CN114772732A - Device and method for removing antibiotics in mariculture wastewater - Google Patents
Device and method for removing antibiotics in mariculture wastewater Download PDFInfo
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Images
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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a device and a method for removing antibiotics in mariculture wastewater, and belongs to the technical field of wastewater treatment. The removing 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 close to the closed end is provided with a water inlet, the position of the second reaction chamber 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 the marine aquaculture wastewater. The corresponding removal method is simple to operate, the process is easy to control, and the tetracycline in the marine culture wastewater can be efficiently removed.
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 mariculture wastewater.
Background
Aquaculture is the fastest growing food production sector in the world in the last 40 years, with marine aquaculture being the whole 1/3. Tetracycline, one of the most widespread antibiotics, is used in large quantities for the prevention and treatment of diseases in fish and other marine animals. The total amount of tetracycline consumed in europe and the united states is statistically about 5500 tons per year. Unfortunately, antibiotics are not efficiently metabolized by animals, which results in discharge of mariculture wastewater containing a large amount of antibiotics into receiving water bodies, thereby causing environmental pollution and ecological damage.
The circulating aquaculture mode (RAS) is one of the modes of aquaculture with the highest industrialization degree, and can realize the production mode of energy conservation, emission reduction, environment-friendly production and even zero emission through online sewage treatment. However, most of these treatment units use conventional aerobic biological treatment or biofilter technology, which cannot effectively remove nitrate nitrogen and antibiotics accumulated in the system.
The traditional biological treatment process is reported to have a common removal effect on typical antibiotics, such as that the average removal rate of lincomycin is only 42.1%, that of chlortetracycline is 58.8%, and that of sulfamethoxazole and tetracycline is about 66%.
Therefore, a process for economically and efficiently removing tetracycline is urgently needed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a device and a method for removing antibiotics in mariculture wastewater, so as to solve the technical problem.
The application can be realized as follows:
in a first aspect, the present application provides a device for removing antibiotics from mariculture wastewater, comprising a reactor, the reactor comprising a reaction column;
the lower end of the reaction column is a closed end;
the reaction column is internally provided with a baffle plate, the baffle plate is connected to the inner wall of the reaction column and vertically divides the interior 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 from the first reaction chamber to the second reaction chamber in the treatment process;
the position of the first reaction chamber close to the closed end is provided with a water inlet, the position of the second reaction chamber 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 further provided with a controller for controlling the water inlet condition and the water outlet condition.
In an optional embodiment, a protection barrel is further sleeved at the top of the reaction column (to prevent the overflow of abnormal water during the operation of the system), the upper end of the protection barrel is open, the lower end of the protection barrel is closed, and a second water outlet is formed in the side wall of the protection barrel.
In a second aspect, the present application provides a method for removing tetracycline from mariculture wastewater, comprising the steps of: the removal device of any one of the preceding embodiments is used to remove antibiotics from the mariculture 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 order, a water inlet phase, an anaerobic phase, an aerobic phase, a settling phase, a water outlet phase, and a resting phase;
introducing the marine aquaculture wastewater to be treated into a reaction column containing granular sludge through a water inlet in a water inlet stage; and then carrying out anaerobic stage treatment, introducing air into the reaction column through an aerator after the reaction column enters an aerobic stage, settling the granular sludge in a settling stage, and discharging the treated mariculture wastewater through a first water outlet in a water outlet stage.
In an alternative embodiment, the volume of mariculture wastewater displaced each time during treatment is 1/2 the volume of the reaction column.
In an alternative embodiment, the ratio of the treatment times for the stages is 10:50-70:130-160:5:10:10 in sequence.
In an alternative embodiment, each processing cycle is 4 h.
In an optional embodiment, in the removing process, the addition amount of the granular sludge in the reaction column is 1300-2500mg/L, and the particle size of the granular sludge is 0.8-2.5 mm.
In an alternative embodiment, the hydraulic retention time in the reaction column is 8h throughout the removal process.
In an alternative embodiment, during the anaerobic phase, the dissolved oxygen level in the reaction column is no more than 0.4 mg/L.
In an alternative embodiment, the dissolved oxygen level in the reactor column is not less than 4mg/L during the aerobic phase.
In an alternative embodiment, the water temperature is 20-35 ℃ during the removal process.
