated, and the problem of low total nitrogen and antibiotic removal efficiency in the existing circulating culture mode is solved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of a device for removing antibiotics from marine culture wastewater provided by the application;
FIG. 2 shows SVI corresponding to sludge in S1 and S2 in the test example 30 Results;
FIG. 3 shows the MLVSS results corresponding to the sludge in S1 and S2 in the test example;
FIG. 4 shows average diameters corresponding to sludge in S1 and S2 in the test example;
FIG. 5 is a graph showing the kinetics of particle attrition in S2 in the test example;
FIG. 6 shows the COD results in S1 and S2 in the test examples;
FIG. 7 is NH in S1 and S2 in the test example 4 + -N results;
FIG. 8 shows TN results in S1 and S2 in the test examples;
FIG. 9 shows the results of specific removal performance and total removal efficiency of tetracycline (TET) in S1 and S2 in the test examples;
FIG. 10 shows EPS concentration in S1 and S2 in the test examples;
FIG. 11 shows adsorption results of TET by AS at different concentrations in the test example;
FIG. 12 shows the adsorption results of GS to TET at different concentrations in the test example;
FIG. 13 shows the biodegradation results of TET by AS at different concentrations in the test examples;
FIG. 14 shows the biodegradation results of TET with GS at various concentrations in the test examples;
FIG. 15 shows TET removal efficiency and adsorption and biodegradation rates at various concentrations in the test examples.
Icon: 1-a reaction column; 2-baffle plates; 11-a first reaction chamber; 12-a second reaction chamber; 3-a water inlet; 4-an aerator; 51-a first water outlet; 52-sampling port; 6, a protection cylinder; 61-a second water outlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The device and the method for removing antibiotics in marine culture wastewater provided by the application are specifically described below.
The application provides a device for removing antibiotics in marine culture wastewater, which comprises a reactor, wherein the reactor comprises a reaction column 1, as shown in figure 1.
By way of example and not limitation, the reaction column 1 may be a column having an inner diameter of 50mm, a height of 1000mm, and a volume of about 1.1L.
The lower end of the reaction column 1 is a closed end, and the upper end is an open end. The interior of the reaction column 1 provides a treatment space for the water treatment stage, so that the granular sludge can effectively adsorb (primary) and biodegrade (secondary) tetracycline in the marine culture wastewater to be treated in the treatment space.
The reaction column 1 is internally provided with a baffle plate 2, and the baffle plate 2 is connected to the inner wall of the reaction column 1 and vertically divides the interior of the reaction column 1 into a first reaction chamber 11 and a second reaction chamber 12.
Preferably, the baffle plate 2 equally divides the interior of the reaction column 1 into a first reaction chamber 11 and a second reaction chamber 12 of equal volume.
It should be noted that the first reaction chamber 11 and the second reaction chamber 12 are connected to each other at the upper end and the lower end of the reaction column 1, so that the granular sludge in the reaction column 1 and the seafood culture wastewater to be treated can flow circularly (can be understood as flowing in the counterclockwise direction) along the first reaction chamber 11 to the second reaction chamber 12 during the treatment.
The first reaction chamber 11 is provided with a water inlet 3 near the closed end (lower end), and the water inlet 3 can be connected with a peristaltic pump to introduce the marine culture wastewater to be treated into the reaction column 1 from the water inlet 3.
The above-mentioned counterclockwise direction is based on that the firstly added marine product cultivation wastewater is collected downwards in the first reaction chamber 11 under the action of self gravity and flows into the second reaction chamber 12 through the closed end of the lower end of the reaction column 1, then more and more waste water is continuously introduced into the first reaction chamber 11, meanwhile, the marine product cultivation wastewater amount entering into the second reaction chamber 12 is increased, the liquid level in the second reaction chamber 12 is gradually increased until the marine product cultivation wastewater flows back to the first reaction chamber 11 again through the upper end of the reaction column 1, and impact force is generated on the waste water in the first reaction chamber 11, which is close to the lower end of the reaction column 1, so that the waste water in the reaction column 1 can continuously flow in the counterclockwise direction. Through the flowing mode, the granular sludge can obtain better treatment effect under the action of shearing force.
An aerator 4 is connected to the second reaction chamber 12 at a position close to the closed end of the lower end of the reaction column 1, and the aerator 4 is used for introducing oxygen into the reaction column 1 in a specific treatment stage (an aerobic stage described below).
