CN109734156B - Antibiotic wastewater treatment device and treatment method - Google Patents
Antibiotic wastewater treatment device and treatment method Download PDFInfo
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- CN109734156B CN109734156B CN201910146973.9A CN201910146973A CN109734156B CN 109734156 B CN109734156 B CN 109734156B CN 201910146973 A CN201910146973 A CN 201910146973A CN 109734156 B CN109734156 B CN 109734156B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000003115 biocidal effect Effects 0.000 title claims description 48
- 238000004065 wastewater treatment Methods 0.000 title claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
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Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The device comprises a reactor, a cathode and an anode which are positioned in the reactor, a direct current power supply connected with the cathode and the anode, and a water flow circulating device, wherein the reactor is provided with a roller horizontal groove body, the cathode is a porous cylinder type cathode which is horizontally arranged in the roller horizontal groove body, the anode is horizontally arranged in the porous cylinder type cathode, one end of the anode is connected with the positive pole of the direct current power supply, the porous cylinder type cathode is connected with the negative pole of the direct current power supply, the water flow circulating device is connected with the water inlet and the water outlet of the roller horizontal reactor, and the water flow circulating device is used for enabling wastewater containing antibiotics to continuously flow circularly through the roller horizontal reactor in the treatment process and fully contact with the cathode and the anode to generate electrochemical advanced oxidation reaction. The invention has good degradation effect, high mass transfer efficiency, continuous operation, low energy consumption and low cost. The device has the advantages of small volume, small occupied area and simpler operation.
Description
Technical Field
The invention relates to wastewater treatment, in particular to an antibiotic wastewater treatment device and a treatment method.
Background
Pharmaceutical and Personal Care Products (PPCPs) mainly include various prescription and over-the-counter drugs (e.g., antibiotics, anti-inflammatory analgesics, cholesterol, etc.), and various skin care products and cosmetics, fragrances, personal hygiene products, etc., and metabolites of these products. Among the numerous PPCPs, antibiotics are commonly used in medicine, livestock and aquaculture, and residual antibiotics can greatly threaten ecological environment, particularly ecological safety of water bodies and potential human health through environmental water bodies, plants, soil, food chains and the like. The traditional sewage treatment process is mainly designed with the main aim of reducing BOD and denitrification and dephosphorization, and has no effective removal effect on the novel pollutant PPCPs. In recent years, PPCPs pollutants such as antibiotics are detected in the effluent medium frequency of sewage treatment plants at home and abroad. Many wastewater treatment plants also have no specific method for antibiotic wastewater treatment, resulting in the inability of such contaminants to be effectively removed. Therefore, a process and a method for treating antibiotic wastewater have become an important subject.
The current antibiotic wastewater treatment methods mainly comprise a coagulation method, an adsorption method, a biological method, a chemical oxidation method, a membrane separation method and the like. The coagulation method can be used for treating antibiotic pollutants with large molecular weight and non-polarity, but has little removal effect on antibiotic pollutants with small molecular weight and strong polarity, and is generally used for pretreatment of antibiotic wastewater. The adsorption method is a common antibiotic wastewater treatment method, particularly activated carbon adsorption, has the advantages of easily available adsorption materials, low reaction cost and the like, but the adsorption method only realizes the transfer of pollutants and can not mineralize the pollutants, and the risk of the pollutants still exists. The biological method mainly refers to an aerobic and anaerobic treatment method, and because the wastewater contains a large amount of biological toxic substances, the biological method is only used for treatment, the effect is unstable, the occupied area is large, and the period is long. Chemical oxidation methods include photocatalytic oxidation, ozone oxidation, and the like. The photocatalytic oxidation method utilizes a photocatalyst to generate hydroxyl free radicals to treat antibiotic wastewater, but the method is carried out under the illumination condition, so that the limitation is large, the catalyst is