CN114634241B - Method for simultaneously removing sulfate and florfenicol in water - Google Patents
Method for simultaneously removing sulfate and florfenicol in water Download PDFInfo
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- CN114634241B CN114634241B CN202210359928.3A CN202210359928A CN114634241B CN 114634241 B CN114634241 B CN 114634241B CN 202210359928 A CN202210359928 A CN 202210359928A CN 114634241 B CN114634241 B CN 114634241B
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 111
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 title claims abstract description 81
- 229960003760 florfenicol Drugs 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 17
- 239000011593 sulfur Substances 0.000 description 17
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000057297 Pepsin A Human genes 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000008239 natural water Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229940111202 pepsin Drugs 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Biodiversity & Conservation Biology (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for simultaneously removing sulfate and florfenicol in water, which comprises the following steps: (1) Adding domesticated sulfate reducing bacteria sulfate matrix into an anaerobic bottle, and carrying out ventilation reaction in a constant-temperature oscillation state; (2) Adding the bacterial liquid and the sulfate matrix obtained in the step (1) into a cathode chamber of a photoelectric coupling microbial reactor, wherein the anode liquid of the photoelectric coupling microbial reactor is sulfate solution with the concentration of 5 g/L; (3) Placing the anode of the reactor in the step (2) under an ultraviolet light source to generate electricity by the photo anode; (4) Florfenicol was added to the cathode chamber of the reactor of step (3) and incubated at 27℃and 1.2V for one week to remove sulfate and florfenicol. The invention improves on the basis of photoelectrochemistry battery, adds microorganism at the cathode, builds photoelectric coupling microorganism electrolysis system, and the combination of photoanode electricity generation and microorganism degradation technology can effectively remove sulfate and florfenicol in water, thereby reducing the biotoxicity of the system.
Description
Technical Field
The invention relates to the field of water pollution control, in particular to a method for simultaneously removing sulfate and florfenicol in water.
Background
Antibiotics are chemical substances produced by the metabolism of microorganisms and inhibit the growth and activity of microorganisms. Is widely applied to industries such as medical treatment, agriculture, animal husbandry, aquaculture and the like. However, the traditional sewage biological treatment cannot effectively remove the antibiotics, the part of the antibiotics which can be metabolized by organisms is very limited, and most of the antibiotics can be discharged into natural water in the form of raw medicines to cause pollution. Along with the migration of antibiotics in water environments, various antibiotics are currently detected in surface water, groundwater and some drinking water all over the world. Antibiotics in the environment have various effects on animals, plants and humans, such as toxicity to aquatic organisms, reduction of human immunity, promotion of generation of resistant bacteria and resistant genes, and the like, thereby destroying ecological balance.
The florfenicol is taken as one of antibiotics and is widely applied to the fields of livestock, poultry, aquaculture and the like. At present, florfenicol is frequently detected in water bodies in the global scope, bacterial drug resistance can be induced in the environment for a long time, and serious harm is caused, so that the pollution control of florfenicol is particularly important.
At present, the treatment of antibiotics mainly comprises a physicochemical method and a biological method. Although the physical and chemical methods can effectively reduce the concentration of antibiotics in sewage, a large amount of electric energy is consumed, the material synthesis mode is complex, the methods only convert the antibiotics into relatively stable complex compounds with relatively low toxicity through the approaches such as hydroxyl oxidation or bond breaking, and the like, and some intermediate products with higher toxicity than the original substances can be generated even in the degradation process. Biological methods achieve antibiotic removal by using plant and microbial (bacterial, fungal, algal) growth metabolism, biocatalysts (enzymes) and the like. However, biodegradation of organic contaminants requires electron donors (acetate or hydrogen) to remove their sterilizing activity, and thus microorganisms may have some limitations in situ repair due to the limitations of the relevant electron donors.
In addition to antibiotics, sulfate is one of the non-negligible water pollutants. Sulfate is the most stable existence form of sulfur element in water, so that sulfate wastewater can exist in water stably for a long time and is difficult to be purified and eliminated naturally. The sulfate wastewater can cause environmental problems such as water acidification, soil hardening, death of aquatic plants and the like after entering the natural environment, and the benign development of an ecological system is affected; in addition, sulfate also causes human digestive system diseases by inhibiting pepsin activity when entering drinking water through a water supply system, and presents a great threat to human health.