The middle part of the second reaction chamber 12 is provided with a first water outlet 51 for discharging the treated marine culture wastewater from which the tetracycline is removed.
For reference, the first water outlet 51 may be provided at 1/2 height of the reaction column 1. The reaction column 1 is provided with a sampling port 52 at a position flush with the first water outlet 51.
In addition, the bottom of the reaction column 1 is also provided with a controller (not shown) for controlling water inlet conditions and water outlet conditions, and timely controlling and adjusting water inlet and water outlet conditions. For reference, the controller may be a time-controlled switch.
Preferably, when the top of the reaction column 1 is an open top, the top of the reaction column 1 may be further sleeved with a protection tube 6 (preventing abnormal system running water from overflowing), the upper end of the protection tube 6 is open, the lower end is closed, and the side wall of the protection tube 6 is provided with a second water outlet 61.
By sleeving the protection cylinder 6, when the first water outlet 51 has a problem or the controller has a fault, the overflowed water in the reaction column 1 can be timely discharged to the designated wastewater collection container.
In some embodiments, a sampling port may be further provided on the reaction column 1 at a position flush with the first water outlet 51, so that part of the liquid in the reaction column 1 can be taken out from the measuring port at any time during the treatment process for detection.
The other structures of the above-mentioned removing device can refer to a Sequencing Batch Reactor (SBR), and will not be described in detail herein.
Correspondingly, the application also provides a method for removing antibiotics in marine culture wastewater, which comprises the following steps: the antibiotics in the marine culture wastewater to be treated are removed by adopting the removing device.
The antibiotic may be, by way of example and not limitation, tetracycline.
By way of reference, the removal process comprises at least 1 treatment cycle, in particular, the treatment cycles may be, for example, 1, 2, 3, 4 or more.
Each treatment period sequentially comprises a water inlet stage, an anaerobic stage, an aerobic stage, a sedimentation stage, a water outlet stage and a standing stage.
The marine culture wastewater to be treated is introduced into a reaction column 1 containing granular sludge through a water inlet 3 in the water inlet stage; then, anaerobic treatment is performed, after the anaerobic treatment enters an aerobic treatment, air is introduced into the reaction column 1 through the aerator 4, granular sludge is settled in a settling treatment, and the treated marine culture wastewater is discharged through the first water outlet 51 in a water outlet treatment.
When the treatment period is more than 2, the water inflow of the rest treatment periods is 1/2 of the volume of the reaction column 1 except the first treatment period; and the water yield of the rest treatment periods is 1/2 of the volume of the reaction column 1 except the last treatment period. That is, the volume of the seafood culture waste water per replacement during the treatment is 1/2 of the volume of the reaction column 1.
The required treatment period varies depending on the specific volume of the reaction column 1 to be used and the volume of the seafood culture wastewater to be treated. For example, if the volume of the reaction column 1 to be used is larger under the condition that the volume of the marine culture wastewater to be treated is constant, the larger the volume of water to be replaced per time, the shorter the required treatment time (the smaller the number of treatment cycles) will be, correspondingly; conversely, if the volume of the reaction column 1 to be used is smaller, the smaller the volume of water to be replaced per time, the longer the treatment time (the larger the number of treatment cycles) is required. Similarly, under the condition that the volume of the reaction column 1 is fixed, the volume of water replaced each time is fixed, and if the volume of the seafood culture wastewater to be treated is larger, the corresponding treatment time is longer (the number of treatment cycles is larger); conversely, if the volume of seafood culture wastewater to be treated is smaller, the corresponding treatment time is shorter (the number of treatment cycles is smaller).
Preferably, the ratio of the processing times of the stages is 10:50-70:130-160:5:10:10, more preferably 10:60:145:5:10:10.
The treatment time of the water inlet stage is 10min, the treatment time of the anaerobic stage is 60min, the treatment time of the aerobic stage is 145min, the treatment time of the sedimentation stage is 5min, the treatment time of the water outlet stage is 10min, and the treatment time of the standing stage is 10min.
In some preferred embodiments, each treatment cycle is 4 hours. The hydraulic retention time in the reaction column 1 is 8h in the whole treatment process.
The term "hydraulic retention time" refers to the average retention time of the seafood cultivation wastewater to be treated (e.g., 1.1L) in the reaction column 1 in the same volume as the reaction column, that is, the average reaction time of the seafood cultivation wastewater to be treated in the same volume as the reaction column with microorganisms contained in the granular sludge in the reaction column 1.