easy to run off and is not easy to be used for the second time, and the cost is high. Ozone oxidation has relatively good treatment effect on various antibiotic wastewater, but the technology is limited by low solubility and low utilization rate of ozone, and the ozone oxidation has selectivity, and preferentially oxidizes organic matters with unsaturated bonds, such as organic matters with benzene ring structures, etc., however, the oxidation efficiency of ozone on some high-stability and nondegradable organic matters with saturated bonds is very low, and higher ozone concentration is often required to better control the concentration of PPCPs in water, and excessive ozone can remain in water, so that bromine ions in the water can be converted into bromate, thereby bringing cancerogenic risks. The membrane separation method, in particular to a reverse osmosis membrane, can efficiently intercept pollutants in antibiotic wastewater, has relatively simple operation and small occupied area, but the reverse osmosis membrane plays a role in separation and enrichment, the produced concentrated water rich in antibiotics still faces the problem of how to treat, and the reverse osmosis membrane has high price, is easy to pollute and has a large influence on the physical and chemical properties of target pollutants and the types of membranes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a treatment device and a treatment method for antibiotic wastewater.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the utility model provides an antibiotic effluent treatment plant, is electrochemical advanced oxidation unit, is including the reactor, be located negative pole and positive pole in the reactor, with the negative pole with the direct current power and the rivers circulating device that positive pole links to each other, the reactor has cylinder horizontal cell body, the negative pole is for transversely putting the porous cylinder negative pole in the cylinder horizontal cell body, the positive pole is transversely put in porous cylinder negative pole, the one end of positive pole with the positive pole of direct current power links to each other, porous cylinder negative pole with the negative pole of direct current power links to each other, rivers circulating device connects the water inlet and the delivery port of cylinder horizontal reactor, rivers circulating device is used for making antibiotic-containing waste water constantly pass through in the treatment process cylinder horizontal reactor circulation flow, with the negative pole with the positive pole fully contacts and takes place electrochemical advanced oxidation reaction.
Further:
the roller horizontal tank body is made of organic glass PMMA material, preferably, the inner diameter of the roller horizontal tank body is 12-18cm, more preferably 15cm, and the height of the roller horizontal tank body is 15-35cm, more preferably 25cm.
The anode is microporous titanium oxide Ti 4 O 7 Ceramic tube, preferably, the microporous titanium oxide Ti 4 O 7 The pipe diameter of the ceramic pipe is 10-20mm, more preferably 15mm, and the microporous titanium suboxide Ti 4 O 7 The ceramic tube is 10-30cm in height, more preferably 20cm. The anode adopts titanium dioxide anode ceramic tube, which has excellent corrosion resistance and electrochemical performance and strong activity.
Preferably, the cathode is a stainless steel porous cylinder cathode, preferably the diameter of the porous cylinder cathode is 3-8 cm, the pore diameter is 3-6mm, more preferably 4mm.
The spacing between the cathode and the anode is 0.05-5 cm.
One end of the anode is fixed on one side of the reactor, preferably directly welded, and the other end of the anode is connected with the positive electrode of the direct current power supply through a titanium wire; one end of the cathode is fixed on one side of the reactor, and the other end of the cathode is connected with the negative electrode of the direct current power supply through a titanium wire.
The water inlet of the reactor is arranged at the lower part and one side of the horizontal tank body of the roller, preferably water is simultaneously fed from the water inlets at the lower part and one side, and the water outlet of the reactor is arranged at the upper part of the horizontal tank body of the roller, preferably, the wastewater containing antibiotics circulates in the reactor for 40-200 times in the reaction period.
The water flow circulating device also comprises a peristaltic pump, and the wastewater containing antibiotics is circularly fed into the reactor through the peristaltic pump.
The antibiotic waste water treatment method adopts the antibiotic waste water treatment device to treat the waste water containing the antibiotics, and preferably, the antibiotics in the water body are degraded under the condition that the electric quantity is 1-10 ampere.h/liter and the pH value is 3-10.