In the prior art, a method for simply and efficiently removing florfenicol antibiotics in water and simultaneously removing sulfate in water is lacking, so that a good water purifying effect is achieved.
Disclosure of Invention
In order to solve the technical problems and solve the defects in the prior art, the invention provides a method for simultaneously removing sulfate and florfenicol in water, which utilizes an autotrophic biological cathode of a photoelectric coupling microbial electrolysis system to realize simultaneous removal of sulfate and florfenicol in water, has short treatment period and good treatment effect, improves the photoelectrochemistry battery, adds microorganisms in the cathode, and builds the photoelectric coupling microbial electrolysis system. The combination of photoanode electricity generation and microbial degradation technology can effectively remove sulfate and florfenicol in water, and lighten the biotoxicity of a system, and is realized by the following technical scheme: a method for removing sulfate and florfenicol in water simultaneously comprises the following steps:
a method for removing sulfate and florfenicol in water simultaneously comprises the following steps:
(1) Adding domesticated sulfate reducing bacteria sulfate matrix into an anaerobic bottle, and carrying out ventilation reaction in a constant-temperature oscillation state;
(2) Adding the bacterial liquid and the sulfate matrix obtained in the step (1) into a cathode chamber of a photoelectric coupling microbial reactor, wherein the anode liquid of the photoelectric coupling microbial reactor is sulfate solution with the concentration of 5 g/L;
(3) Placing the anode of the reactor in the step (2) under an ultraviolet light source to generate electricity by the photo anode;
(4) Florfenicol was added to the cathode chamber of the reactor of step (3) and incubated at 27℃and 1.2V for one week to remove sulfate and florfenicol.
In one embodiment, in step (2), the ratio of the bacterial liquid to the sulfate substrate is 1:1.
In one embodiment, in step (2), the externally applied voltage of the photo-coupled microbial reactor is 1.2V; in the step (3), the intensity of the ultraviolet light source is 13mW/cm < 2 >, and the reaction time for generating electricity by the photo-anode is 36 hours.
In one embodiment, the step (1) specifically includes:
1) Adding domesticated sulfate reducing bacteria and sulfate matrixes into a 100ml anaerobic bottle;
2) H with the mixing ratio of 1:4 is introduced into the anaerobic bottle every 2 days 2 -CO 2 Semi-replacing the bacterial liquid in the step 1) with fresh matrix every 4 days by mixed gas;
the anaerobic bottle is arranged in a constant temperature oscillator.
In one embodiment, the condition of the constant temperature oscillator is 30 ℃ and 180r/min.
In one embodiment, the acclimatized sulfate-reducing bacteria and sulfate substrate in step 1) are incorporated in a ratio of 1:10, and the aeration time in step 2) is 5min.
In one embodiment, in step (2), the photo-coupled microbial reactor is built using the following steps:
(a) Ultrasonically cleaning FTO conductive glass by using water and a mixed solution of acetone and isopropanol in a ratio of 1:1:1, and naturally airing;
(b) Mixing 40mL of pure water with 40mL of concentrated hydrochloric acid with the mass concentration of 36.5% -38%, adding into a polytetrafluoroethylene lining of a reaction kettle, and then adding 1.3mL of butyl titanate;
(c) Placing the FTO conductive glass in the step (a) into the inner liner of the reaction kettle in the step (b), with the conductive surface facing upwards, and transferring the reaction kettle to a blast drying box after the cover is covered;
(d) A carbon brush is woven by graphite fiber bundles, and each strand of the carbon brush is connected by titanium wires and screwed by pliers;
(e) Placing the carbon brush in the step (d) in a muffle furnace for heat treatment;
(f) Building a reactor, wherein the anode electrode is coated with TiO prepared in the step (c) 2 FTO conductive glass of (2), cathode isAnd (3) separating the two electrode chambers of the carbon brush electrode prepared in the step (e) by using a cation exchange membrane.
In one embodiment, in the step (c), the reaction temperature is 150 ℃ and the reaction time is 5h.
In one embodiment, in the step (d), the carbon brush is 16 strands, which are 4cm long and 3.5cm wide.