In the removal process of the present application, the amount of the granular sludge added in the reaction column 1 may be 1300-2500mg/L, such as 1300mg/L, 1500mg/L, 1800mg/L, 2000mg/L, 2200mg/L or 2500mg/L, and may be any other value within the range of 1300-2500 mg/L.
The particle size of the granular sludge may be, for example, 0.8 to 2.5mm, such as 0.8mm, 1mm, 1.5mm, 2mm or 2.5mm, etc., and may be any other value within the range of 0.8 to 2.5mm. The sludge smaller than 0.8mm belongs to common sludge, and has poor aggregation; in the range of 0.8-2.5mm, the particle shape and morphology are both better.
The sludge volume index is 41.5-68mL/g, such as 41.5mL/g, 45mL/g, 50mL/g, 55mL/g, 60mL/g, 65mL/g or 68mL/g, etc., and can be any other value within the range of 41.5-68mL/g.
For reference, the above granular sludge may be obtained by culturing in the following manner: domesticating activated sludge from sewage treatment plant.
Specifically, the domestication is to put the activated sludge into a reaction column 1 provided by the application, wherein the addition amount of the activated sludge can be 2500-2700mg/L (preferably 2600 mg/L), and then, artificially synthesized mariculture wastewater is introduced for cultivation so as to adapt to the mariculture wastewater. The culture process was also carried out according to the above-mentioned treatment cycle.
The main component of the synthetic seawater culture wastewater comprises yeast extract and K 2 HPO 4 、KH 2 PO 4 、 MgCl 2 ·6H 2 O and CaCl 2 . During the treatment, the salinity in the reaction column 1 was gradually increased from 5ppt to 35ppt by gradually adding artificial sea salt to the synthetic mariculture wastewater.
In the process of culturing the activated sludge, glucose and sodium acetate are used as carbon sources, and the Chemical Oxygen Demand (COD) of the inflow water is controlled to be kept at about 400 mg/L. As the COD in the synthetic wastewater is derived from glucose and sodium acetate, the C/N is proper, and is easy to be absorbed and converted by flocs and particles. The ammonia nitrogen content in the synthetic seawater culture wastewater can be controlled to be 15mg/L, the nitrate content can be controlled to be 30mg/L, the nitrite content can be controlled to be 0.1mg/L, and the total phosphorus content can be controlled to be 10mg/L.
Through the domestication, not only can the floc sludge and small particles be eliminated, but also the particle system can be quickly constructed; but also can promote the enrichment of the optimal functional flora so as to ensure that the system achieves the effect of stably removing COD, ammonia nitrogen and total nitrogen.
And (3) after the domesticated granular sludge is obtained, the mariculture wastewater to be treated is used for replacing the synthetic mariculture wastewater to carry out tetracycline removal operation. In the process of treating mariculture wastewater to be treated, in an anaerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not more than 0.4mg/L. In the aerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not lower than 4mg/L. In the whole removing process, the water temperature is controlled at 20-35 ℃.
The granular sludge provided by the application has larger specific surface area, rich Extracellular Polymer (EPS) and various functional groups containing aldehyde, amine, carboxylic acid and the like, and provides a good condition for the adsorption of tetracycline. Meanwhile, the external aerobic internal anaerobic environment of the granular sludge can provide a unique anaerobic environment for removing nitrate nitrogen.
On the premise of bearing, the device and the method provided by the application can stably run for more than 200 days (more than 6 months), and in the process, the granular sludge is stable in form and is not cracked. In the stable period, the average removal efficiency of the tetracycline can reach 85.3 percent, and compared with the common activated sludge reactor, the removal rate of the tetracycline is improved by more than 15 percent. The granular sludge for removing the tetracycline comprises adsorption and biodegradation, wherein the adsorption can reach 0.158mg/g, the biodegradation performance can reach 0.0359mg/g, the mg in the mg/g refers to the removal amount of the tetracycline, and the g refers to the weight of the granular sludge.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a device for removing tetracycline in marine culture wastewater, which comprises a reactor, wherein the reactor comprises a reaction column 1.
The reaction column 1 was a column having an inner diameter of 50mm, a height of 1000mm and a volume of about 1.1L.
The lower end of the reaction column 1 is a closed end, and the upper end is an open end. The reaction column 1 is internally provided with a water body treatment space.