Further:
sodium hydroxide or dilute hydrochloric acid is added into the water body containing the antibiotics to adjust the pH value of the solution to 3-10.
Sodium sulfate or sodium chloride is added into the water body containing the antibiotics, and the content of the sodium sulfate or the sodium chloride added into the water body is 1.5-5 g/L.
The invention has the following beneficial effects:
the antibiotic wastewater treatment device for implementing the electrochemical advanced oxidation reaction has the advantages of good degradation effect, high mass transfer efficiency, continuous operation, low energy consumption and low cost. The device has the advantages of small volume, small occupied area, simpler operation, easy automatic control and convenient management, and two main factors to be controlled are current and voltage. The device and the method have multiple functions, can be used for phase separation of poison conversion, suspension or colloid systems, are convenient for comprehensive treatment, can be coupled with other treatment modes, and enhance the treatment effect of the whole system. The preferred solution provides further advantages, for example, the addition of a small amount of electrolyte, such as sodium sulfate, sodium ions, in the electrochemical treatment of antibiotic wastewaterThe conductivity of the solution is enhanced, sulfate ions can be electrochemically oxidized into sulfate radicals in a high level under an electrochemical system, and the method can assist an electrochemical method to remove antibiotic pollutants. Preferably, the invention adopts microporous titanium dioxide Ti 4 O 7 The ceramic tube is an anode, has excellent corrosion resistance and electrochemical performance, is not easy to inactivate, and has long service life. The invention is worth popularizing and applying in the sewage treatment industry, and is especially suitable for domestic sewage treatment, landfill leachate treatment, toilet human body excrement and urine wastewater treatment, printing and dyeing wastewater treatment, petrochemical wastewater treatment, coal chemical wastewater treatment, biological medicine wastewater treatment and the like.
Drawings
FIG. 1 is a schematic diagram of an antibiotic wastewater treatment apparatus according to an embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
Referring to fig. 1, in one embodiment, an antibiotic wastewater treatment device is an electrochemical advanced oxidation device, and comprises a reactor, a cathode 3 and an anode 4 which are positioned in the reactor, a direct current power supply 1 connected with the cathode 3 and the anode 4, and a water flow circulation device, wherein the reactor is provided with a roller horizontal tank body 2, the cathode 3 is a porous cylinder type cathode transversely arranged in the roller horizontal tank body 2, the anode 4 is transversely arranged in the porous cylinder type cathode, one end of the anode 4 is connected with the positive electrode of the direct current power supply 1, the porous cylinder type cathode is connected with the negative electrode of the direct current power supply 1, the water flow circulation device is connected with the water inlet and the water outlet of the roller horizontal reactor, and the water flow circulation device is used for enabling wastewater containing antibiotics to continuously flow circularly through the roller horizontal reactor in the treatment process and fully contact with the cathode 3 and the anode 4 to perform electrochemical advanced oxidation reaction. The water flow circulation device can comprise a liquid storage tank 5 communicated with the water inlet and the water outlet of the horizontal groove body 2 of the roller and a driving device for driving water flow. A water outlet valve 7 can be arranged on the liquid storage tank 5 and is used for discharging water treated by the reactor.
In a preferred embodiment, the drum horizontal tank 2 is made of plexiglass PMMA material, preferably the inner diameter of the drum horizontal tank 2 is 12-18cm, more preferably 15cm. Preferably, the height of the roller horizontal tank body 2 is 15-35cm. In one embodiment, the roller horizontal tank 2 is 25cm in height.
The anode 4 is microporous titanium oxide Ti 4 O 7 Ceramic tube, preferably, the microporous titanium oxide Ti 4 O 7 The diameter of the ceramic tube is 10-20mm, more preferably 15mm. Preferably, the microporous titanium suboxide Ti 4 O 7 The height of the ceramic tube is 10-30cm. In one embodiment, the microporous titanium suboxide Ti 4 O 7 The ceramic tube was 20cm in height. Preferably, the cathode 3 is a stainless steel porous cylinder cathode. Preferably, the diameter of the porous cylindrical cathode is 3-8 cm, and the pore diameter is 3-6mm, more preferably 4mm.