In one embodiment, in step (e), the heat treatment conditions are 450 ℃ for 30min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses titanium dioxide as photoelectric material, and combines the photoelectrochemical cell with the autotrophic microorganism electrolytic cell to construct a photoelectric coupling microorganism electrolytic system. Photoelectrochemical cells can combine water decomposition and solar energy absorption into one reactor, reducing external energy supply. The autotrophic microorganism electrolytic cell can realize sulfate reduction and organic matter degradation. In addition, part of oxygen generated by the anodic electrolytic water of the photoelectric coupling microbial electrolysis system formed by combining the oxygen and the water can be transferred to the cathode through the ion exchange membrane, so that the biological cathode becomes a micro-oxygen environment, aerobic, anaerobic and facultative microorganisms can coexist in the same system in the micro-oxygen environment, the types of the microorganisms of the system are rich, and the microorganisms can interact to finish the degradation of organic substances together. Therefore, the photoelectric coupling microorganism electrolysis system is used for treating water polluted by the florfenicol, is beneficial to further removing sulfate and florfenicol by sulfate reducing bacteria on the cathode, overcomes the defects of the prior art, and realizes the good effect of simultaneously removing the sulfate and the florfenicol.
(2) The method has the advantages of short treatment period, good treatment effect, and more than 80 percent of sulfate and more than 90 percent of florfenicol.
Drawings
FIG. 1 is a graph showing the effect of florfenicol concentration on reaction current
FIG. 2 is a graph showing the effect of florfenicol concentration on sulfate reduction rate
FIG. 3 is a graph showing the effect of florfenicol concentration on sulfate reduction
FIG. 4 is a graph showing the effect of florfenicol concentration on the rate of divalent sulfur production
FIG. 5 is a graph showing the effect of florfenicol concentration on the production of sulfur
FIG. 6 is a graph showing the effect of various initial florfenicol concentrations on removal efficiency
FIG. 7 is a schematic diagram of the reduction reaction of florfenicol in a photo-electrically coupled microbial electrolysis system
FIG. 8 is a schematic diagram of the reduction reaction of florfenicol in a photovoltaic system
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
Example 1
The embodiment provides a method for removing sulfate and florfenicol in water simultaneously, which comprises the following steps:
(1) Adding domesticated sulfate reducing bacteria and sulfate matrixes into a 100ml anaerobic bottle; h with the mixing ratio of 1:4 is introduced into the anaerobic bottle every 2 days 2 -CO 2 Semi-replacing the reacted bacterial liquid with fresh matrix every 4 days by mixed gas; the anaerobic bottle is placed in a constant temperature oscillator with the condition of 30 ℃ and 180r/min.
(2) Adding the bacterial liquid and the sulfate matrix obtained in the step (1) into a cathode chamber of a photoelectric coupling microbial reactor, wherein the anode liquid of the photoelectric coupling microbial reactor is sulfate solution with the concentration of 5 g/L;
(3) Placing the anode of the reactor in the step (2) under an ultraviolet light source to generate electricity by the photo anode;
(4) Florfenicol was added to the cathode chamber of the reactor of step (3) and incubated at 27℃and 1.2V for one week to remove sulfate and florfenicol.
Wherein the access ratio of the domesticated sulfate reducing bacteria to the sulfate matrix in the step (1) is 1:10, and the ventilation time is 5min.
In the step (2), the ratio of the bacterial liquid to the sulfate matrix is 1:1; the externally applied voltage of the photoelectric coupling microorganism reactor is 1.2V; in the step (3), the intensity of the ultraviolet light source is 13mW/cm < 2 >, and the reaction time for generating electricity by the photo-anode is 36 hours.
In the step (2), the photoelectric coupling microbial reactor is built by adopting the following steps:
(a) Ultrasonically cleaning FTO conductive glass by using water and a mixed solution of acetone and isopropanol in a ratio of 1:1:1, and naturally airing;
(b) Mixing 40mL of pure water with 40mL of concentrated hydrochloric acid with the mass concentration of 36.5% -38%, adding into a polytetrafluoroethylene lining of a reaction kettle, and then adding 1.3mL of butyl titanate;
(c) Placing the FTO conductive glass in the step (a) into the inner liner of the reaction kettle in the step (b), with the conductive surface facing upwards, and transferring the reaction kettle to a blast drying box after the cover is covered;
(d) A carbon brush is woven by graphite fiber bundles, and each strand of the carbon brush is connected by titanium wires and screwed by pliers;
(e) Placing the carbon brush in the step (d) in a muffle furnace for heat treatment;
(f) Building a reactor, wherein the anode electrode is coated with TiO prepared in the step (c) 2 The FTO conductive glass is characterized in that a cathode is a carbon brush electrode prepared in the step (e), and two pole chambers are separated by a cation exchange membrane.