The inside of the reaction column 1 is provided with a baffle plate 2, and the baffle plate 2 is connected to the inner wall of the reaction column 1 and vertically divides the inside of the reaction column 1 into a first reaction chamber 11 and a second reaction chamber 12 with equal volumes. The first reaction chamber 11 and the second reaction chamber 12 are communicated with each other at both upper and lower ends of the reaction column 1.
The position of the first reaction chamber 11, which is close to the closed end, is provided with a water inlet 3, and the water inlet 3 is connected with a peristaltic pump.
An aerator 4 is connected to the second reaction chamber 12 at a position near the closed end of the reaction column 1. The second reaction chamber 12 is provided with a first water outlet 51 at 1/2 height of the corresponding reaction column 1.
The bottom of the reaction column 1 is provided with a time control switch for controlling water inlet conditions and water outlet conditions.
The top of the reaction column 1 is sleeved with a protection cylinder 6, the upper end of the protection cylinder 6 is open, the lower end is closed, and the side wall of the protection cylinder 6 is provided with a second water outlet 61.
The reaction column 1 is provided with a sampling port 52 at a position flush with the first water outlet 51.
Example 2
The embodiment provides a method for removing tetracycline in marine culture wastewater, which adopts the removing device provided in the embodiment 1 to remove tetracycline in marine culture wastewater to be treated.
The removal process is 129 days, each treatment period is 4 hours, and each treatment period comprises a water inlet stage (10 min), an anaerobic stage (60 min), an aerobic stage (145 min), a sedimentation stage (5 min), a water outlet stage (10 min) and a standing stage (10 min) which are sequentially carried out. In the whole removal process, the hydraulic retention time in the reaction column 1 is 8h.
Before the marine product culture wastewater to be treated is introduced, the granular sludge is placed into a reaction column 1, the adding amount of the granular sludge in the reaction column 1 is 2000mg/L, the particle size of the granular sludge is 0.8-2.5mm, and the sludge volume index is 41.5-68mL/g.
The marine culture wastewater to be treated is introduced into a reaction column 1 containing granular sludge through a water inlet 3 in the water inlet stage; then, anaerobic treatment is performed, after the anaerobic treatment enters an aerobic treatment, air is introduced into the reaction column 1 through the aerator 4, granular sludge is settled in a settling treatment, and the treated marine culture wastewater is discharged through the first water outlet 51 in a water outlet treatment. The water inflow in the first treatment cycle is equal to the total volume of the reaction column 1, the water outflow in the last cycle is equal to the total volume of the reaction column 1, and the water in the other treatment cycles is replaced by 1/2 of the water in each treatment cycle.
In the process of treating mariculture wastewater to be treated, in an anaerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not more than 0.4mg/L. In the aerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not lower than 4mg/L. The water temperature was controlled at 20 ℃ throughout the removal process.
The salinity of the mariculture wastewater to be treated is 35ppt, the COD value is 60mg/L, the ammonia nitrogen content is 8mg/L, the nitrate content is 25mg/L, the nitrite content is 0.1mg/L, the total phosphorus content is 5mg/L, and the tetracycline content is 300 mug/L.
The granular sludge is obtained by culturing in the following way: activated sludge (with the size of 0.09-0.15 mm) obtained from a sewage treatment plant (australia, china) was added to the reaction column 1 of the removal device provided in example 1 at an addition amount of 2600mg/L, and artificially synthesized mariculture wastewater was introduced to culture so as to accommodate the mariculture wastewater, and culture was performed in accordance with the above treatment cycle.
The main component of the synthetic seawater culture wastewater comprises yeast extract and K 2 HPO 4 、KH 2 PO 4 、 MgCl 2 ·6H 2 O and CaCl 2 . During the treatment, the salinity in the reaction column 1 was gradually increased from 5ppt to 35ppt by gradually adding artificial sea salt to the synthetic mariculture wastewater. In the process of culturing the activated sludge, glucose and sodium acetate are used as carbon sources, and the Chemical Oxygen Demand (COD) of the inflow water is controlled to be kept at about 400 mg/L. The ammonia nitrogen content in the synthetic seawater culture wastewater can be controlled to be 15mg/L, the nitrate content can be controlled to be 30mg/L, the nitrite content can be controlled to be 0.1mg/L, the total phosphorus content can be controlled to be 10mg/L, and the culture time is 80 days.
