CN112939184A - Method for degrading tetracycline antibiotics in wastewater by using hydraulic cavitation system based on amplification orifice plate - Google Patents
Method for degrading tetracycline antibiotics in wastewater by using hydraulic cavitation system based on amplification orifice plate Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 40
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- 238000003199 nucleic acid amplification method Methods 0.000 title claims abstract description 22
- 230000000593 degrading effect Effects 0.000 title claims abstract description 20
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- PTNZGHXUZDHMIQ-UHFFFAOYSA-N 4-(dimethylamino)-1,5,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2C(C)C(C(O)C3C(C(O)=C(C(N)=O)C(=O)C3N(C)C)(O)C3=O)C3=C(O)C2=C1O PTNZGHXUZDHMIQ-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 22
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
-
- 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
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/005—Valves
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
Abstract
The invention relates to a method for degrading tetracycline antibiotics in wastewater by a hydrodynamic cavitation system based on an amplification orifice plate. The technical scheme is as follows: putting the wastewater containing the tetracycline antibiotics into a degradation pool by using a hydraulic cavitation system based on an amplifying orifice plate, starting a circulating pump, enabling the tetracycline antibiotics wastewater to flow through the amplifying orifice plate device for hydraulic cavitation degradation, returning to the degradation pool, and circularly degrading for 60 min; the auxiliary circulating pipeline is provided with a throttle valve for controlling the pressure at the water inlet end of the amplifying orifice plate device to be 1.0-5.0 bar. The method has the advantages of low treatment cost, simple device, simple and convenient operation, no secondary pollution and suitability for large-scale treatment of the tetracycline antibiotics in the wastewater.
Description
Technical Field
The invention belongs to the field of hydrodynamic cavitation application, and particularly relates to a method for effectively degrading tetracycline antibiotics in wastewater by taking an amplifying orifice plate as a cavitator.
Background
In recent years, antibiotics have been widely used for the treatment and prevention of diseases caused by bacterial infections. Generally, the main sources of antibiotics are hospitals, animal husbandry, agriculture, aquaculture, untreated wastewater, sewer leaks, surface runoff, and the pharmaceutical industry. Although tetracycline brings many benefits to human beings, the tetracycline brings many non-negligible negative effects, and the environmental harm is more serious due to the excessive use of tetracycline. These tetracycline residues can increase bacterial resistance and exacerbate the spread of antibiotic resistance genes, posing a serious threat to public health. According to the results of recent studies, tetracycline antibiotic residues cause various adverse reactions in organisms, including acute and chronic toxicity, destruction of local microbial populations, inhibition of growth of aquatic photosynthetic organisms, and the like. In addition, the residue of such drugs may affect the production of steroids, which in turn may destroy the endocrine of aquatic organisms. Therefore, the search for effective tetracycline removal techniques has become an urgent necessity.
The main methods for degrading tetracycline antibiotics in wastewater include physical adsorption and biological treatment. The traditional physical methods such as adsorption, membrane separation and the like have high cost and low efficiency when purifying wastewater, and can only separate out organic pollutants in water but cannot achieve the aim of completely removing the organic pollutants. Biodegradation processes are generally slow to treat contaminants, primarily converting organic contaminants into some intermediates that may still accumulate in the environment and require further treatment. Therefore, these conventional methods cannot effectively and thoroughly remove the antibiotic molecules in the wastewater, and the use of these methods often causes secondary pollution.
Hydrodynamic cavitation is a promising approach for the degradation of organic pollutants as an advanced oxidation technique. In the process of hydrodynamic cavitation, when the treated wastewater passes through a throttling device such as an orifice plate, the flow velocity of the liquid is suddenly increased. According to the bernoulli principle, as the flow rate increases, the pressure inside the liquid decreases. When the pressure is lower than the saturation vapor pressure of the liquid, a gas core is formed inside the solution in the constriction region. After the liquid flows through the orifice plate, the pressure is gradually restored with the gradual reduction of the liquid flow rate, and the formed gas nuclei grow into cavitation bubbles with larger volume, and the cavitation bubbles collapse in the cavitation area with the further reduction of the pressure. This process releases a large amount of energy in a very short time interval, creating localized high temperatures and pressures. Under these extreme conditions, water molecules are split into species with strong oxidizing properties, such as hydroxyl radicals and hydrogen radicals. These free radical molecules with strong oxidizing properties are beneficial for the degradation of organic pollutants.