In a preferred embodiment, the spacing between the cathode 3 and the anode 4 is 0.05-5 cm.
In a preferred embodiment, one end of the anode 4 is fixed at one side of the reactor, preferably by direct welding, and the other end is connected with the positive electrode of the direct current power supply 1 through a titanium wire; one end of the cathode 3 is fixed on one side of the reactor, and the other end is connected with the negative electrode of the direct current power supply 1 through a titanium wire.
In a preferred embodiment, the water inlet of the reactor is arranged at the lower part and one side of the horizontal drum tank body, preferably water is fed from the water inlet at the lower part and one side at the same time, and the water outlet of the reactor is arranged at the upper part of the horizontal drum tank body.
In a preferred embodiment, the antibiotic-containing wastewater is circulated in the reactor 40 to 200 times during the reaction cycle.
In a preferred embodiment, the water circulation device further comprises a peristaltic pump 6, through which peristaltic pump 6 the antibiotic-containing waste water is circulated into the reactor.
An antibiotic wastewater treatment method, wherein the antibiotic wastewater treatment device according to any one of the embodiments is used for treating wastewater containing antibiotics.
In a preferred embodiment, the antibiotics in the body of water are degraded at a power level of 1 to 10 amp hour/liter, ph=3 to 10.
In a preferred embodiment, sodium hydroxide or dilute hydrochloric acid is added to the water containing the antibiotic to adjust the pH of the solution to 3-10.
In a preferred embodiment, the electrolyte sodium sulfate or sodium chloride is added to the water containing the antibiotic, wherein the content of the sodium sulfate or sodium chloride added to the water is 1.5-5 g/L. According to the content, electrolytes such as sodium sulfate, sodium chloride and the like are added into the water body containing the antibiotics, so that the conductivity of the solution can be effectively improved.
In a more preferred embodiment, sodium sulfate is added, wherein sodium ions can enhance the conductivity of the solution, and sulfate ions can be electrochemically oxidized into sulfate radicals in an electrochemical system, thereby assisting the electrochemical method in removing antibiotic pollutants.
In a preferred embodiment, the antibiotic-containing wastewater is circulated in the reactor 40 to 200 times during the reaction cycle.
In a typical embodiment, the cell body for performing the electrochemical advanced oxidation reaction is made of a Plexiglas (PMMA) material, 15cm in diameter and 25cm in height. The reactor is a roller horizontal reactor, and the cathode and anode are transversely arranged in the roller. The anode of the electrode is a microporous titanium dioxide (Ti 4O 7) ceramic tube with the diameter of 15mm and the height of 20cm. One end of the anode is directly welded on one side of the reactor, and the other end is connected with the positive electrode of the direct current power supply through a titanium wire. The cathode is a stainless steel porous cylinder cathode, the diameter of the cathode is 3-8 cm, and the porous aperture is 4mm. The cathode is outside, the anode is inside, and the interval between the cathode and the anode is 0.05 cm to 5cm. One end of the cathode is fixed on one side of the reactor, and the other end of the cathode is connected with the negative electrode of the direct current power supply through a titanium wire. During operation, water containing antibiotics is added into the reactor through the peristaltic pump, and when the solution completely passes through the electrode, the direct current power supply is connected. And circulating the wastewater containing the antibiotics in the reactor for 40-200 times in the reaction period. The electrochemical advanced oxidation process mainly comprises a direct electron transfer process and a process of generating hydroxyl radicals by anodic oxidation of water. The hydroxyl radical generated in the process can be directly reacted with organic pollutants in the wastewater in an indiscriminate manner, and no chemical reagent is generally added in the treatment process, so that secondary pollution can be avoided. The water body treated by the antibiotic wastewater treatment device can be used for detecting the content of each antibiotic by using a triple quaternary rod liquid phase dual mass spectrum (LC-MS/MS) and detecting the mineralization rate of each antibiotic by using an organic total carbon (TOC) analyzer, and has excellent purification effect.