Test examples
2 reactors (SBR) as provided in example 1 were taken. Referring to example 2, each SBR was operated by a time control switch (BULLGND-1) with a period of 4 hours, each period comprising 6 successive phases: a water inlet stage (10 minutes), an anaerobic stage (60 minutes), an aerobic stage (145 minutes), a sedimentation stage (5 minutes), a water outlet stage (10 minutes) and a standing stage (10 minutes). The volume exchange per cycle per reactor was set to 50%, and correspondingly the Hydraulic Retention Time (HRT) in both SBR was maintained at 8 hours. The Dissolved Oxygen (DO) levels in the anaerobic and aerobic phases were maintained below 0.4mg/L and above 4mg/L, respectively. The water temperature was about 20 ℃.
The tetracycline (TET, purity > 99%) was added to the feed solution to each reactor, shanghai Biotechnology Co., ltd.
Activated sludge was collected from a sewage treatment plant (australia, china) and granular sludge was acclimatized prior to the test in the manner of example 2. Then normal activated sludge (floc, AS) and granular sludge (granule, GS) are injected into SBR1 (S1) and SBR2 (S2), respectively. The initial Mixed Liquid Volatile Suspended Solids (MLVSS) of the two reactors remained unchanged (-2000 mg/L). The sludge sizes in S1 and S2 are 0.09-0.15mm and 0.8-2.5mm, respectively. The experiment used synthetic mariculture wastewater containing TET (300. Mu.g/L). Artificial sea salt (beneficial bioengineering limited, guangzhou, china) was added to the synthetic wastewater to achieve a salinity of 35ppt in both reactors. Glucose and sodium acetate were used as carbon sources, and the Chemical Oxygen Demand (COD) of the feed water was maintained at 60mg/L during the test period, respectively.
The specific components of the synthetic seawater culture wastewater are shown in table 1.
TABLE 1 Synthesis of specific Components of mariculture wastewater
(1) Physicochemical analysis
COD、NH 4 + -N、NO 2 - -N、NO 3 - Determination of N, TP and Sludge Volume Index (SVI) is performed according to the potassium dichromate method (APHA, 2012). Total Nitrogen (TN) and Total Organic Carbon (TOC) were measured using a total organic carbon analyzer (SHIMADZU). Mixed Liquor Suspended Solids (MLSS) and MLVSS were tested using gravimetric methods. The pH and DO values were measured by a Multi-probe instrument (Multi 3630IDS, WTW). Particle Size Distribution (PSD) was measured using a laser particle size analyzer (LSI 3 320). The morphology of the sludge was examined using an Olympus CX41 microscope equipped with a digital camera (Olympus C550D Zoom).
Extraction and analysis of EPS: the sludge sample is extracted by EDTA and stored at 4 ℃ for 3 hours. After centrifugation of the mixture at 5000rpm for 20 minutes, the supernatant was filtered using a 0.22 μm filter. The luer and phenol-sulfuric acid methods are used to analyze the main EPS components, including Proteins (PN) and Polysaccharides (PS).
(2) Other tests
(1) Quantification of TET
Samples were collected weekly from each bioreactor and then filtered using a PTFE syringe filter (0.22 μm, sartorius). Using a detector equipped with 2998PDA (photodiode array) and WatersCSH TM The filtered solution (50. Mu.L) was quantified on a Fluoro-Phenyl column (diameter 2.1mm, length 150 mm, pore size 2.5 μm). The mobile phase was 0.1% (v/v) aqueous acetic acid and 0.1% (v/v) acetonitrile acetic acid at a flow rate of 0.4mL/min. The detection wavelength was set to 268.5nm.
(2) TET-conversion products
The mixture was collected from each stage in one cycle at the end of the second test period and then filtered using a 0.22 μm PTFE syringe filter. The filtered solution (15 mL) was further extracted through a solid phase extraction column (HLB, 3cc/60mg, waters, USA) according to the manufacturer's instructions. The conversion intermediate of TET was measured using a UPLC (Agilent 1290, USA) -QTOF-MS/MS spectrometer (Agilent 6550, USA). The separation was carried out on a C18 column (diameter 2.1mm, length 100mm, pore size 1.7 μm, waters BEH) with a sample loading of 2. Mu.L. The mobile phase consisted of methanol (solvent A) and 0.1% formic acid (solvent B) at a flow rate of 0.3mL/min with different volume ratios (see Table 2). Tandem mass spectrometry was performed in a full scan of 100-1000m/z using ESI+ (4 kV) and ESI- (3.2 kV) modes, respectively. The capillary temperature was 350℃and the cone gas flow rate was 12L/min.