Disclosure of Invention
In order to solve the problem that a large amount of tetracycline antibiotic wastewater cannot be completely, efficiently, quickly and thoroughly treated, the invention provides a method for degrading tetracycline antibiotics in wastewater by a hydraulic cavitation system based on an amplification orifice plate.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for degrading tetracycline antibiotics in wastewater by using a hydraulic cavitation system based on an amplification orifice plate is characterized in that the hydraulic cavitation system based on the amplification orifice plate is structured as follows: a cooling water circulation cavity is arranged outside the degradation tank, the degradation tank is connected with a main pipeline through a water pumping pipeline and a circulating pump, the main pipeline is respectively provided with a main circulation pipeline and an auxiliary circulation pipeline which are connected in parallel, the main circulation pipeline is sequentially provided with a pressure gauge, a flowmeter and an amplifying orifice plate device, and the main circulation pipeline returns to the degradation tank through a return pipe I; the auxiliary circulating pipeline is provided with a throttle valve and returns to the degradation tank through a return pipe II; the amplifying orifice plate device is characterized in that an orifice plate is installed in a cylindrical main body pipe, 1-100 through holes are formed in the orifice plate, the orifice plate divides an inner cavity of the cylindrical main body pipe into a water inlet cavity and a water outlet cavity, and the inner diameter of the cylindrical main body pipe is larger than that of a main circulation pipeline and a backflow pipe I.
The method for degrading tetracycline antibiotics in wastewater comprises the following steps: putting the wastewater containing the tetracycline antibiotics into a degradation pool, starting a circulating pump, allowing the tetracycline antibiotics wastewater to flow through an amplifying orifice plate device for hydrodynamic cavitation degradation, returning to the degradation pool, and performing cyclic degradation for 60 min; the auxiliary circulating pipeline is provided with a throttle valve for controlling the pressure at the water inlet end of the amplifying orifice plate device to be 1.0-5.0 bar.
Preferably, in the method, the inner diameter of the cylindrical main pipe is 30-40 mm, and the inner diameters of the main circulation pipeline and the return pipe I are 15-20 mm.
Preferably, in the method, the length of the water inlet cavity in the cylindrical main body pipe is 100-500 mm; the length of the water outlet cavity is 100-500 mm.
Preferably, in the method, the diameter of the through hole is 1-3 mm, and the thickness of the pore plate is 2-6 mm.
Preferably, in the method, the initial concentration of the wastewater containing the tetracycline antibiotics is adjusted to be 5-15 mg/L, and the pH value is adjusted to be 5.0-9.0.
Preferably, in the method, the temperature of the degradation tank is controlled to be 30-50 ℃.
Preferably, in the above method, the tetracycline antibiotic is selected from chlortetracycline hydrochloride, tetracycline hydrochloride, oxytetracycline, and doxycycline hydrochloride.
