CN113501631A - Treatment process of livestock and poultry wastewater containing antibiotics - Google Patents
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Abstract
The invention relates to a treatment process of antibiotic-containing livestock and poultry wastewater, which comprises the following steps: 1) carrying out sludge-water separation on the livestock wastewater, and conveying the sludge to a sludge anaerobic process; 2) adding an alkaline agent into the clear liquid; 3) conveying the supernatant after standing treatment to an electric separation process, wherein the electric separation process is carried out in an electric separation tank, an anode and a cathode are arranged in the electric separation tank, and an anion exchange membrane is arranged in the electric separation tank to divide the electric separation tank into an anode chamber and a cathode chamber; 4) the effluent of the anode chamber is conveyed to a high-level oxidation process for treatment; 5) the sludge anaerobic process mixed liquor is subjected to ultrasonic filter pressing treatment, mud cakes obtained by filter pressing are subjected to aerobic composting and/or are returned to the sludge anaerobic process treatment, and the effluent of the ultrasonic filter pressing treatment is conveyed to the alkalization process; 6) and liquid in the cathode chamber and/or effluent of the advanced oxidation process are conveyed to a biochemical process. According to the treatment process disclosed by the invention, the primary concentration of the antibiotics can be efficiently carried out.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a livestock wastewater treatment process.
Background
With the continuous development of the large-scale breeding industry in China in recent years, a large amount of feed additive antibiotics are applied to the breeding industry, and the antibiotics commonly used in the breeding industry comprise tetracyclines, sulfonamides, macrolides and quinolones, wherein the quinolone antibiotics account for a large proportion.
At the present stage, the treatment process of the aquaculture wastewater in China mainly aims at the control of conventional indexes such as COD (chemical oxygen demand), nitrogen and phosphorus and the like, antibiotics are not subjected to targeted treatment, and because antibiotics with higher concentration still exist in the discharge process of livestock wastewater, the increasingly serious problem of antibiotic pollution is solved by the method CN 109052720B.
CN108002605B discloses a method for treating antibiotics in mariculture wastewater, which can achieve a very excellent effect of removing antibiotic pollutants by controlling a proper current density, generating ferrate ions through an electrolytic reaction by an iron electrode and matching with a powerful promoting effect of sodium hypochlorite generated in the system by an insoluble anode graphite electrode.
CN112340818B discloses a method for removing antibiotics in aquaculture wastewater, which is characterized in that a calcined kaolin-ferroferric oxide composite catalytic material and a modified mesoporous silicon adsorption material are added into the wastewater simultaneously, and peroxymonosulfate and hydrogen peroxide are added into the wastewater for reaction.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a livestock and poultry wastewater treatment process.
In order to solve the technical problem, the invention discloses a treatment process of livestock and poultry wastewater containing antibiotics, which comprises the following steps.
1) Separating mud from water: carrying out sludge-water separation on the livestock and poultry wastewater, separating insoluble substances in the livestock and poultry wastewater from the wastewater to obtain sludge and clear liquid, and conveying the sludge to a sludge anaerobic digestion process;
2) an alkalization process: adding an alkaline agent into the clear liquid, adjusting the pH to 8.5-10, and standing for 1-3 h;
3) an electric separation process: conveying the supernatant subjected to standing treatment to an electric separation process, wherein the electric separation process is carried out in an electric separation tank, an anode and a cathode are arranged in the electric separation tank, an anion exchange membrane is arranged in the electric separation tank, the anion exchange membrane divides the electric separation tank into an anode chamber and a cathode chamber, the cathode chamber is provided with a water inlet and a water outlet, and the supernatant is conveyed to the water inlet;
4) an advanced oxidation process: the effluent of the anode chamber is conveyed to a high-level oxidation process for treatment;
5) ultrasonic filter pressing: the mixed liquor of the sludge anaerobic digestion process is subjected to ultrasonic filter pressing treatment, mud cakes obtained by filter pressing are subjected to aerobic composting and/or are returned to the sludge anaerobic digestion process for treatment, and the effluent of the ultrasonic filter pressing treatment is conveyed to the alkalization process;
6) the biochemical process comprises the following steps: and liquid in the cathode chamber and/or effluent of the advanced oxidation process are conveyed to a biochemical process.
Further, the ultrasonic filter pressing process is carried out simultaneously with the ultrasonic treatment and the filter pressing treatment.
Further, the alkaline agent is quicklime and/or hydrated lime.