TABLE 2 Mobile phase Condition
(3) Batch testing
To study the mechanism of sludge removal TET, a series of reactions was performed in glass beakers with 100mL each working volumeSeries of batch experiments. Well-adapted sludge was removed from S1 and S2 and rinsed 3 times with deionized water prior to adsorption experiments. Then, 0.3% (w/v) of sodium azide (NaN) 3 ) (Sigma) was added to each glass beaker to inhibit the microbial activity of the TET that might be biodegradable. Adsorption experiments were performed at TET concentrations of 100, 300 and 500mg/L in a thermostatic water bath shaker (Lichen, china) at 200rpm for 35 hours. About 2mL of the mixture was taken at 0, 0.5, 1, 2, 3, 4, 6, 8, 10, 12, 21, 23, 25, 27, 29, 31, 33, 35 hours after the experiment, and the TET concentration was measured immediately after filtration with a 0.22- μΜptfe syringe filter. To and without addition of NaN 3 The total removal kinetics experiments were performed in the same manner as the adsorption experiments of (a). For degradation kinetics, the amount of sludge degradation to TET was calculated by subtracting the adsorbed amount from the total removed amount.
The amount of TET adsorbed and biodegraded by AS and GS was determined using equations (1) and (2).
A t ＝(C 0 -C t )/MLSS (1)；
Wherein C is 0 (mg/L) represents the initial TET concentration; c (C) t (mg/L) represents the residual TET concentration at time t; a is that t (mg/g) represents the amount of TET adsorbed at time t.
B t ＝(C 0 -C r -A t ·MLSS)/MLSS (2)；
Wherein C is r (mg/L) represents the residual TET concentration after the removal experiment; b (B) t (mg/g) represents the amount of TET degradation at time t.
(4) Particle strength test
The strength of the particles was determined according to the method of Pereboom (1997). 10mL of settled particles were placed in a vertical cylinder of 3cm diameter and run at an upstream air speed of 1.5 cm/s. The test was continued for 120 minutes, and the concentration of fines was measured every 20 minutes.
In attrition experiments, the generation of fines per unit volume and time at a constant shear rate was found to be the primary process for concentration of larger particles. The equation after solving the boundary condition becomes:
In[(X 0 -X F )/X 0 ]＝-kt (3)；
wherein X is 0 X is the initial concentration of the granular sludge F The concentration of the fine powder after settling for 1 min; k (coefficient of wear rate) represents the strength of the particles under the application conditions.
At the beginning of the experiment, trained equivalent biomass GS and AS were injected into S2 and S1, respectively, and tes were added to the sample wastewater. SVI 30 、SVI 5 /SVI 30 The mean diameters of MLVSS, AS and GS and the kinetics of particle wear are shown in fig. 5.
As shown in FIG. 2, SVI30 of S1 and S2 is maintained at 73-99 and 41.5-68mL/g, respectively, SVI in S2 5 /SVI 30 Stabilization around 1.06 indicates that GS is operating in the bioreactor as a whole.
During the first 50 days of the test period (days 80-130), the biomass in both reactors gradually decreased due to the adaptation to the TET dose, and the particle size of the S2 particles also decreased, ranging from-1323 to-1095 μm (fig. 3 and 4). The attrition kinetics indicated that the particle strength in S2 was weaker on day 140 than at the start of the test (day 80) (fig. 5). As the microorganisms adapt to TET, the biomass of S1 and S2 increases from 1320 to 1843mg/L and 1560 to 2254mg/L, respectively, during the last two months of the test period (FIG. 3). Accordingly, the particle strength recovered at the end of the second phase and was stronger than day 140 (fig. 5).
(3) System performance
COD and NH in S1 and S2 4 + The concentrations and removal efficiencies of N, TN and TP are shown in FIGS. 6 to 8. The average effluent COD concentrations during the test period S1 and S2 were about 37 and 13mg/L, respectively. For NH 4 + N, the average water concentration in S1 and S2 is lower than 1mg/L. In contrast, S1 and S2 are removing NH 4 + N and COD aspects are equally effective. As the COD in the synthetic wastewater is derived from glucose and sodium acetate, the C/N is proper, and is easy to be absorbed and converted by flocs and particles.