The beneficial effect of this application includes:
the application provides a remove device can make granular sludge produce better treatment effect to the antibiotic under the effect of shear force. Concretely, the marine product aquaculture waste water that adds from the water inlet collects downwards in first reaction cavity and flows to the second reaction cavity through the closed end of reaction column lower extreme under self action of gravity in, more and more waste water constantly lets in to first reaction cavity afterwards, make the marine product aquaculture waste water volume that gets into in the second reaction cavity more and more simultaneously, liquid level in the second reaction cavity rises gradually until marine product aquaculture waste water flows back to first reaction cavity once more through the upper end of reaction column, and produce the impact force to the waste water that is close to the lower extreme of reaction column in the first reaction cavity, thereby make waste water in the reaction column can be continuous along the counter clockwise flow formation stronger shearing force.
The antibiotic removing device in the mariculture 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 the mariculture wastewater. The corresponding removal method is simple to operate, the process is easy to control, the antibiotics in the marine culture wastewater can be efficiently removed, COD (chemical oxygen demand), ammonia nitrogen and total nitrogen contained in the wastewater are stably treated, and the problem of low removal efficiency of the total nitrogen and the antibiotics in the conventional circulating culture mode is solved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic structural diagram of an apparatus for removing antibiotics from mariculture wastewater provided by the present application;
FIG. 2 is a SVI corresponding to the sludge in S1 and S2 in the experimental example30The result is;
FIG. 3 shows MLVSS results corresponding to sludge in S1 and S2 in the test example;
FIG. 4 shows the average diameters of the sludge in S1 and S2 in the test examples;
FIG. 5 shows the dynamic course of the abrasion of the particles in S2 in the test example;
FIG. 6 shows COD results in S1 and S2 in the experimental examples;
FIG. 7 shows NH in S1 and S2 in test examples4 +-N results;
FIG. 8 shows TN results in S1 and S2 in the test examples;
FIG. 9 is the results of the specific removal performance and the total removal efficiency of tetracycline (TET) in S1 and S2 in the test examples;
FIG. 10 shows EPS concentrations in S1 and S2 in the test examples;
FIG. 11 shows adsorption results of TET by AS at different concentrations in the experimental examples;
FIG. 12 shows adsorption results of TET by GS at different concentrations in the test examples;
FIG. 13 shows the results of biodegradation of TET by AS at various concentrations in the experimental examples;
FIG. 14 shows the results of biodegradation of TET by GS at various concentrations in the experimental examples;
FIG. 15 shows TET removal efficiency and adsorption and biodegradation rates at different concentrations in the experimental examples.
An icon: 1-a reaction column; 2-a baffle plate; 11-a first reaction chamber; 12-a second reaction chamber; 3-water inlet; 4-an aerator; 51-a first water outlet; 52-a sampling port; 6-a protective cylinder; 61-second water outlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a specific description of the device and method for removing antibiotics from mariculture wastewater provided by the present application.
The application provides a removing device for antibiotics in mariculture wastewater, which comprises a reactor and a reaction column 1, and is shown in figure 1.
As a reference, the reaction column 1 may be used, for example, but not limited to, 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, in which granular sludge is effectively adsorbed (mainly) and biodegraded (secondarily) to tetracycline in the mariculture wastewater to be treated.
The baffle plate 2 is arranged in the reaction column 1, 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 inside of the reaction column 1 into the first reaction chamber 11 and the second reaction chamber 12 of equal volume.
It should be noted that the first reaction chamber 11 and the second reaction chamber 12 are communicated with each other at both the upper end and the lower end of the reaction column 1, so that the granular sludge in the reaction column 1 and the mariculture wastewater to be treated can circularly flow (can be understood as flowing along the counterclockwise direction) from the first reaction chamber 11 to the second reaction chamber 12 during the treatment process.
A water inlet 3 is arranged at the position of the first reaction chamber 11 close to the closed end (lower end), and the water inlet 3 can be connected with a peristaltic pump so as to lead the mariculture wastewater to be treated into the reaction column 1 from the water inlet 3.
