CN115739066A - Biochar catalyst, preparation method thereof, and landfill leachate treatment system and method - Google Patents
Biochar catalyst, preparation method thereof, and landfill leachate treatment system and method Download PDFInfo
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Abstract
The invention discloses a biochar catalyst and a preparation method thereof, and a landfill leachate treatment system and a method; the preparation method of the biochar catalyst comprises the following steps: obtaining sludge raw materials, and drying to obtain completely dried sludge; wherein the sludge raw material is sludge subjected to dehydration treatment in a sewage treatment plant; grinding the completely dried sludge to obtain sludge powder; and calcining the sludge powder under an anaerobic condition, and cooling to obtain the biochar catalyst. A biochar catalyst, a preparation method thereof, a landfill leachate treatment system and a method; the invention realizes resource utilization of sludge, has low preparation cost and higher catalytic performance, and can realize cyclic and repeated utilization of activated sludge; the catalytic ozonation method is simple and easy to control, and can effectively assist the activated sludge method in removing pollutants in the landfill leachate.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a biochar catalyst, a preparation method thereof, a landfill leachate treatment system and a method.
Background
The landfill leachate mainly refers to high-concentration organic wastewater containing various metabolic substances and water generated by anaerobic fermentation, organic matter decomposition, rainfall leaching and scouring, surface water and underground water soaking and the like in the process of landfill stacking of the garbage; because the landfill leachate contains a large amount of soluble organic matters, salts, heavy metal ions and other organic compounds, and the content of various substances in the landfill leachate also has larger difference according to different landfill time; in general, the treatment of landfill leachate is a big problem to be solved at present due to the reasons of multiple pollutant types, high organic matter concentration, high ammonia nitrogen, imbalance of element proportion, multiple heavy metals, high salinity and the like.
At present, the existing landfill leachate treatment methods can be classified into typical physical and chemical methods, biological methods and combined process methods; wherein, most garbage percolate treatment plants adopt a membrane treatment method, and carry out advanced treatment on high-concentration percolate so that the wastewater of the percolate reaches the standard or meets the discharge requirement; although the treatment method has good effect, in the operation process, a plurality of intermediate factors need to be controlled; for example: the problem of pollution to the membrane surface caused by high-load sewage needs to be solved, and the cost of the membrane treatment technology is high; meanwhile, in the treatment process, concentrated water can be generated due to the reverse osmosis effect, and the subsequent treatment of the concentrated water is also a difficult point.
Secondly, the coagulating sedimentation method is widely used for treating the landfill leachate due to simple operation, and only needs to add a medicament into the landfill leachate for simple sedimentation separation; at present, a general coagulant is generally adopted for pretreatment and advanced treatment; however, the existing coagulating sedimentation method cannot remove high-solubility organic matters in the landfill leachate, and the generated sedimentation waste also needs to be subjected to subsequent solid waste treatment, so that the cost of landfill leachate treatment is increased.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a biochar catalyst, a preparation method thereof, a garbage leachate treatment system and a method, and aims to solve the technical problems that high-solubility organic matters in garbage leachate cannot be effectively treated by the conventional general coagulant, and a large amount of concentrated water is easily generated due to the reverse osmosis effect in a membrane treatment method, so that the treatment cost of the concentrated water is increased.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a biochar catalyst, which comprises the following steps:
obtaining sludge raw materials, and drying to obtain completely dried sludge; wherein the sludge raw material is sludge subjected to dehydration treatment in a sewage treatment plant;
grinding the completely dried sludge to obtain sludge powder;
and calcining the sludge powder under an anaerobic condition, and cooling to obtain the biochar catalyst.
Further, in the drying process, the sludge raw material is dried at 105-110 ℃; the completely dried sludge is in a hard granular structure, and the water content is less than 10 percent.
Furthermore, the fineness of the sludge powder is 5-150 meshes.
Further, under the nitrogen atmosphere, placing the sludge powder in a tubular vacuum muffle furnace, and calcining under the anaerobic condition of introducing nitrogen; wherein, in the calcining process, the heating rate is 20-25 ℃/min, the calcining temperature is 600-900 ℃, and the calcining time is 1.9-2.1h.
The invention also provides a biochar catalyst which is prepared by the preparation method of the biochar catalyst.
The invention also provides a landfill leachate treatment system, which comprises an ozone generator, an ozone catalytic reactor, an aeration pump, a biochemical reactor, a first peristaltic pump and a second peristaltic pump;
the gas outlet of the ozone generator is connected with the first inlet of the ozone catalytic reactor, and the ozone generator is used for intermittently introducing ozone gas into the ozone catalytic reactor; the outlet end of the ozone catalytic reactor is connected with the inlet end of the second peristaltic pump, and the outlet end of the second peristaltic pump is connected with the first inlet of the biochemical reactor;
an air outlet of the aeration pump is connected with a second inlet of the biochemical reactor, and the aeration pump is used for intermittently aerating the biochemical reactor; the outlet end of the biochemical reactor is connected with the inlet end of the first peristaltic pump, and the outlet end of the first peristaltic pump is connected with the second inlet of the ozone catalytic reactor;
wherein the biochar catalyst is added into the ozone catalytic reactor; the biochemical reactor stores landfill leachate stock solution to be treated.