Further, the advanced oxidation is one or more of ozone oxidation, Fenton oxidation and supercritical treatment.
Further, the antibiotic is a quinolone antibiotic.
Further, the quinolone antibiotic is one or more of norfloxacin, ofloxacin, ciprofloxacin and fleroxacin.
Further, the concentration of the antibiotic in the wastewater is 10-55 mug/L.
Further, the voltage between the anode and the cathode in the electric separation process is controlled to be 3-6V, and the retention time is 15-30 min.
Further, the anode chamber is provided with cation exchange resin.
Furthermore, a regeneration device is arranged between the anode chamber and the advanced oxidation process.
Further, the ultrasonic treatment frequency is 25-35kHz, and the acoustic energy density is 0.05-0.15 w/mL.
The treatment process of the antibiotic-containing livestock and poultry wastewater disclosed by the invention has the following advantages:
1. the invention solves the problems that the antibiotic concentration in the antibiotic-containing livestock wastewater is low, the general biochemical treatment is difficult to remove in a targeted manner, and the medicament/energy consumption of the advanced oxidation technology is overlarge. Antibiotics in the wastewater and waste residues in the wastewater are difficult to separate due to adsorption, sludge and clear liquid are separated by sludge-water separation, then the waste residues are subjected to sludge anaerobic digestion process treatment, the antibiotics are adsorbed on the sludge due to electrostatic adsorption in the acidified sludge, and the sludge-water separation is performed by adopting an ultrasonic filter pressing mode, so that the antibiotics can be efficiently transferred to a liquid state to perform primary concentration of the antibiotics;
2. the invention finds that the antibiotic wastewater after primary separation is easier to exist in the wastewater in an ionic state after the pH value of the antibiotic wastewater is adjusted to 8.5-10, an electric separation process is arranged in the ionic state process to concentrate the ionic antibiotic to an anode chamber, so that the concentration of the antibiotic in the wastewater entering a biochemical process is reduced, and the concentrated antibiotic wastewater is decomposed under the advanced oxidation action of less oxidant and finally removed;
3. in order to prevent the sludge from re-adsorbing the antibiotics, ultrasonic treatment and filter pressing treatment are simultaneously carried out, and the antibiotics in the sludge can be released into the wastewater;
4. in the wastewater treated by the electric separation process, on the basis of quick and efficient consideration, the voltage between an anode and a cathode in the electric separation process is controlled to be 3-8V, and the concentration of the antibiotics is reduced by 60-85% when the retention time is 15-30min, but the concentration of the antibiotics is reduced to more than 90% when the retention time is further increased;
5. the concentration of antibiotics in the concentrated solution in the anode chamber is obviously improved and is about 50-100 times of the concentration of the antibiotics in the original wastewater, and the oxidant loss in the advanced oxidation process is greatly reduced.
Drawings
FIG. 1 is a schematic view of a treatment process of antibiotic-containing livestock wastewater;
FIG. 2 is a schematic diagram of voltage-effluent concentration in treating norfloxacin-containing wastewater by an electrical separation process;
FIG. 3 is a schematic diagram of voltage-effluent concentration in the treatment of ofloxacin-containing wastewater by an electric separation process.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," when used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The embodiment treats the production wastewater from a certain livestock and poultry breeding plant:
through detection: COD8450mg/L, norfloxacin 37.2 mu g/L and Cu2+13.52mg/L;
1) Separating mud from water: conveying the livestock and poultry wastewater to a sedimentation tank for sedimentation treatment, separating insoluble substances in the livestock and poultry wastewater from the wastewater to obtain sludge and clear liquid, wherein COD of the clear liquid of the precipitated wastewater is 2410mg/L, norfloxacin is 18.3 mu g/L, and the sludge is conveyed to a sludge anaerobic digestion process;
2) an alkalization process: adding an alkaline agent into the clear liquid, adjusting the pH to 10, standing for 1h, and discharging COD1720 mg/L;
3) an electric separation process: conveying the supernatant subjected to standing treatment to an electric separation process, wherein the electric separation process is carried out in an electric separation tank, an anode and a cathode are arranged in the electric separation tank, the voltage between the anode and the cathode in the electric separation process is controlled to be 5V, an anion exchange membrane is arranged in the electric separation tank, the electric separation tank is divided into an anode chamber and a cathode chamber by the anion exchange membrane, the cathode chamber is provided with a water inlet and a water outlet, the supernatant is conveyed to the water inlet, the residence time is 20min, and the norfloxacin yielding water is 2.11 mug/L;