Theoretically, the total nitrogen concentration of the inlet water is 33 mg/liter, but the actually measured total nitrogen concentration of the inlet water is slightly lower. After TET is added into the inlet water, TN removal performance in S2 is better than that of S1. The inflow TN mainly contains NH 4 + -N、NO 2 - -N and NO 3 - -N. The high removal of TN indicates that the denitrification in S2 is more efficient because of the NH removed by both 4 + The amount of N is almost the same. GS includes spherical compact aggregates formed by self-fixation of activated sludge, providing a powerful microbial structure by promoting the growth of various microorganisms. Compared with AS in SBR with the same structure, the spherical dense aggregate can provide more anoxic environment for denitrification. Although the aerobic and anaerobic operation times of S1 and S2 are the same, the large particle size GS can provide more anaerobic environment, which is beneficial to denitrification.
(4) Results of TET in S1 and S2
During the running phase, the concentration of TET in the inlet water is 0.3mg/L. The specific removal performance and total removal efficiency of TET in S1 and S2 are shown in fig. 9. The results show that: the total removal efficiency of tetracycline in S2 was stronger, with average removal efficiencies in S1 and S2 of 69.7% and 85.3%, respectively. In particular to the removal performance, the granular sludge can remove 0.74g of tetracycline per cubic meter per day, while the common activated sludge only removes 0.60 g/(m) 3 Tetracycline of d).
From the EPS point of view, S2 corresponds to a value of approximately 163.77mg/L, which is higher than 143.44mg/L of S1 (FIG. 10). The EPS composition secreted by two different types of sludge is basically the same and mainly contains protein. EPS can capture tetracyclines by pi-pi stacking reactions of TET benzene rings and extracellular proteins (tyrosine and tryptophan). The granular sludge with higher EPS protein content showed stronger TET adsorption performance (fig. 10, 11 and 12). In the process of forming the granular sludge, environmental pressure and signal molecules can induce more EPS secretion, promote microorganism aggregation and maintain the stability of the granular sludge. The increase in EPS secretion protects microorganisms from toxic compounds and harsh environments, which helps to maintain higher biomass and better sludge performance in S2, as well as promotes removal of tetracycline by the granular sludge (fig. 2-5 and 9).
A series of adsorption and biodegradation batch tests were performed with normal activated sludge and granular sludge (fig. 11-15). The results show that: as the initial concentration of tetracycline increased, the adsorption and biodegradation amount of TET by normal activated sludge and granular sludge increased (fig. 11 to 14). From the results, it is clear that the adsorption capacity of the granular sludge to tetracycline is obviously higher than that of the common activated sludge, and the biodegradability of the granular sludge is slightly higher than that of the common activated sludge.
At initial concentrations of 0.1, 0.3 and 0.5mg/L, the adsorption amounts of the ordinary activated sludge to the tetracyclines were 0.031, 0.080 and 0.118mg/g, respectively, while the adsorption amounts of the granular sludge to the tetracyclines were 0.037, 0.105 and 0.158mg/g, respectively. When the operation time exceeds 30 hours, the adsorption of the tetracycline by the common activated sludge and the granular sludge is balanced. Adsorption of tetracycline by normal activated sludge and granular sludge in seawater can be divided into three processes: (1) boundary layer diffusion, (2) intra-particle diffusion, (3) final equilibrium phase. FIGS. 11 and 12 show that surface adsorption initially accounts for the majority of the adsorption of tetracycline by the sludge, then intra-granular diffusion begins to slow down, eventually reaching adsorption equilibrium, and the concentration of tetracycline in the solution decreases. The larger specific surface area and particle size (FIG. 4) compared to the flocs contributes to the faster boundary layer and intra-particle diffusion rates of tetracycline, thus making the particles more adsorptive.