The invention has the beneficial effects that: the invention creatively provides a hydrodynamic cavitation system based on an amplifying orifice plate and a method for degrading tetracycline antibiotics by utilizing hydrodynamic cavitation. In the process of degrading tetracycline antibiotic wastewater by hydrodynamic cavitation, the hydrodynamic cavitation system can generate the following cavitation process by amplifying the orifice plate: when the waste water flows through the amplifying orifice plate device, the flow velocity is suddenly increased and the pressure is suddenly reduced due to the throttling effect generated by the amplifying orifice plate device, when the pressure at the through hole of the amplifying orifice plate device is reduced to the critical pressure of the liquid (the local pressure is lower than the saturated vapor pressure of the solution at the operating temperature), a non-soluble gas core is formed inside the liquid at the through hole, and the gas core grows into a large cavitation bubble along with the gradual recovery of the pressure in the pipeline along with the outflow of the liquid from the orifice of the intercepting orifice and then collapses. At the moment of collapse of the cavitation bubbles, high temperature, high pressure and a series of chemical effects can be produced, leading to the splitting of water molecules to generate hydroxyl radicals with strong oxidizing property and hydrogen radicals with strong reducing property. The resulting large amount of hydroxyl radicals then diffuse into the liquid medium and are capable of oxidizing the tetracyclic antibiotic molecules present in water. The generated hydrogen radicals are combined with dissolved oxygen in water to generate superoxide radicals, and the tetracycline antibiotics can be effectively removed.
Compared with the traditional orifice plate-based hydrodynamic cavitation device, the enlarged orifice plate can increase the hole distance under the same orifice arrangement and number, and avoid the interference when hydrodynamic cavitation effect is generated between the adjacent orifices; the outlet area of the orifice plate can also provide enough space for the cavitation process, so that stronger hydrodynamic cavitation effect and higher degradation rate are obtained.
Drawings
FIG. 1 is a schematic structural diagram of a hydrodynamic cavitation system based on an enlarged orifice plate according to the present invention.
Fig. 2 is a schematic view of an enlarged orifice plate device.
FIG. 3 is a graph for enlarging the effect of the diameter (X) of the cylindrical main tube in the orifice plate device on the degradation of tetracycline antibiotics.
FIG. 4 is a diagram for enlarging the influence of the length (Y) of the cylindrical main body tube water inlet cavity in the orifice plate device on the degradation of tetracycline antibiotics.
FIG. 5 is a diagram for amplifying the influence of the length (Z) of the water outlet cavity of the cylindrical main tube in the orifice plate device on the degradation of tetracycline antibiotics.
FIG. 6 shows different inorganic anions (Cl)-,CO3 2-And SO4 2-) The effect on degrading tetracycline antibiotics.
FIG. 7 shows different metal cations (Na)+,Mg2+And Ca2+) The effect on degrading tetracycline antibiotics.
FIG. 8 shows different chlortetracycline hydrochloride and H2O2The effect of molar ratio of (A) to (B) on degradation of tetracycline antibiotics.
Wherein, 1-degradation pool; 2-cooling water circulation cavity; 3-water outlet; 4-water inlet; 5-water pumping pipeline; 6-circulating pump; 7-main pipeline; 8-auxiliary circulation pipeline; 9-a main circulation pipeline; 10-pressure gauge; 11-a flow meter; 12-an enlarged orifice plate device; 13-a return pipe I; 14-a throttle valve; 15-reflux pipe II.
Detailed Description
Example 1
As shown in fig. 1 and fig. 2, a hydrodynamic cavitation system based on an enlarged orifice plate has the following structure:
a cooling water circulation cavity (2) is arranged outside the degradation pool (1), a water outlet (3) is arranged at the upper end of the cooling water circulation cavity (2), and a water inlet (4) is arranged at the lower end. The reaction temperature in the degradation pool (1) is controlled by the cooling water circulation cavity (2).
The degradation pool (1) is connected with a main pipeline (7) through a water pumping pipeline (5) and a circulating pump (6).
The main pipeline (7) is respectively provided with a main circulating pipeline (9) and an auxiliary circulating pipeline (8) which are connected in parallel.