The anticlockwise direction is based on that the mariculture wastewater added firstly downwards collects in the first reaction chamber 11 under the action of self gravity and flows to the second reaction chamber 12 through the closed end at the lower end of the reaction column 1, then more and more wastewater is continuously introduced into the first reaction chamber 11, the amount of the mariculture wastewater entering the second reaction chamber 12 is increased and increased, the liquid level in the second reaction chamber 12 gradually rises until the mariculture wastewater flows back to the first reaction chamber 11 again through the upper end of the reaction column 1, impact force is generated on the wastewater close to the lower end of the reaction column 1 in the first reaction chamber 11, and therefore the wastewater in the reaction column 1 can continuously flow along the anticlockwise direction. Through the flowing form, 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 near 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 at a specific treatment stage (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 aquaculture wastewater from which tetracycline is removed.
Referring to this, the first water outlet 51 may be disposed at the 1/2 level of the reaction column 1. The sampling port 52 is provided at a position flush with the first water outlet 51 of the reaction column 1.
In addition, the bottom of the reaction column 1 is provided with a controller (not shown) for controlling the water inlet condition and the water outlet condition so as to control and adjust the water inlet condition and the water outlet condition in time. The controller may be a time-controlled switch, for example.
Preferably, when the top of the reaction column 1 is opened, the top of the reaction column 1 may be further sleeved with a protection barrel 6 (to prevent abnormal water outflow and overflow of the system), the upper end of the protection barrel 6 is opened, the lower end is closed, and the side wall of the protection barrel 6 is provided with a second water outlet 61.
Through the protection section of thick bamboo 6 of establishing of cover, can be when first delivery port 51 goes wrong or the controller breaks down, can in time discharge the water that overflows in the reaction column 1 to appointed waste water collection container.
In some embodiments, a sampling port may be further provided at a position of the reaction column 1 flush with the first water outlet 51, so that a 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.
Other structures of the removing device can refer to a Sequencing Batch Reactor (SBR), and are not described in detail herein.
Correspondingly, the application also provides a method for removing antibiotics in mariculture wastewater, which comprises the following steps: the removal device is used for removing antibiotics in the mariculture wastewater to be treated.
Among these, the antibiotic may be, for example, but not limited to, tetracycline.
It is to be noted that the removal process includes at least 1 processing cycle, and specifically, the processing cycle may be 1, 2, 3, 4 or more by way of example.
Each treatment cycle comprises a water inlet stage, an anaerobic stage, an aerobic stage, a sedimentation stage, a water outlet stage and a standing stage in sequence.
Introducing the marine aquaculture wastewater to be treated into a reaction column 1 containing granular sludge through a water inlet 3 in a water inlet stage; then, anaerobic stage treatment is carried out, after the aerobic stage, air is introduced into the reaction column 1 through the aerator 4, granular sludge is settled in the settling stage, and the treated mariculture wastewater is discharged through the first water outlet 51 in the water outlet stage.
When the treatment period is more than 2, the water inflow of the rest treatment periods except the first treatment period is 1/2 of the volume of the reaction column 1; and the water yield of the rest of the treatment cycles except the last treatment cycle is 1/2 of the volume of the reaction column 1. That is, the volume of the mariculture wastewater displaced each time during the treatment was 1/2 of the volume of the reaction column 1.
It should be noted that the treatment period is different depending on the specific volume of the reaction column 1 used and the volume of the mariculture wastewater to be treated. For example, given a given volume of mariculture wastewater to be treated, the larger the volume of the reaction column 1 used, the more water it displaces per time, and correspondingly, the shorter the treatment time required (the fewer the number of treatment cycles); conversely, the smaller the volume of the reaction column 1 used, the smaller the volume of water it displaces per time, and correspondingly, the longer the treatment time required (the larger the number of treatment cycles). Similarly, under the condition of a certain volume of the reaction column 1, the volume of water to be replaced each time is fixed, and if the volume of the mariculture wastewater to be treated is larger, the treatment time is correspondingly longer (the number of treatment cycles is larger); conversely, a smaller volume of mariculture wastewater requires a correspondingly shorter treatment time (fewer treatment cycles).
Preferably, the ratio of the processing time of each stage is 10:50-70:130-160:5:10:10, more preferably 10:60:145:5:10: 10.
In min, 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 10 min.
In some preferred embodiments, each treatment cycle is 4 h. In the whole treatment process, the hydraulic retention time in the reaction column 1 is 8 h.