Like adsorption, ordinary activated sludge and granular sludge tend to stabilize against biodegradation of tetracycline when operating for more than 30 hours. The maximum biodegradation amounts of normal activated sludge with initial tetracycline concentrations of 0.1, 0.3 and 0.5mg/L were 0.0053, 0.0228 and 0.0315mg/g, respectively, while the maximum biodegradation amounts of granular sludge were 0.0072, 0.0237 and 0.0359mg/g, respectively. The biodegradability of the granular sludge is slightly better than that of common activated sludge. Compared with adsorption, the biological degradation difference of two different types of sludge is not large. Most of the tetracyclines are able to adsorb first on the sludge surface, with only small amounts available for biodegradation, which appears to have no significant contribution to the overall removal of tetracyclines. As shown in FIG. 15, the adsorption-removal efficiencies of the normal activated sludge were 61.9%, 53.2% and 47.0%, respectively, at the initial concentrations of 0.1, 0.3 and 0.5mg/L tetracycline. Accordingly, the adsorption removal efficiencies of the granular sludge were 74.5%, 70.4% and 63.1%, respectively. In terms of biodegradation, the average removal efficiencies of normal activated sludge and granular sludge were 12.8% and 14.8%, respectively. The results show that: the tetracycline of more than 80% is removed through the absorption to both types of mud, and the adsorption capacity of granule mud is obviously stronger, and it contains more EPS, the granule of bigger particle diameter and specific surface area can adapt to abominable water environment and absorb more tetracyclines.
In conclusion, the device for removing antibiotics in marine culture wastewater has the advantages of simple structure and low cost, and can be popularized and applied in the aspect of removing antibiotics (such as tetracycline) in marine culture wastewater. The corresponding removal method is simple to operate, the process is easy to control, antibiotics in marine culture wastewater can be efficiently removed, COD, ammonia nitrogen and total nitrogen contained in the wastewater are stably treated, and the problem of low total nitrogen and antibiotic removal efficiency in the existing circulating culture mode is solved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The method for removing the antibiotics in the marine culture wastewater is characterized in that a device for removing the antibiotics in the marine culture wastewater is adopted to remove the antibiotics in the marine culture wastewater to be treated;
the removal device comprises a reactor, wherein the reactor comprises a reaction column;
the lower end of the reaction column is a closed end;
the inside of the reaction column is provided with a baffle plate which is connected to the inner wall of the reaction column and vertically separates the inside of the reaction column into a first reaction chamber and a second reaction chamber, and the first reaction chamber and the second reaction chamber are communicated with each other at the upper end and the lower end of the reaction column, so that granular sludge in the reaction column and marine aquaculture wastewater to be treated can circularly flow along the first reaction chamber to the second reaction chamber in the treatment process;
the position of the first reaction chamber, which is close to the closed end, is provided with a water inlet, the position of the second reaction chamber, which is close to the closed end, is connected with an aerator, and the middle part of the second reaction chamber is provided with a first water outlet;
the top of the reaction column is also sleeved with a protection cylinder, the upper end of the protection cylinder is open, the lower end of the protection cylinder is closed, and the side wall of the protection cylinder is provided with a second water outlet;
the removing process comprises at least 1 treatment period, and each treatment period sequentially comprises a water inlet stage, an anaerobic stage, an aerobic stage, a sedimentation stage, a water outlet stage and a standing stage; the ratio of the treatment time of each stage is 10:50-70:130-160:5:10:10 in sequence;
the chemical oxygen demand of the marine culture wastewater to be treated is kept at 60mg/L;
the removal method and the removal device have a steady operation time of greater than 200 days.
2. The removal method according to claim 1, wherein the bottom of the reaction column is further provided with a controller for controlling water inlet conditions and water outlet conditions.
3. The removal method of claim 1, wherein the antibiotic is tetracycline;
the marine culture wastewater to be treated is introduced into the reaction column containing the granular sludge through the water inlet in the water inlet stage; then anaerobic stage treatment is carried out, after the anaerobic stage is carried out, air is introduced into the reaction column through the aerator, granular sludge is settled in a settling stage, and treated marine culture wastewater is discharged through the first water outlet in a water outlet stage;
in the treatment process, the volume of the marine culture wastewater replaced each time is 1/2 of the volume of the reaction column;
each treatment cycle was 4h.
4. The method according to claim 1, wherein the amount of the added granular sludge in the reaction column is 1300-2500mg/L, and the particle size of the granular sludge is 0.8-2.5mm.
5. The removal method according to claim 1, wherein the hydraulic retention time in the reaction column is 8 hours throughout the removal process.
6. The removal process of claim 1, wherein the dissolved oxygen level in the reaction column is no more than 0.4mg/L during the anaerobic phase.
7. The method according to claim 1, wherein the dissolved oxygen level in the reaction column is not lower than 4mg/L in the aerobic stage.
8. The method of claim 1, wherein the water temperature during the removal is 20-35 ℃.
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