4) an advanced oxidation process: the effluent of the anode chamber (norfloxacin is 214.3 mug/L) is conveyed to a high-level oxidation process for treatment, the high-level oxidation technology is ozone oxidation, and the ozone addition concentration is 15 mg/L;
5) ultrasonic filter pressing: carrying out ultrasonic filter pressing treatment on the sludge anaerobic digestion process mixed liquor, carrying out aerobic composting and/or returning to the sludge anaerobic digestion process treatment on a mud cake obtained by filter pressing, and conveying the effluent of the ultrasonic filter pressing treatment to the alkalization process, wherein the frequency of ultrasonic treatment is 25kHz, and the sound energy density is 0.05 w/mL;
6) the biochemical process comprises the following steps: the liquid in the cathode chamber and/or the effluent of the advanced oxidation process are conveyed to a biochemical process, the biochemical process sequentially comprises an anaerobic process (DO is 0.3mg/L and the retention time is 24 h) and an aerobic process (DO is 3mg/L and the retention time is 12 h), the COD of the effluent is 23mg/L, the norfloxacin is 0.02 mu g/L, and the Cu is2+It was 0.02 mg/L. Meets the primary standard of pollutant discharge Standard of livestock and poultry Breeding (GB18596-2001) and the primary standard of Integrated wastewater discharge Standard (GB 8978-1996).
Example 2
The embodiment treats the production wastewater from a certain livestock and poultry breeding plant:
through detection: COD11000mg/L, ofloxacin 23.1 mug/L;
1) separating mud from water: conveying the livestock and poultry wastewater to a sedimentation tank for sedimentation treatment, separating insoluble substances in the livestock and poultry wastewater from the wastewater to obtain sludge and clear liquid, wherein COD of the clear liquid of the precipitated wastewater is 2689mg/L, ofloxacin is 11.6 mu g/L, and the sludge is conveyed to a sludge anaerobic digestion process;
2) an alkalization process: adding an alkaline agent into the clear liquid, adjusting the pH to 9, standing for 1.5h, and obtaining effluent COD of 2013 mg/L;
3) an electric separation process: conveying the supernatant subjected to standing treatment to an electric separation process, wherein the electric separation process is carried out in an electric separation tank, an anode and a cathode are arranged in the electric separation tank, the voltage between the anode and the cathode in the electric separation process is controlled to be 6V, an anion exchange membrane is arranged in the electric separation tank, the electric separation tank is divided into an anode chamber and a cathode chamber by the anion exchange membrane, the cathode chamber is provided with a water inlet and a water outlet, the supernatant is conveyed to the water inlet, the residence time is 15min, and the ofloxacin outlet is 1.98 mug/L;
4) an advanced oxidation process: the effluent of the anode chamber (ofloxacin is 199.1 mug/L) is conveyed to a high-level oxidation process for treatment, the high-level oxidation technology is ozone oxidation, and the ozone addition concentration is 15 mg/L;
5) ultrasonic filter pressing: carrying out ultrasonic filter pressing treatment on the sludge anaerobic digestion process mixed liquor, carrying out aerobic composting and/or returning to the sludge anaerobic digestion process treatment on a mud cake obtained by filter pressing, and conveying the effluent of the ultrasonic filter pressing treatment to the alkalization process, wherein the frequency of ultrasonic treatment is 30kHz, and the sound energy density is 0.08 w/mL;
6) the biochemical process comprises the following steps: and conveying the liquid in the cathode chamber and/or the effluent of the advanced oxidation process to a biochemical process, wherein the biochemical process sequentially comprises an anaerobic process (DO is 0.3mg/L and the retention time is 24 h) and an aerobic process (DO is 3mg/L and the retention time is 12 h), the COD of the effluent is 31mg/L, and the ofloxacin is 0.06 mu g/L. Meets the primary standard of pollutant discharge Standard of livestock and poultry Breeding (GB18596-2001) and the primary standard of Integrated wastewater discharge Standard (GB 8978-1996).
Example 3
On the basis of example 1, the effect of voltage on antibiotic removal in an electrical separation process was investigated. Specific values are shown in figure 2. It can be seen that the separation effect is optimal when the voltage is 5V and the residence time is 20 min.