By "hydraulic retention time" is meant the average retention time in the reaction column 1 of the volume of the mariculture wastewater to be treated equal to the volume of the reaction column (e.g. 1.1L), i.e. the average reaction time of the volume of the mariculture wastewater to be treated equal to the volume of the reaction column to the action of the 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, or may be any other value within the range of 1300-2500 mg/L.
The particle size of the granular sludge may illustratively be 0.8-2.5mm, such as 0.8mm, 1mm, 1.5mm, 2mm, or 2.5mm, etc., and may also be any other value in the range of 0.8-2.5 mm. It should be noted that the sludge smaller than 0.8mm belongs to common sludge and has poor aggregation property; the particle shape and morphology are preferred within the range of 0.8-2.5 mm.
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, and can be any other value within the range of 41.5-68 mL/g.
For reference, the granular sludge can be obtained by culturing in the following way: domesticating activated sludge taken from a sewage treatment plant.
Specifically, the acclimatization is to place the activated sludge in the reaction column 1 provided by the present application, in this case, the addition amount of the activated sludge may be 2500-. The cultivation process is also carried out according to the above treatment cycle.
The synthetic wastewater for mariculture mainly comprises yeast extract and K2HPO4、KH2PO4、 MgCl2·6H2O and CaCl2. 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 activated sludge culture process, glucose and sodium acetate are used as carbon sources, and the Chemical Oxygen Demand (COD) of inlet 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 content of ammonia nitrogen in the synthetic mariculture wastewater can be controlled to be 15mg/L, the content of nitrate can be controlled to be 30mg/L, the content of nitrite can be controlled to be 0.1mg/L, and the content of total phosphorus can be controlled to be 10 mg/L.
Through the domestication, floc sludge and small particles can be eliminated, and a particle system is promoted to be constructed quickly; but also promote the enrichment of optimal functional flora so as to ensure that the system achieves the effect of stably removing COD, ammonia nitrogen and total nitrogen.
After the domesticated granular sludge is obtained, the mariculture wastewater to be treated is used for replacing synthetic mariculture wastewater to carry out tetracycline removal operation. In the treatment process of the mariculture wastewater to be treated, in the anaerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not more than 0.4 mg/L. In the aerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not less than 4 mg/L. During the whole removing process, the water temperature is controlled at 20-35 ℃.
The granular sludge provided by the application has a large specific surface area, abundant Extracellular Polymeric Substances (EPS) and various functional groups including aldehyde, amine, carboxylic acid and the like, and provides a good condition for adsorbing tetracycline. Meanwhile, the external aerobic and internal anaerobic environment of the granular sludge can provide a unique anaerobic environment for removing nitrate nitrogen.
In conclusion, the device and the method provided by the application can stably operate for more than 200 days (more than 6 months), and the granular sludge is stable in shape and is not cracked in the process. In the stable period, the average tetracycline removal efficiency can reach 85.3 percent, and compared with a common activated sludge reactor, the tetracycline removal rate is improved by more than 15 percent. And the tetracycline removal of the granular sludge comprises adsorption and biodegradation, wherein the adsorption can reach 0.158mg/g, the biodegradation can reach 0.0359mg/g, the mg in the mg/g refers to the tetracycline removal amount, and the g refers to the weight of the used granular sludge.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a device for removing tetracycline in mariculture 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 baffle plate 2 is arranged in the reaction column 1, and the baffle plate 2 is connected to the inner wall of the reaction column 1 and vertically and evenly divides the interior of the reaction column 1 into a first reaction chamber 11 and a second reaction chamber 12 which are equal in volume. The first reaction chamber 11 and the second reaction chamber 12 are communicated with each other at the upper end and the lower end of the reaction column 1.
The first reaction chamber 11 is provided with a water inlet 3 at a position close to the closed end, and the water inlet 3 is connected with a peristaltic pump.
An aerator 4 is connected to the second reaction chamber 12 near the closed end of the reaction column 1. The second reaction chamber 12 is provided with a first water outlet 51 at the 1/2 height corresponding to the reaction column 1.
The bottom of the reaction column 1 is provided with a time switch for controlling the water inlet condition and the water outlet condition.
The top cover of reaction column 1 is equipped with a protection section of thick bamboo 6, and the upper end of a protection section of thick bamboo 6 is uncovered, and the lower extreme is sealed, and the lateral wall of a protection section of thick bamboo 6 has seted up second delivery port 61.