Wherein, in the step (c), the reaction temperature is 150 ℃ and the reaction time is 5 hours; in the step (d), the carbon brush is 16 strands, and the length is 4cm and the width is 3.5cm; in the step (e), the heat treatment condition is 450 ℃ for 30min.
Example 2
Effects of florfenicol concentration on reaction currents
The concentration of florfenicol can change the activity, the electron utilization effect and the sulfate reducing capacity of sulfate reducing bacteria in a solution, and is an important factor for influencing whether the sulfate reducing bacteria in a system can work normally. The photoelectric coupling microorganism system is constructed to reduce and remove the norflorfenicol in water, the gradient of the florfenicol is set to be 0mg/L, 1mg/L, 3mg/L and 5mg/L, and the influence of the florfenicol on the activity and the electron utilization effect of sulfate reducing bacteria is explored.
The result shows that (see figure 1) the presence of the florfenicol enhances the utilization of electrons by sulfate reducing bacteria, and the current intensity of the reactor is obviously improved under the condition that the florfenicol with low concentration (1 mg/L) exists, which indicates that the florfenicol with the concentration does not inhibit the growth of the sulfate reducing bacteria; when the florfenicol concentration is increased to 3mg/L, the current intensity is slightly reduced; as the florfenicol concentration increased to 5mg/L, the current intensity rose back and was substantially the same as the current intensity in the presence of 1mg/L florfenicol. The method of the invention does not have inhibition effect on sulfate reducing bacteria, but the strengthening effect of the low-concentration florfenicol on the sulfate reducing bacteria is far higher than the inhibition effect of the florfenicol on the sulfate reducing bacteria. In summary, the addition of florfenicol to the system is beneficial to enhancing the biological activity of sulfate-reducing bacteria and the ability to utilize electrons.
Example 3
Influence of florfenicol concentration on sulfate reduction
The reduction of sulfate depends on sulfate reducing bacteria to transfer electrons on the electrode to an electron acceptor, namely sulfate, and the florfenicol and the sulfate can be used as electron acceptors, which belong to the relationship of competing electrons. 0mg/L, 1mg/L, 3mg/L and 5mg/L of florfenicol are added into the cathode solution, sampling is carried out every 6 hours, and detection is carried out by an ultraviolet spectrophotometer, so that the influence of the florfenicol concentration on sulfate reduction by sulfate reducing bacteria is investigated.
The results show (see FIGS. 2, 3) that 5mg/L FLO inhibits sulfate reduction by sulfate-reducing bacteria, whereas 1mg/L and 3mg/L FLO promote sulfate reduction by sulfate-reducing bacteria, as compared to the case where FLO is not added. Before FLO is added, the reduction efficiency of sulfate reducing bacteria to sulfate with initial concentration of 400mg/L in 36h is 96%; after adding 1mg/L of FLO, the reduction efficiency of sulfate reducing bacteria to sulfate with the initial concentration of 400mg/L in 36 hours is 93 percent, which is not quite different from the reduction efficiency before adding, but the reduction rate of sulfate in the presence of 1mg/L of FLO is always higher than that of the sulfate reducing bacteria without adding FLO; the concentration of FLO is increased to 3mg/L, and the reduction efficiency of sulfate is greatly reduced to 78% within 36 hours, but the reduction rate of sulfate is not quite different from that of the sulfate when FLO is not added; continuing to increase the FLO concentration to 5mg/L, the sulfate reduction efficiency was reduced to 66% within 36 hours, and the sulfate reduction rate was also relatively low. This is mainly due to the high concentration of FLO which reduces the activity of sulfate reducing bacteria, and the competition of florfenicol and sulfate for electrons also plays a role in inhibiting the reduction of sulfate. In conclusion, when the concentration of florfenicol is low, the sulfate reducing efficiency of sulfate reducing bacteria is not inhibited.