Further, a ceramic filter membrane is arranged at the outlet end of the ozone catalytic reactor; and a polyvinylidene fluoride hollow fiber membrane is arranged at the outlet end of the biochemical reactor.
The invention also provides a first vacuum pressure gauge and a second vacuum pressure gauge;
the first vacuum pressure gauge is arranged between the second inlet of the ozone catalytic reactor and the outlet end of the first peristaltic pump; and the second vacuum pressure gauge is arranged between the outlet end of the ozone catalytic reactor and the inlet end of the second peristaltic pump.
The invention also provides a landfill leachate treatment method, which utilizes the landfill leachate treatment system; the landfill leachate treatment method comprises the following steps:
adding the landfill leachate stock solution to be treated into the biochemical reactor, and carrying out intermittent aeration in the biochemical reactor by using the aeration pump;
pumping the aerated landfill leachate in the biochemical reactor into the ozone catalytic reactor by using a first peristaltic pump;
when the aerated landfill leachate in the ozone catalytic reactor reaches a preset volume, adding the biochar catalyst as claimed in the claim; then, utilizing the ozone generator to introduce ozone gas into the ozone catalytic reactor in a gap mode to perform catalytic reaction;
wherein, during operation of the ozone generator, the first peristaltic pump and the second peristaltic pump operate simultaneously; the hydraulic retention time of the landfill leachate in the ozone catalytic reactor is 2-2.5h by adjusting the pump speed of the first peristaltic pump and the second peristaltic pump.
Further, in the process of carrying out intermittent aeration in the biochemical reactor by using the aeration pump, the aeration time is 3.5-4h, and the interval time is 2.5-3h;
and in the process of introducing ozone gas into the ozone catalytic reactor in a gap mode by using the ozone generator, the aeration time is 5-10min, and the interval time is 5-10min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a biochar catalyst and a preparation method thereof, wherein the biochar catalyst is obtained by drying, grinding and calcining sludge subjected to dehydration treatment in a sewage treatment plant; the biochar catalyst has an irregular structure, and a large number of pore structures exist on the surface of the biochar catalyst, so that the biochar catalyst can be used as an adsorption space of pollutants, can effectively adsorb high-solubility organic matters in the landfill leachate, and effectively promotes the decomposition efficiency of the high-solubility organic matters in the landfill leachate; meanwhile, the biochar catalyst contains a large amount of calcium oxide and silicon oxide, so that the biochar catalyst has good mechanical strength, the recovery of the catalyst is facilitated, and secondary pollution is avoided; secondly, the biochar is used as a catalyst for catalytic oxidation of ozone, so that the catalytic effect of the ozone can be greatly improved, and the utilization rate of the ozone can be increased; in the catalytic ozonation treatment, all the landfill leachate can be subjected to oxidation treatment, so that concentrated water cannot be generated; realizes the resource utilization of the sludge, has low preparation cost and higher catalytic performance, and can realize the cyclic reuse of the activated sludge.
The invention also provides a system and a method for treating the landfill leachate, which utilize an ozone catalytic oxidation method, are simple and easy to control, and can effectively assist an activated sludge method in removing pollutants in the landfill leachate; wherein, the ozone is used as a strong oxidant, and the reaction with the pollutants comprises a direct oxidation reaction and an indirect oxidation reaction between free radicals; the method comprises the following steps of performing direct oxidation reaction, activating to generate active oxides in the direct oxidation reaction and performing radical indirect oxidation reaction, wherein toxic and nonbiodegradable macromolecular substances in high-solubility organic matters in the landfill leachate are degraded into easily biodegradable and degradable micromolecular substances by the action of electrophilic substitution reaction and dipole addition reaction in the direct oxidation reaction and the action of the active oxides generated by activation in the radical indirect oxidation reaction, so that the high-efficiency treatment of the high-solubility organic matters in the landfill leachate is realized, and the generation of concentrated water is avoided; secondly, adding a charcoal catalyst to catalyze the ozone oxidation process, so that the utilization rate of the wastewater to ozone is increased, and the reaction efficiency of ozone oxidation is improved, so that the ozone oxidation can better play a role in degrading pollutants; in addition, ozone can destroy chromophoric groups in the wastewater so as to reduce the chromaticity of the wastewater; and various microorganisms in the activated sludge act synergistically to achieve the effect of removing nitrogen-containing pollutants in the landfill leachate.