The position of the reaction column 1 flush with the first water outlet 51 is provided with a sampling port 52.
Example 2
The embodiment provides a method for removing tetracycline in mariculture wastewater, and the removal device provided in embodiment 1 is adopted to remove tetracycline in the mariculture wastewater to be treated.
The removal process is 129 days, each treatment cycle is 4h, and each treatment cycle comprises a water inlet stage (10min), an anaerobic stage (60min), an aerobic stage (145min), a sedimentation stage (5min), a water outlet stage (10min) and a standing stage (10min) which are sequentially performed. In the whole removing process, the hydraulic retention time in the reaction column 1 is 8 h.
Before introducing the mariculture wastewater to be treated, granular sludge is put into a reaction column 1, the addition 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 41.5-68 mL/g.
Introducing the marine aquaculture wastewater to be treated into a reaction column 1 containing granular sludge through a water inlet 3 in a water inlet stage; then, anaerobic stage treatment is carried out, after the aerobic stage, air is introduced into the reaction column 1 through the aerator 4, granular sludge is settled in the settling stage, and the treated mariculture wastewater is discharged through the first water outlet 51 in the water outlet stage. 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 treatment cycle is equal to the total volume of the reaction column 1, and the water in the reaction column 1/2 is displaced each time in the remaining treatment cycles.
In the treatment process of the mariculture wastewater to be treated, the dissolved oxygen level in the reaction column 1 is controlled to be not more than 0.4mg/L in the anaerobic stage. In the aerobic stage, the dissolved oxygen level in the reaction column 1 is controlled to be not less than 4 mg/L. The water temperature was controlled at 20 ℃ throughout the removal process.
The seawater culture wastewater to be treated has the salinity of 35ppt, the COD value of 60mg/L, the ammonia nitrogen content of 8mg/L, the nitrate content of 25mg/L, the nitrite content of 0.1mg/L, the total phosphorus content of 5mg/L and the tetracycline content of 300 mu g/L.
The granular sludge is obtained by culturing in the following way: activated sludge (size 0.09-0.15mm) from a sewage treatment plant (Australian, China) was added to the reaction column 1 of the removal apparatus provided in example 1 in an amount of 2600mg/L, and the artificially synthesized mariculture wastewater was introduced and cultured to be suitable for mariculture wastewater, and the culture was performed according to the above treatment cycle.
The synthetic wastewater for mariculture mainly comprises yeast extract and K2HPO4、KH2PO4、 MgCl2·6H2O and CaCl2. 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 activated sludge culture process, glucose and sodium acetate are used as carbon sources, and the Chemical Oxygen Demand (COD) of inlet water is controlled to be about 400 mg/L. The content of ammonia nitrogen in the synthetic mariculture wastewater can be controlled to be 15mg/L, the content of nitrate can be controlled to be 30mg/L, the content of nitrite can be controlled to be 0.1mg/L, the content of total phosphorus 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 run by a time controlled switch (bollgnd-1) in 4 hour cycles, each cycle comprising 6 successive phases: water inlet phase (10min), anaerobic phase (60min), aerobic phase (145min), settling phase (5min), water outlet phase (10min) and standing phase (10 min). The volumetric exchange rate per cycle per reactor was set at 50%, and accordingly 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 kept below 0.4mg/L and above 4mg/L, respectively. The water temperature was about 20 deg.c.
Experiments tetracycline (TET, purity > 99%, Shanghai Denshi Biotech Co., Ltd.) was added to the feed solution in each reactor.
Activated sludge was collected from a sewage treatment plant (Australia, China) and the granular sludge was acclimatized as in example 2 before the experiment. Ordinary activated sludge (floc, AS) and granular sludge (granule, GS) were then injected into SBR1(S1) and SBR2(S2), respectively. The initial Mixed Liquor Volatile Suspended Solids (MLVSS) of the two reactors remained unchanged (-2000 mg/L). The sizes of the sludge in S1 and S2 are 0.09-0.15mm and 0.8-2.5mm respectively. Synthetic mariculture wastewater containing TET (300. mu.g/L) was used in this experiment. Artificial sea salt (wel bioengineering limited, guangzhou, china) was added to the synthesis 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 mariculture wastewater are shown in table 1.