The main circulating pipeline (9) is sequentially provided with a pressure gauge (10), a flowmeter (11) and an amplifying orifice plate device (12), and the main circulating pipeline (9) returns to the degradation tank (1) through a return pipe I (13). The amplifying orifice plate device (12) is characterized in that an orifice plate (12-2) is installed on a cylindrical main body pipe (12-1), 1-100 through holes (12-3) are formed in the orifice plate (12-2), the orifice plate (12-2) divides an inner cavity of the cylindrical main body pipe (12-1) into a water inlet cavity (12-4) and a water outlet cavity (12-5), the water inlet cavity (12-4) is communicated with a main circulation pipeline (9), the water outlet cavity (12-5) is communicated with a return pipe I (13), and the inner diameter of the pipe of the cylindrical main body pipe (12-1) is larger than those of the main circulation pipeline (9) and the return pipe I (13). Preferably, the orifice plate (12-2) is connected to the cylindrical main body tube (12-1) by a flange.
Preferably, the inner diameter of the pipe of the cylindrical main pipe (12-1) is 30-40 mm, and the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 15-20 mm.
Preferably, the length of the water inlet cavity (12-4) in the cylindrical main body pipe (12-1) is 100-500 mm; the length of the water outlet cavity (12-5) is 100-500 mm.
Preferably, the diameter of the through hole (12-3) is 1-3 mm, and the thickness of the pore plate (12-2) is 2-6 mm.
And a throttle valve (14) is arranged on the auxiliary circulating pipeline (8), and the auxiliary circulating pipeline (8) returns to the degradation tank (1) through a return pipe II (15).
This example illustrates the degradation of chlortetracycline hydrochloride.
The method for degrading aureomycin hydrochloride wastewater by adopting the hydrodynamic cavitation system based on the amplifying orifice plate in the embodiment 1 comprises the following steps:
placing the wastewater containing aureomycin hydrochloride in a degradation tank (1), and adjusting the initial concentration of the wastewater containing aureomycin hydrochloride to 5-15 mg/L and the pH value to 5.0-9.0. Starting a circulating pump (6), enabling the aureomycin hydrochloride wastewater to flow through an amplifying orifice plate device (12) for hydraulic cavitation degradation, and then returning to the degradation pool (1) for cyclic degradation for 60 min; the pressure at the water inlet end of the amplifying orifice plate device (12) is controlled to be 1.0-5.0 bar through a throttle valve (14) on the auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2).
And (3) measuring the concentration of the aureomycin hydrochloride by using a UV-Vis spectrophotometer at the wavelength of K200-500 nm, wherein the aureomycin hydrochloride has a maximum absorption peak near 370nm, and measuring a standard curve of the concentration and the absorbance to obtain the linear relation between the concentration and the absorbance.
Degradation ratio(％)＝[C0-Ct]/C0×100％
Wherein, C0Is the initial concentration of the aureomycin hydrochloride solution, CtIs the instantaneous concentration after a certain time (T) of hydrodynamic cavitation.
Research on influence of pipe diameter (X) of cylindrical main body pipe in amplification orifice plate device on degradation of aureomycin hydrochloride
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the amplifying orifice plate device (12), the length (Y) of the water inlet cavity (12-4) is 300 mm; the length (Z) of the water outlet cavity (12-5) is 300mm, the diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm. The tube inner diameter (X) of the cylindrical main tube (12-1) was 19mm, 32mm and 40mm, respectively, where X ═ 19mm is a conventional, unamplified orifice plate device, and is used as a comparative example in this section.
The method comprises the following steps: the method comprises the steps that a circulating pump (6) is started, waste water (5.0L) containing aureomycin hydrochloride in a degradation pool (1) is provided, the initial concentration is 10mg/L, the pH value is 7.0, and the waste water flows through a water pumping pipeline (5), the circulating pump (6), a main pipeline (7), a main circulating pipeline (9) and an amplification orifice plate device (12) in sequence, then flows back to the degradation pool (1) through a return pipe I (13), and the pressure of the water inlet end of the amplification orifice plate device (12) is controlled to be 3.0bar through a throttle valve (14) on an auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
The degradation effect of the cylindrical main tube (12-1) with the diameter of 19mm, 32mm and 40mm on chlortetracycline hydrochloride is shown in figure 3. As can be seen from fig. 3, the degradation efficiency of the hydrodynamic cavitation device with each X value is improved with the increase of the cycle time, and the efficiency of degrading aureomycin hydrochloride wastewater by using an amplifying orifice plate device with X being 32mm is the highest and can reach 70.11%.