Furthermore, through the arrangement of the first vacuum pressure gauge and the second vacuum pressure gauge, the pressure value of the citrus vacuum pressure gauge can be read, and the cleanliness of the membrane module can be monitored in real time.
Drawings
Fig. 1 is a block diagram of a landfill leachate treatment system in embodiment 5.
Wherein, 1 ozone generator, 2 ozone catalytic reactor, 3 aeration pump, 4 biochemical reactors, 5 first vacuum pressure gauge, 6 first peristaltic pump, 7 second vacuum pressure gauge, 8 second peristaltic pump.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention more apparent, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
In this embodiment 1, a preparation method of a biochar catalyst is provided, which includes the following steps:
In the embodiment 1, the biochar catalyst prepared at the carbon pyrolysis temperature of 600 ℃ has a good effect of removing the chromaticity of the landfill leachate when the landfill leachate is subjected to ozone catalytic oxidation treatment; wherein, the detection is carried out by using a dilution multiple method, and the chroma of the landfill leachate can be reduced from 100 ℃ to 10 ℃ within a short-time reaction of 2h, thereby meeting the discharge standard.
Example 2
In this embodiment 2, a preparation method of a biochar catalyst is provided, which includes the following steps:
When the biochar catalyst prepared in the embodiment 2 is used for carrying out catalytic ozonation treatment on landfill leachate, due to the fact that the structure of the biochar catalyst is compact, turbidity can be well removed within 2 hours of reaction time, the removal rate can reach over 60%, and the removal rate of COD can reach about 10%.
Example 3
In this embodiment 3, a preparation method of a biochar catalyst is provided, which includes the following steps:
The charcoal catalyst prepared in the embodiment 3 has low preparation difficulty and is convenient for practical application, and the chroma can reach about 50 within 2h of reaction time to the decolorization effect of the leachate during ozone catalytic oxidation under the condition that the effect of degrading other pollutants is not reduced. More than 15% of ammonia nitrogen can be removed within 2h, and the removal rate of COD and the ammonia nitrogen can reach about 40%. The mechanical strength is better because of the larger grain diameter, and the turbidity removal rate after reaction is as high as 70%.
Example 4
In this embodiment 4, a preparation method of a biochar catalyst is provided, which includes the following steps:
In the case of performing catalytic ozonation on landfill leachate, the removal rate of COD can reach more than 35%, and in the aspect of removing chromaticity, the chromaticity after reaction can be reduced from 400 degrees to about 80 degrees; the analysis shows that the method has good effect of removing humic acid substances and other macromolecular organic matters in the leachate.
The biochar catalysts prepared in examples 1-4, which have irregular structures and a large number of pore structures on the surface, provide a large amount of adsorption space for pollutants; and provides more adsorption sites for ozone, so that the ozone can oxidize pollutants more fully to achieve the effect of degrading pollutants; through detection, the biochar catalyst mainly comprises calcium oxide and silicon oxide, and before and after reaction, the crystal structure of the biochar catalyst is not greatly changed, so that the material has good mechanical strength.
Example 5
As shown in fig. 1, this embodiment 5 provides a landfill leachate treatment system, which includes an ozone generator 1, an ozone catalytic reactor 2, an aeration pump 3, a biochemical reactor 4, a first vacuum pressure gauge 5, a first peristaltic pump 6, a second vacuum pressure gauge 7, and a second peristaltic pump 8.
The ozone generator 1 is used for intermittently introducing ozone gas into the ozone catalytic reactor 2; wherein, in the process of utilizing the ozone generator 1 to introduce ozone gas into the ozone catalytic reactor 2 in a gap mode, the aeration time is 5-10min, and the interval time is 5-10min.
An air outlet of the ozone generator 1 is connected with a first inlet of the ozone catalytic reactor 2, and an outlet end of the ozone catalytic reactor 2 is connected with an inlet end of the second peristaltic pump 8 through a first pipeline; wherein, a ceramic filter membrane is arranged at the outlet end of the ozone catalytic reactor 2; the second vacuum pressure gauge 7 is arranged on the first pipeline; the second vacuum pressure gauge 7 is used for monitoring the pollution degree of the ceramic filter membrane; when the numerical value of the second vacuum pressure gauge 7 is more than or equal to 0.03Mpa, the ceramic filter membrane needs to be physically or chemically cleaned; the outlet end of the second peristaltic pump 8 is connected with the first inlet of the biochemical reactor 4 through a second pipeline.
The aeration pump 3 is used for intermittently aerating the biochemical reactor 4; wherein, in the process of carrying out intermittent aeration in the biochemical reactor 4 by the aeration pump 3, the aeration time is 3.5-4h, and the interval time is 2.5-3h.