TABLE 1 specific composition of synthetic mariculture wastewater
(1) Physical and chemical analysis
COD、NH4 +-N、NO2 --N、NO3 --N, TP and determination of Sludge Volume Index (SVI) were carried out 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). The Mixed Liquor Suspended Solids (MLSS) and MLVSS were tested gravimetrically. The pH and DO values were measured by a Multi-probe instrument (Multi 3630IDS, WTW). The Particle Size Distribution (PSD) was measured using a laser particle size analyzer (LSI 3320). Using a camera equipped with a digital camera (Olympus C550D Zoom)The morphology of the sludge was examined microscopically by Olympus CX 41.
Extraction and analysis of EPS: the sludge sample is extracted by EDTA and stored for 3 hours at 4 ℃. After the mixture was centrifuged at 5000rpm for 20 minutes, the supernatant was filtered using a 0.22 μm filter. The luerly and phenol-sulfuric acid methods are used to analyze major EPS components, including Proteins (PN) and Polysaccharides (PS).
(2) Other tests
[ quantification of TET
Samples were collected from each bioreactor every week and then filtered using a PTFE syringe filter (0.22 μm, Sartorius). Using a 2998PDA (photodiode array) equipped detector and Waters
CSHTMThe 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 acetate solution at a flow rate of 0.4 mL/min. The detection wavelength was set at 268.5 nm.
② TET-conversion product
The mixed liquor 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 (15mL) was further extracted by a solid phase extraction column (HLB, 3cc/60mg, Waters, USA) according to the manufacturer's instructions. Conversion intermediates of TET were measured using 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) in a sample size 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, varying in volume ratio (Table 2). Tandem mass spectrometry was performed in a full scan of 100-1000m/z using ESI + (4kV) and ESI- (3.2kV) modes, respectively. The capillary temperature was 350 ℃ and the cone gas flow rate was 12L/min.
TABLE 2 mobile phase situation
(iii) batch testing
To investigate the mechanism of sludge removal TET, a series of batch experiments were performed in glass beakers with each working volume of 100 mL. Prior to the adsorption experiments, well-adapted sludge was taken from S1 and S2 and rinsed 3 times with deionized water. Then, 0.3% (w/v) of sodium azide (NaN)3) (Sigma) was added to each glass beaker to inhibit the microbial activity of TET which could biodegrade. The adsorption experiments were carried out at TET concentrations of 100, 300 and 500mg/L for 35 hours in a constant temperature water bath shaker (Lichen, China) at 200 rpm. Approximately 2mL of the mixture was started 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 determined immediately after filtration through a 0.22- μm PTFE syringe filter. With or without the addition of NaN3The total removal kinetics experiment was performed in the same manner as the adsorption experiment. For the degradation kinetics, the amount of TET degradation by sludge was calculated by subtracting the adsorption amount from the total removal amount.
The amount of TET adsorbed and biodegraded by AS and GS was determined using equations (1) and (2).
At＝(C0-Ct)/MLSS (1)；
Wherein, C0(mg/L) represents the initial TET concentration; ct(mg/L) represents the residual TET concentration at time t; a. thet(mg/g) represents the amount of TET adsorbed at time t.
Bt＝(C0-Cr-At·MLSS)/MLSS (2)；
Wherein, Cr(mg/L) represents the residual TET concentration after the removal experiment; b ist(mg/g) represents the amount of TET degradation at time t.
(iv) particle Strength test
The intensity of the granules 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 velocity of 1.5 cm/s. The test lasted 120 minutes, with the fines concentration measured every 20 minutes.
In attrition experiments, it was found that the generation of fines per unit volume and time at a constant shear rate is the first stage of the concentration of larger particles. The equation after solving the boundary conditions becomes:
In[(X0-XF)/X0]＝-kt (3)；
in the formula, X0Is the initial concentration of the granular sludge, XFThe concentration of the fine powder after settling for 1 min; k (wear rate coefficient) represents the strength of the particles under the application conditions.
At the beginning of the experiment, trained GS and AS of equal biomass were injected into S2 and S1, respectively, and TETs were added to the injection wastewater. SVI30、SVI5/SVI30The average diameters of MLVSS, AS and GS and the kinetics of particle attrition are shown in fig. 5.