(II) researching influence of length (Y) of water inlet cavity in amplification orifice plate device on degradation of aureomycin hydrochloride
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the enlarged orifice device (12), the inner diameter (X) of a cylindrical main body pipe (12-1) is 32 mm; the length (Z) of the water outlet cavity (12-5) is 300mm, the diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm. The lengths (Y) of the water inlet cavities (12-4) are respectively 100mm, 200mm and 300 mm.
The method comprises the following steps: the method comprises the steps that a circulating pump (6) is started, waste water (5.0L) containing aureomycin hydrochloride in a degradation pool (1) is provided, the initial concentration is 10mg/L, the pH value is 7.0, and the waste water flows through a water pumping pipeline (5), the circulating pump (6), a main pipeline (7), a main circulating pipeline (9) and an amplification orifice plate device (12) in sequence, then flows back to the degradation pool (1) through a return pipe I (13), and the pressure of the water inlet end of the amplification orifice plate device (12) is controlled to be 3.0bar through a throttle valve (14) on an auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
The length (Y) of the water inlet cavity (12-4) is 100mm, and the degradation effect of 200mm and 300mm on chlortetracycline hydrochloride is shown in figure 4. As can be seen from fig. 4, the degradation efficiency of the hydrodynamic cavitation device with each Y value is improved with the increase of the cycle time, and the efficiency of degrading the aureomycin hydrochloride wastewater by using the hydrodynamic cavitation device with the Y of 100mm is the highest and can reach 75.74%.
(III) researching influence of length (Z) of water outlet cavity in amplification orifice plate device on degradation of aureomycin hydrochloride
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the enlarged orifice device (12), the inner diameter (X) of a cylindrical main body pipe (12-1) is 32 mm; the length (Y) of the water inlet cavity (12-4) is 100mm, the diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm. The lengths (Z) of the water outlet cavities (12-5) are respectively 100mm, 200mm and 300 mm.
The method comprises the following steps: the method comprises the steps that a circulating pump (6) is started, waste water (5.0L) containing aureomycin hydrochloride in a degradation pool (1) is provided, the initial concentration is 10mg/L, the pH value is 7.0, and the waste water flows through a water pumping pipeline (5), the circulating pump (6), a main pipeline (7), a main circulating pipeline (9) and an amplification orifice plate device (12) in sequence, then flows back to the degradation pool (1) through a return pipe I (13), and the pressure of the water inlet end of the amplification orifice plate device (12) is controlled to be 3.0bar through a throttle valve (14) on an auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
The length (Z) of the water outlet cavity (12-5) is 100mm, and the degradation effect of 200mm and 300mm on chlortetracycline hydrochloride is shown in figure 5. As can be seen from fig. 5, the degradation efficiency of the hydrodynamic cavitation device of each Z value is improved with the extension of the cycle time, and the efficiency of degrading the aureomycin hydrochloride wastewater by using the hydrodynamic cavitation device with Z of 200mm is the highest and can reach 78.53%.
(IV) investigation of different inorganic anions (Cl)-，CO3 2-And SO4 2-) Effects on degradation of tetracycline antibiotics
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the enlarged orifice device (12), the inner diameter (X) of a cylindrical main body pipe (12-1) is 32 mm; the length (Y) of the water inlet cavity (12-4) is 100mm, and the length (Z) of the water outlet cavity (12-5) is 200 mm. The diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm.