Example 4
On the basis of example 2, the effect of voltage on antibiotic removal in an electrical separation process was investigated. Specific values are shown in figure 3. It can be seen that the separation effect is optimal when the voltage is 6V and the retention time is 15 min.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (10)
1. A treatment process of livestock and poultry wastewater containing antibiotics is characterized by comprising the following steps:
1) separating mud from water: carrying out sludge-water separation on the livestock and poultry wastewater, separating insoluble substances in the livestock and poultry wastewater from the wastewater to obtain sludge and clear liquid, and conveying the sludge to a sludge anaerobic digestion process;
2) an alkalization process: adding an alkaline agent into the clear liquid, adjusting the pH to 8.5-10, and standing for 1-3 h;
3) an electric separation process: conveying the supernatant subjected to standing treatment to an electric separation process, wherein the electric separation process is carried out in an electric separation tank, an anode and a cathode are arranged in the electric separation tank, an anion exchange membrane is arranged in the electric separation tank, the anion exchange membrane divides the electric separation tank into an anode chamber and a cathode chamber, the cathode chamber is provided with a water inlet and a water outlet, and the supernatant is conveyed to the water inlet;
4) an advanced oxidation process: the effluent of the anode chamber is conveyed to a high-level oxidation process for treatment;
5) ultrasonic filter pressing: the mixed liquor of the sludge anaerobic digestion process is subjected to ultrasonic filter pressing treatment, mud cakes obtained by filter pressing are subjected to aerobic composting and/or are returned to the sludge anaerobic digestion process for treatment, and the effluent of the ultrasonic filter pressing treatment is conveyed to the alkalization process; and
6) the biochemical process comprises the following steps: and liquid in the cathode chamber and/or effluent of the advanced oxidation process are conveyed to a biochemical process.
2. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein the ultrasonic filter pressing process is carried out simultaneously with the filter pressing process, the frequency of the ultrasonic treatment is 25-35kHz, and the sound energy density is 0.05-0.15 w/mL.
3. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein said alkaline agent is quicklime and/or slaked lime.
4. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein said advanced oxidation is one or more of ozone oxidation, Fenton oxidation and supercritical treatment.
5. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein said antibiotic is quinolone antibiotic.
6. The process of claim 5, wherein the quinolone antibiotic is one or more of norfloxacin, ofloxacin, ciprofloxacin and fleroxacin.
7. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein the concentration of said antibiotic in said wastewater is 10-55 μ g/L.
8. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 1, wherein the voltage between the anode and the cathode in the electric separation process is controlled to be 3-6V, and the retention time is 15-30 min.
9. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 8, wherein said anode chamber is provided with cation exchange resin.
10. The process for treating antibiotic-containing livestock and poultry wastewater as claimed in claim 9, wherein a regeneration device is provided between said anode chamber and said advanced oxidation process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929201A (en) * | 2021-11-24 | 2022-01-14 | 太原理工大学 | Application of peroxymonosulfate in degradation of nitrogen heterocyclic compound and degradation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541014A (en) * | 2015-12-29 | 2016-05-04 | 淄博永辰环境影响评价有限公司 | Treatment method of livestock/poultry culture wastewater |
| CN108002605A (en) * | 2017-11-17 | 2018-05-08 | 浙江海洋大学 | The processing method of antibiotic in a kind of marine culture wastewater |
| CN110980895A (en) * | 2019-12-17 | 2020-04-10 | 嘉兴学院 | Method and device for electro-adsorption and degradation removal of antibiotics from water |
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- 2021-09-08 CN CN202111046744.3A patent/CN113501631B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541014A (en) * | 2015-12-29 | 2016-05-04 | 淄博永辰环境影响评价有限公司 | Treatment method of livestock/poultry culture wastewater |
| CN108002605A (en) * | 2017-11-17 | 2018-05-08 | 浙江海洋大学 | The processing method of antibiotic in a kind of marine culture wastewater |
| CN110980895A (en) * | 2019-12-17 | 2020-04-10 | 嘉兴学院 | Method and device for electro-adsorption and degradation removal of antibiotics from water |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929201A (en) * | 2021-11-24 | 2022-01-14 | 太原理工大学 | Application of peroxymonosulfate in degradation of nitrogen heterocyclic compound and degradation method |
| CN113929201B (en) * | 2021-11-24 | 2023-08-04 | 太原理工大学 | Application of peroxymonosulfate in degradation of nitrogen heterocyclic compound and degradation method |
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