Example 4
Effect of florfenicol concentration on sulfide production
The generation of sulfide is that sulfate is reduced by sulfate reducing bacteria to obtain 8 electrons, and sulfur is converted from positive hexavalent to negative bivalent, but sulfide is extremely unstable and is easy to lose electrons to be a sulfur simple substance. 0mg/L, 1mg/L, 3mg/L and 5mg/L of florfenicol was added to the cathode solution to investigate the effect of florfenicol concentration on sulfide conversion.
The results show (see fig. 4, 5) that FLO is able to promote negative divalent sulfur electron loss, the higher the FLO concentration, the stronger the conversion promotion effect on negative divalent sulfur. Before FLO addition; about 3.66mg/L of divalent sulfur was produced in the solution over 6 hours; after adding 1mg/L of FLO, about 3.71mg/L of divalent sulfur can be generated in the solution within 6 hours, the amount of the divalent sulfur is not greatly different from that generated before adding, and the divalent sulfur generation rates of the two are basically the same; the FLO concentration is increased to 3mg/L, and the generation amount of the bivalent sulfur is reduced to 1.44mg/L within 6 hours; when the FLO concentration was further increased to 5mg/L, the amount of generated divalent sulfur was 0.95mg/L in 6 hours, and after the FLO concentration was increased from 1mg/L to 3mg/L and 5mg/L, the rate of generated divalent sulfur was also greatly decreased. This is mainly due to the need for electrons during the reduction of FLO, which, in addition to electrons provided by sulfate reducing bacteria, can also be obtained from negative divalent sulfur that has been converted from sulfate to extremely unstable, making the negative divalent sulfur electron lost to elemental sulfur. In summary, the higher the florfenicol concentration, the less negative divalent sulfur is produced.
Example 5
Effect of different concentration of sulfate on florfenicol removal efficiency
In order to examine the reduction and removal efficiency of florfenicol by sulfate reducing bacteria under the condition of sulfate with different concentrations, the concentration of florfenicol is measured by utilizing high performance liquid chromatography (HPLC-UV) on reaction solutions with different degradation times, and the residual ratio (C/C0) of florfenicol is calculated. Samples taken every 1h during the first 6 hours of reactor operation were taken as subjects, i.e., 0h, 1h, 2h, 3h, 4h, 5h, 6h of reactor solution.
The results show (see FIG. 4) that the reduction rate of florfenicol was relatively fast at a florfenicol initial concentration of 5mg/L without sulfate and at a sulfate concentration of 400 mg/L. Although the removal efficiency of florfenicol can basically reach 100% in 6 hours under different sulfate concentration gradients, the reduction efficiency of florfenicol in the first 3 hours under the conditions of high concentration sulfate concentration and no sulfate is obviously higher, which indicates that when no sulfate exists, florfenicol is taken as the only electron acceptor, electrode electrons can be absorbed more efficiently to reduce florfenicol, and the existence of high concentration sulfate can enhance the activity of sulfate reducing bacteria, efficiently utilize electrons on the electrode and promote the reduction efficiency of florfenicol.
Example 6
Influence of sulfate-reducing bacteria on the florfenicol removal pathway
The florfenicol can continue to exist in various byproducts after being reduced by a BES system, and products with different structures and characteristics can have different toxic effects so as to have different influences on a receiving water body, so that degradation intermediates of the florfenicol are identified and definitely identified
The toxicity of the product is of great significance. And (3) identifying an intermediate product generated by florfenicol in the reaction process of the presence and absence of sulfate reducing bacteria by adopting a liquid chromatography-mass spectrometry (HPLC-MS).
The results show (see figures 7,8 below) that this example identifies a total of 13 florfenicol degradation intermediate structures in the presence of sulfate reducing bacteria and 8 florfenicol degradation intermediate structures in the absence of sulfate reducing bacteria, each degradation product being named "mass to charge ratio (m/z) of the p+ product ion". As shown in FIG. 7, the bioelectrically reduced florfenicol in the presence of sulfate-reducing bacteria has more diverse degradation pathways and produces more simple molecules.