The method comprises the following steps: dissolving chlortetracycline hydrochloride in NaCl and Na solution2CO3Or Na2SO4(chlortetracycline hydrochloride and NaCl, Na)2CO3Or Na2SO4The mass ratio of the components is 1:1), obtaining mixed liquor containing different inorganic anions with the initial concentration of aureomycin hydrochloride of 10mg/L, slowly pouring 5.0L of the mixed liquor into the degradation pool (1), starting the circulating pump (6), and enabling the mixed liquor in the degradation pool (1) to flow in sequenceAfter passing through a water pumping pipeline (5), a circulating pump (6), a main pipeline (7), a main circulating pipeline (9) and an amplifying pore plate device (12), the water flows back to the degradation tank (1) through a return pipe I (13), and the pressure at the water inlet end of the amplifying pore plate device (12) is controlled to be 3.0bar through a throttle valve (14) on an auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
Different inorganic anions (Cl)-，CO3 2-And SO4 2-) The effect of the presence of (A) on the degradation effect of chlortetracycline hydrochloride is shown in FIG. 6. As can be seen from FIG. 6, different inorganic anions (Cl)-，CO3 2-And SO4 2-) Has inhibition effect on the degradation effect of chlortetracycline hydrochloride.
(V) investigation of different Metal cations (Na)+，Mg2+And Ca2+) Influence on degradation of aureomycin hydrochloride
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the enlarged orifice device (12), the inner diameter (X) of a cylindrical main body pipe (12-1) is 32 mm; the length (Y) of the water inlet cavity (12-4) is 100mm, and the length (Z) of the water outlet cavity (12-5) is 200 mm. The diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm.
The method comprises the following steps: dissolving chlortetracycline hydrochloride in NaCl and MgCl2Or CaCl2(chlortetracycline hydrochloride and NaCl, MgCl)2Or CaCl2The mass ratio of the two components is 1:1), mixed liquor containing different metal cations and with the initial concentration of aureomycin hydrochloride of 10mg/L is obtained, 5.0L of the mixed liquor is slowly poured into the degradation tank (1), the circulating pump (6) is started, the mixed liquor in the degradation tank (1) flows back to the degradation tank (1) through the backflow pipe I (13) after sequentially flowing through the water pumping pipeline (5), the circulating pump (6), the main pipeline (7), the main circulating pipeline (9) and the amplification orifice plate device (12), and the pressure of the water inlet end of the amplification orifice plate device (12) is controlled to be 3.0bar through the throttle valve (14) on the auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
Different metal cation (Na)+，Mg2+And Ca2+) The effect of the presence of (a) on the degradation effect of chlortetracycline hydrochloride is shown in figure 7. As can be seen from FIG. 7, the different metal cations (Na)+，Mg2+And Ca2+) Has inhibition effect on the degradation effect of chlortetracycline hydrochloride.
(VI) Studies of different chlortetracycline hydrochloride and H2O2Influence of molar ratio of (A) on degradation of aureomycin hydrochloride
Conditions are as follows: the inner diameters of the main circulation pipeline (9) and the return pipe I (13) are 19 mm. In the enlarged orifice device (12), the inner diameter (X) of a cylindrical main body pipe (12-1) is 32 mm; the length (Y) of the water inlet cavity (12-4) is 100mm, and the length (Z) of the water outlet cavity (12-5) is 200 mm. The diameter of the through holes (12-3) is 2mm, the number of the through holes is 10, and the thickness of the pore plate (12-2) is 4 mm.
The method comprises the following steps: dissolving chlortetracycline hydrochloride in H2O2In the solution, the initial concentration of the chlortetracycline hydrochloride is 10mg/L, and chlortetracycline hydrochloride and H are obtained2O2The method comprises the steps of slowly pouring 5.0L of mixed solution into a degradation tank (1) according to the molar ratio of 1:0.50, 1:0.75 and 1:1.00, starting a circulating pump (6), enabling the mixed solution in the degradation tank (1) to flow back to the degradation tank (1) through a return pipe I (13) after flowing through a water pumping pipeline (5), the circulating pump (6), a main pipeline (7), a main circulating pipeline (9) and an amplification orifice plate device (12) in sequence, and controlling the pressure at the water inlet end of the amplification orifice plate device (12) to be 3.0bar through a throttle valve (14) on an auxiliary circulating pipeline (8). The temperature of the degradation pool (1) is controlled to be 40 ℃ through the cooling water circulation cavity (2) for carrying out cyclic degradation for 60 min.