The electrochemical reactor of the invention can continuously work, has high mass transfer efficiency, low energy consumption, good degradation effect and low cost. The device has the advantages of small volume, small occupied area, simpler operation, and two main factors to be controlled, namely current and voltage, is easy to automatically control and convenient to manage. The device and the method have multiple functions and are convenient for comprehensive treatment. Can be used for poison conversion, suspension or phase separation of colloid systems. Can also be coupled with other methods to enhance the treatment effect of the whole system. Furthermore, a small amount of electrolyte such as sodium sulfate and sodium ions are added in the process of electrochemically treating the antibiotic wastewater, so that the conductivity of the solution can be enhanced, sulfate ions can be electrochemically oxidized into sulfate radicals in a high level under an electrochemical system, and the method can assist an electrochemical method in removing antibiotic pollutants. Preferably, the invention adopts microporous titanium dioxide Ti 4 O 7 The ceramic tube is an anode, has excellent corrosion resistance and electrochemical performance, is not easy to inactivate, and has long service life. The invention is popularized and applied in the sewage treatment industry, and is especially suitable for domestic sewage treatment, landfill leachate treatment, human body excrement and urine wastewater treatment in a toilet, printing and dyeing wastewater treatment, petrochemical wastewater treatment, coal chemical wastewater treatment, biological medicine wastewater treatment and the like.
Example 1:
water containing 50mg/L tetracycline at pH=7, na 2 SO 4 The adding amount is 1.5g/L, and the mineralization rate can reach more than 70% under the condition of 3.75 ampere hour/liter of electric quantity.
Example 2:
na is added to example 1 2 SO 4 The adding amount is changed to 3g/L, and the mineralization rate can reach more than 80%.
Example 3:
in example 1, the mineralization rate can reach more than 90% by changing the pH to 3.
Example 4:
in example 1, the mineralization rate can reach more than 99% by using 7 ampere.h/L of electric quantity.
Example 5:
50ng/L water body containing azithromycin, amoxicillin, lincomycin, erythromycin, tetracycline, roxithromycin, sulfomethazole, clarithromycin, terramycin and ofloxacin respectively, and the pH value is=5 and Na 2 SO 4 The addition amount is 1.5g/L, and the total removal rate can reach more than 90% under the condition of 5 ampere hour/liter of electric quantity.
Example 6:
na is added to example 5 2 SO 4 The adding amount is changed to 5g/L, and the total removal rate can reach more than 99 percent.
Example 7:
in example 5, the pH was changed to 3, and the total removal rate was 95% or more.
Example 8
Water containing azithromycin, amoxicillin, lincomycin, erythromycin, tetracycline, roxithromycin, sulfomethazole, clarithromycin, terramycin and ofloxacin at a concentration of 5mg/L respectively, at pH=5 and Na 2 SO 4 The adding amount is 1.5g/L, and the mineralization rate can reach more than 80% under the condition of 3.75 ampere hour/liter of electric quantity.
Example 9:
in example 8, the mineralization rate can reach more than 90% by changing the pH to 2.