As shown in FIG. 2, the SVI30 of S1 and S2 was maintained at 73-99 and 41.5-68mL/g, respectively, the SVI in S25/SVI30The stability was around 1.06, indicating that GS was operating in the bioreactor as a whole.
On the first 50 days of the test period (days 80-130), the biomass in both reactors decreased gradually as a result of adaptation to the TET dose, and the particle size of the S2 particles also decreased, ranging from-1323 to-1095 μm (FIGS. 3 and 4). The attrition kinetics indicated that the strength of the granules in S2 was weaker at day 140 than at the start of the test (day 80) (fig. 5). As the microorganisms acclimated to TET, the biomass of S1 and S2 increased from 1320 to 1843mg/L and 1560 to 2254mg/L, respectively, during the last two months of the experimental period (FIG. 3). Accordingly, the granule intensity 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 S24 +The concentrations of-N, TN and TP and the removal efficiencies 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 NH4 +-N, having an average water outlet concentration in S1 and S2 of less than 1 mg/L. In contrast, S1 and S2 are removing NH4 +N and COD are also 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 feed water was 33 mg/l, but the actually measured total nitrogen concentration of the feed water was slightly lower. After TET was added to the feed water, TN removal in S2 was better than S1. The influent TN contains mainly NH4 +-N、NO2 --N and NO3 --N. The high removal of TN indicates that denitrification in S2 is more effective because both remove NH4 +The N amounts are almost the same. GS comprises spherical compact aggregates formed by self-immobilization 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 compact aggregate can provide more anoxic environment for denitrification. Although the aerobic and anaerobic running times of S1 and S2 are the same, the GS with large particle size can provide more anaerobic environment, which is beneficial to the denitrification.
(4) Results of TET in S1 and S2
In the running stage, the concentration of TET in the feed water is 0.3 mg/L. The specific removal performance and the total removal efficiency of TET in S1 and S2 are shown in fig. 9. The results show that: the overall removal efficiency of tetracycline in S2 was stronger, with the average removal efficiencies of 69.7% and 85.3% in S1 and S2, respectively. In the aspect of specific 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)3D) tetracycline.
From an EPS point of view, S2 corresponds to a value of approximately 163.77mg/L, higher than 143.44mg/L for S1 (FIG. 10). The EPS compositions secreted by two different sludges are basically the same and mainly comprise protein. EPS can capture tetracycline through the pi-pi stacking reaction 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, fig. 11 and fig. 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 can protect microorganisms from toxic compounds and harsh environments, which helps to maintain higher biomass and better sludge performance in S2, as well as facilitate the removal of tetracycline from the granular sludge (fig. 2-5 and 9).
A series of adsorption and biodegradation batch tests were performed using ordinary activated sludge and granular sludge (fig. 11 to 15). The results show that: as the initial concentration of tetracycline increased, the amount of TET adsorption and biodegradation by ordinary 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 significantly greater than that of the ordinary activated sludge, and the biodegradation capacity of the granular sludge is slightly higher than that of the ordinary activated sludge.
When the initial concentration of the tetracycline is 0.1, 0.3 and 0.5mg/L, the adsorption amounts of the common activated sludge to the tetracycline are 0.031, 0.080 and 0.118mg/g respectively, and the adsorption amounts of the granular sludge to the tetracycline are 0.037, 0.105 and 0.158mg/g respectively. When the operation time exceeds 30h, the adsorption of the tetracycline by the common activated sludge and the granular sludge reaches the equilibrium. The adsorption of common activated sludge and granular sludge to tetracycline in seawater can be divided into three processes: (1) boundary layer diffusion, (2) intraparticle diffusion, and (3) final equilibrium phase. FIGS. 11 and 12 show that surface adsorption initially accounts for most of the adsorption of tetracycline by sludge, then intraparticle diffusion begins to slow, eventually reaching adsorption equilibrium and the tetracycline concentration in solution decreases. The larger specific surface area and particle size (fig. 4) compared to flocs facilitates a faster boundary layer and intra-particle diffusion rate of tetracycline, resulting in a stronger adsorption capacity of the particles.