Different concentrations of H2O2(chlortetracycline hydrochloride and H)2O2The molar ratios of (1: 0.50), (1: 0.75) and (1: 1.00), respectively), the degradation effect on aureomycin hydrochloride is shown in FIG. 8. As can be seen from FIG. 8, H was present at different concentrations2O2(chlortetracycline hydrochloride and H)2O2The molar ratio of 1:0.50, 1:0.75 and 1:1.00) respectively have certain promotion effect on the degradation process of the chlortetracycline hydrochloride when the chlortetracycline hydrochloride and H are mixed2O2The degradation efficiency of chlortetracycline hydrochloride is highest when the molar ratio of (1: 0.75), and can reach 94.65%.
Claims (7)
1. A method for degrading tetracycline antibiotics in wastewater by using a hydraulic cavitation system based on an amplification orifice plate is characterized in that the hydraulic cavitation system based on the amplification orifice plate is structurally characterized in that: a cooling water circulation cavity (2) is arranged outside the degradation tank (1), the degradation tank (1) is communicated with a main pipeline (7) through a water pumping pipeline (5) and a circulating pump (6), the main pipeline (7) is respectively provided with a main circulating pipeline (9) and an auxiliary circulating pipeline (8) which are connected in parallel, the main circulating pipeline (9) is sequentially provided with a pressure gauge (10), a flowmeter (11) and an amplifying orifice plate device (12), and the main circulating pipeline (9) returns to the degradation tank (1) through a return pipe I (13); a throttle valve (14) is arranged on the auxiliary circulating pipeline (8), and the auxiliary circulating pipeline (8) returns to the degradation tank (1) through a return pipe II (15); the amplifying orifice plate device (12) is characterized in that an orifice plate (12-2) is installed on a cylindrical main body pipe (12-1), 1-100 through holes (12-3) are formed in the orifice plate (12-2), the orifice plate (12-2) divides an inner cavity of the cylindrical main body pipe (12-1) into a water inlet cavity (12-4) and a water outlet cavity (12-5), and the inner diameter of the cylindrical main body pipe (12-1) is larger than those of a main circulation pipeline (9) and a return pipe I (13);
the method for degrading tetracycline antibiotics in wastewater comprises the following steps: putting the wastewater containing the tetracycline antibiotics into a degradation pool (1), starting a circulating pump (6), allowing the tetracycline antibiotics wastewater to flow through an amplifying orifice plate device (12) for hydrodynamic cavitation degradation, returning to the degradation pool (1), and performing cyclic degradation for 60 min; the pressure at the water inlet end of the amplifying pore plate device (12) is controlled to be 1.0-5.0 bar by a throttle valve (14) arranged on the auxiliary circulating pipeline (8).
2. The method as claimed in claim 1, wherein the cylindrical main pipe (12-1) has a pipe inner diameter of 30 to 40mm, and the main circulation pipe (9) and the return pipe (13) have a pipe inner diameter of 15 to 20 mm.
3. The method according to claim 1, wherein the length of the water inlet chamber (12-4) in the cylindrical main body tube (12-1) is 100 to 500 mm; the length of the water outlet cavity (12-5) is 100-500 mm.
4. The method according to claim 1, wherein the diameter of the through-hole (12-3) is 1 to 3mm and the thickness of the orifice plate (12-2) is 2 to 6 mm.
5. The method according to claim 1, wherein the initial concentration of the wastewater containing the tetracycline antibiotic is adjusted to 5 to 15mg/L and the pH value is adjusted to 5.0 to 9.0.
6. The method according to claim 1, characterized in that the temperature of the degradation tank (1) is controlled to be 30-50 ℃.
7. The method of claim 1, wherein said tetracycline antibiotic is selected from chlortetracycline hydrochloride, tetracycline hydrochloride, oxytetracycline, and doxycycline hydrochloride.
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