Example 10:
in example 8, the electric quantity is changed to 10 ampere.h/liter, and the mineralization rate can reach more than 98 percent.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (7)
1. The antibiotic wastewater treatment method is characterized in that the antibiotic wastewater treatment device comprises a reactor, a cathode and an anode which are positioned in the reactor, a direct current power supply connected with the cathode and the anode and a water flow circulation device, wherein the reactor is provided with a roller horizontal tank body, the cathode is a porous cylinder type cathode transversely arranged in the roller horizontal tank body, the anode is transversely arranged in the porous cylinder type cathode, one end of the anode is connected with the positive electrode of the direct current power supply, the porous cylinder type cathode is connected with the negative electrode of the direct current power supply, the water flow circulation device is connected with the water inlet and the water outlet of the roller horizontal reactor, and the water flow circulation device is used for enabling wastewater containing antibiotics to continuously flow circularly through the roller horizontal reactor in the treatment process and fully contact with the cathode and the anode to generate electrochemical advanced oxidation reaction; the inner diameter of the horizontal groove body of the roller is 12-18cm, the height of the horizontal groove body of the roller is 15-35cm, and the anode is microporous titanium dioxide Ti 4 O 7 Ceramic tube, said microporous titanium oxide Ti 4 O 7 The pipe diameter of the ceramic pipe is 10-20mm, and the microporous titanium dioxide Ti 4 O 7 The ceramic tube is 10-30cm in height, the cathode is a stainless steel porous cylinder type cathode, the diameter of the porous cylinder type cathode is 3-8 cm, and the aperture of the porous cylinder type cathode is 3-6mm; the method comprises the steps of adopting the antibiotic wastewater treatment device to treat wastewater containing antibiotics, and controlling pH to be 3-5 and Na 2 SO 4 Degrading antibiotics in the water body under the condition that the addition amount is 1.5-5 g/L and the electric quantity is 5 ampere/hour; thereby achieving removal of ng/L grade antibiotic contaminants including azithromycin, amoxicillin, lincomycin, erythromycin, tetracycline, roxithromycin, sulfamethoxazole, clarithromycin, terramycin, ofloxacin.
2. The antibiotic wastewater treatment method of claim 1, wherein the drum horizontal tank is made of a plexiglass PMMA material, the inner diameter of the drum horizontal tank is 15cm, and the height of the drum horizontal tank is 25cm.
3. The antibiotic wastewater treatment method according to claim 1 or 2, wherein the microporous titanium suboxide Ti 4 O 7 The pipe diameter of the ceramic pipe is 15mm, and the microporous titanium dioxide Ti 4 O 7 The height of the ceramic tube is 20cm; the pore diameter of the porous cylinder type cathode is 4mm.
4. The antibiotic wastewater treatment method according to claim 3, wherein a distance between the cathode and the anode is 0.05 to 5cm.
5. The antibiotic wastewater treatment method according to any one of claims 1 to 2, wherein one end of the anode is fixed at one side of the reactor, is directly welded, and the other end is connected with the positive electrode of the direct current power supply through a titanium wire; one end of the cathode is fixed on one side of the reactor, and the other end of the cathode is connected with the negative electrode of the direct current power supply through a titanium wire.
6. The antibiotic wastewater treatment method according to any one of claims 1 to 2, wherein a water inlet of the reactor is provided at a lower portion and one side of the horizontal reactor, water is simultaneously introduced from the water inlets at the lower portion and one side, a water outlet of the reactor is provided at an upper portion of the horizontal reactor, and wastewater containing an antibiotic is circulated in the reactor 40 to 200 times in a reaction cycle.
7. The antibiotic wastewater treatment method according to any one of claims 1 to 2, wherein the water flow circulation device further comprises a peristaltic pump by which the wastewater containing the antibiotic is circulated into the reactor.
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| WO2016127942A1 (en) * | 2015-02-11 | 2016-08-18 | 清华大学 | Method for removing ppcps micropollutants from secondary settling tank wastewater |
| CN106082399A (en) * | 2016-06-01 | 2016-11-09 | 深圳市大净环保科技有限公司 | A kind of electrochemical advanced oxidation device |
| CN206289019U (en) * | 2016-12-14 | 2017-06-30 | 哈尔滨工业大学 | A kind of tubular electrochemical reactor for processing dyeing waste water |
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