Like adsorption, common activated sludge and granular sludge tend to stabilize against tetracycline biodegradation when the operation time exceeds 30 hours. The maximum biodegradation amounts of ordinary activated sludge having 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 granular sludge is slightly superior to that of ordinary activated sludge. Compared with adsorption, the biodegradation of two different sludges has a small difference. Most tetracycline can be adsorbed first on the sludge surface, with only a small amount available for biodegradation, which seems to make no significant contribution to the overall removal of tetracycline. As shown in FIG. 15, the adsorption removal efficiency of the common activated sludge was 61.9%, 53.2% and 47.0% at the initial concentrations of 0.1, 0.3 and 0.5mg/L tetracycline, respectively. Accordingly, the adsorption removal efficiency of the granular sludge was 74.5%, 70.4%, and 63.1%, respectively. The average removal efficiency of ordinary activated sludge and granular sludge was 12.8% and 14.8%, respectively, in terms of biodegradation. The results show that: more than 80% of tetracycline in the two kinds of sludge is removed through adsorption, the adsorption capacity of the granular sludge is obviously stronger, and the granules containing more EPS, larger particle size and specific surface area can adapt to severe water environment and absorb more tetracycline.
To sum up, antibiotic remove device in marine product farming waste water that this application provided simple structure, it is with low costs, can popularize and apply in the aspect of getting rid of antibiotic (like tetracycline) in marine product farming waste water. The corresponding removal method is simple to operate, the process is easy to control, the antibiotics in the marine culture wastewater can be efficiently removed, COD (chemical oxygen demand), ammonia nitrogen and total nitrogen contained in the wastewater are stably treated, and the problem of low removal efficiency of the total nitrogen and the antibiotics in the conventional 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, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A device for removing antibiotics in mariculture wastewater is characterized by comprising a reactor, wherein the reactor comprises a reaction column;
the lower end of the reaction column is a closed end;
the reaction column is internally provided with a baffle plate, the baffle plate is connected to the inner wall of the reaction column and vertically divides the interior 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 mariculture wastewater to be treated can circularly flow from the first reaction chamber to the second reaction chamber in the treatment process;
the first reaction chamber is provided with a water inlet at a position close to the closed end, the second reaction chamber is connected with an aerator at a position close to the closed end, and the middle part of the second reaction chamber is provided with a first water outlet.
2. The removing apparatus according to claim 1, wherein the bottom of the reaction column is further provided with a controller for controlling the inflow condition and the outflow condition.
3. The removing device according to claim 1, wherein a protective cylinder is further sleeved on the top of the reaction column, the upper end of the protective cylinder is open, the lower end of the protective cylinder is closed, and a second water outlet is formed in the side wall of the protective cylinder.
4. A method for removing antibiotics in mariculture wastewater is characterized by comprising the following steps: removing antibiotics in the mariculture wastewater to be treated by using the removing device of any one of claims 1 to 3;
preferably, the antibiotic is tetracycline.
5. The removal process of claim 4, wherein the removal process comprises at least 1 treatment cycle, each treatment cycle comprising, in order, a water-in phase, an anaerobic phase, an aerobic phase, a settling phase, a water-out phase, and a resting phase;
introducing the mariculture wastewater to be treated into the reaction column containing granular sludge through the water inlet in a water inlet stage; then carrying out anaerobic stage treatment, introducing air into the reaction column through the aerator after entering an aerobic stage, settling granular sludge in a settling stage, and discharging the treated mariculture wastewater through the first water outlet in a water outlet stage;
preferably, during the treatment, the volume of the mariculture wastewater displaced each time is 1/2 of the volume of the reaction column;
preferably, the ratio of the treatment time of each stage is 10:50-70:130-160:5:10:10 in sequence;
preferably, each processing cycle is 4 h.
6. The removing method as claimed in claim 5, wherein the amount of the granular sludge added in the reaction column is 1300-2500mg/L, and the particle diameter of the granular sludge is 0.8-2.5 mm.
7. The removal process according to claim 5, wherein the hydraulic retention time in the reaction column is 8h during the entire removal process.
8. The removal method according to claim 5, wherein the dissolved oxygen level in the reaction column is not more than 0.4mg/L in the anaerobic phase.
9. The removal method according to claim 5, wherein in the aerobic stage, the dissolved oxygen level in the reaction column is not less than 4 mg/L.
10. A removal process as claimed in claim 5, wherein the water temperature during removal is in the range of 20-35 ℃.
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