The invention utilizes the autotrophic biological cathode of the photoelectric coupling microorganism electrolysis system to remove sulfate and florfenicol in water simultaneously, has short treatment period and good treatment effect, improves the photoelectrochemistry battery, adds microorganisms at the cathode and builds the photoelectric coupling microorganism electrolysis system. The combination of photoanode electricity generation and microbial degradation technology can effectively remove sulfate and florfenicol in water, and reduce the biotoxicity of the system. The method has the advantages of short treatment period, good treatment effect, and more than 80 percent of sulfate and more than 90 percent of florfenicol.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the scope of the invention, but any simple modification, equivalent variation and variation, or direct/indirect application in other related technical fields, which are included in the present invention, are included in the scope of the present invention.
Claims (9)
1. A method for removing sulfate and florfenicol in water simultaneously comprises the following steps:
(1) Adding domesticated sulfate reducing bacteria and sulfate matrixes into an anaerobic bottle, and carrying out ventilation reaction in a constant-temperature oscillation state;
(2) Building a photoelectric coupling microbial reactor, wherein the photoelectric coupling microbial reactor is divided into an anode chamber and a cathode chamber by a cation exchange membrane, and bacterial liquid and sulfate matrixes obtained in the step (1) are added into the cathode chamber of the photoelectric coupling microbial reactor, wherein the anode liquid of the photoelectric coupling microbial reactor is sulfate solution with the concentration of 5 g/L;
(3) Placing the anode of the reactor in the step (2) under an ultraviolet light source to generate electricity by the photo anode;
(4) Adding florfenicol into the cathode chamber of the reactor in the step (3), and culturing for one week at 27 ℃ and 1.2V voltage to remove sulfate and florfenicol;
wherein, the step (1) specifically comprises:
1) Adding domesticated sulfate reducing bacteria and sulfate matrixes into a 100ml anaerobic bottle;
2) H with the mixing ratio of 1:4 is introduced into the anaerobic bottle every 2 days 2 -CO 2 Semi-replacing the bacterial liquid in the step 1) with fresh matrix every 4 days by mixed gas; the anaerobic bottle is arranged in a constant temperature oscillator;
wherein the concentration of the florfenicol in the cathode chamber is 1-5mg/L.
2. The method of claim 1, wherein in step (2), the ratio of bacterial fluid to sulfate substrate is 1:1.
3. The method according to claim 1, wherein in step (2), the externally applied voltage of the photo-coupled microbial reactor is 1.2V; in the step (3), the intensity of the ultraviolet light source is 13mW/cm 2 The reaction time for generating electricity by the photo-anode is 36 hours.
4. The method of claim 1, wherein the conditions of the constant temperature oscillator are 30 ℃,180r/min.
5. The method according to claim 1, wherein the acclimatized sulfate-reducing bacteria and sulfate substrate are incorporated in a ratio of 1:10 in step 1) and the aeration time is 5min in step 2).
6. The method according to claim 1, wherein in step (2), the photo-coupled microbial reactor is built up using the following steps:
(a) Ultrasonically cleaning FTO conductive glass by using a mixed solution of water, acetone and isopropanol in a ratio of 1:1:1, and naturally airing;
(b) Mixing 40mL of pure water with 40mL of concentrated hydrochloric acid with the mass concentration of 36.5% -38%, adding into a polytetrafluoroethylene lining of a reaction kettle, and then adding 1.3mL of butyl titanate;
(c) Placing the FTO conductive glass in the step (a) into the inner liner of the reaction kettle in the step (b), with the conductive surface facing upwards, and transferring the reaction kettle to a blast drying box after the cover is covered;
(d) A carbon brush is woven by graphite fiber bundles, and each strand of the carbon brush is connected by titanium wires and screwed by pliers;
(e) Placing the carbon brush in the step (d) in a muffle furnace for heat treatment;
(f) Building a reactor, wherein the anode electrode is coated with TiO prepared in the step (c) 2 The cathode is a carbon brush electrode prepared in the step (e), and the cathode chamber and the anode chamber are separated by a cation exchange membrane.
7. The method of claim 6, wherein in the step (c), the reaction temperature is 150℃and the reaction time is 5 hours.
8. The method according to claim 6, wherein in the step (d), the carbon brush is 16 strands, which is 4cm long and 3.5cm wide.
9. The method of claim 6, wherein in step (e), the heat treatment conditions are 450 ℃ for 30min.
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| Haiping Luo etal. ."Efficient reduction of nitrobenzene by sulfate-reducer enriched biocathode in microbial electrolysis cell".《Science of the Total Environment》.2019,第336-337页摘要、第2节，第338-342页第3节. * |
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