An air outlet of the aeration pump 3 is connected with a second inlet of the biochemical reactor 4, an outlet end of the biochemical reactor 4 is connected with an inlet end of the first peristaltic pump 6 through a third pipeline, and an outlet end of the first peristaltic pump 6 is connected with a second inlet of the ozone catalytic reactor 2 through a fourth pipeline; wherein, the outlet end of the biochemical reactor 4 is provided with a polyvinylidene fluoride hollow fiber membrane; the first vacuum pressure gauge 5 is arranged on the fourth pipeline; the first vacuum pressure gauge 5 is used for monitoring the pollution degree of the polyvinylidene fluoride hollow fiber membrane; and when the numerical value of the first vacuum pressure gauge 5 is more than or equal to 0.03Mpa, the polyvinylidene fluoride hollow fiber membrane needs to be physically or chemically cleaned.
Wherein, the physical cleaning is that the filter cake layer on the surface of the membrane is washed off by using clean water, and the polluted substances are further fallen off by backwashing; the chemical cleaning method comprises the steps of soaking the membrane module in hydrochloric acid solution with the pH =2 for 4 hours, and then cleaning the membrane module with clear water; then soaking the membrane module for 2 hours by using a mixed solution of 0.5g/L of sodium hydroxide and 5ml/L of sodium hypochlorite, and then washing the membrane module by using clean water again.
In this embodiment 4, the ozone catalytic reactor 2 is filled with the biochar catalyst as described in embodiments 1 to 3; the biochemical reactor 4 stores the landfill leachate stock solution to be treated.
The embodiment 4 further provides a landfill leachate treatment method, which includes the following steps:
adding the landfill leachate stock solution to be treated into the biochemical reactor 4, and performing intermittent aeration in the biochemical reactor 4 by using the aeration pump 3; pumping the aerated landfill leachate in the biochemical reactor 4 into the ozone catalytic reactor 2 by using a first peristaltic pump 6;
when the aerated landfill leachate in the ozone catalytic reactor 2 reaches a preset volume, adding the biochar catalyst; wherein, the proportion of the biochar catalyst to the aerated landfill leachate is as follows: 3-5g/L;
then, the ozone generator 1 is used for introducing ozone gas into the ozone catalytic reactor 2 in a gap mode to carry out catalytic reaction; wherein the generation amount of ozone gas is 10g/h, and the feeding speed is 1m 3 H; wherein, the reaction time can be effectively improved by adjusting the feeding rate of the ozone gas, but the reaction effect can be influenced.
In this embodiment 4, during the operation of the ozone generator 1, the first peristaltic pump 6 and the second peristaltic pump 8 operate simultaneously; the pump speed of the first peristaltic pump 6 and the second peristaltic pump 8 is adjusted, so that the hydraulic retention time of the landfill leachate in the ozone catalytic reactor 2 is 2-2.5h.
The working principle is as follows:
in the landfill leachate treatment system described in this embodiment 4, before operation, untreated landfill leachate stock solution is added to the biochemical reactor 4; meanwhile, intermittent aeration is carried out in the biochemical reactor 4, and the landfill leachate is pumped into the ozone catalytic reactor 2 through the first peristaltic pump 6; when the volume of the landfill leachate in the ozone catalytic reactor 2 reaches the preset volume, adding the biomass charcoal catalyst, and starting the formal operation of the whole treatment system.
When in operation, intermittently introducing ozone gas into the ozone catalytic reactor 2 through the ozone generator 1; meanwhile, the first peristaltic pump 6 and the second peristaltic pump 8 work simultaneously in the running process of the ozone generator 1, and the garbage percolate in the biochemical reactor is pumped to the ozone catalytic reactor 2 through the polyvinylidene fluoride hollow fiber membrane by utilizing the first peristaltic pump 6; and pumping the landfill leachate in the ozone catalytic reactor to the biochemical reactor 4 through a ceramic filter membrane by using a second peristaltic pump 8.
In this embodiment 4, the hydraulic retention time of the landfill leachate in the ozone catalytic reactor 2 is ensured to be 2-2.5h by adjusting the pump speed of the first peristaltic pump 6 and the second peristaltic pump 8, so that ozone is fully utilized, the ozone is promoted to act on organic pollutants in the wastewater, active oxygen species are generated, and a chain reaction is induced, so that the organic pollutants are removed until the landfill leachate in the circulating device reaches the pollution control standard of the domestic refuse landfill.
In this embodiment 4, in the operation process of the whole processing system, the pressure value readings of the first vacuum pressure gauge 5 and the second vacuum pressure gauge 7 are recorded in real time; when the reading of the pressure value is more than 0.03MPa, the membrane pollution is serious, namely, the corresponding membrane material needs to be cleaned or replaced.
The biochar catalyst and the preparation method thereof realize resource utilization of sludge in municipal sewage plants, the catalyst prepared by calcination has low cost, the addition amount in the reactor is small, and the operation cost is further reduced; in the treatment of wastewater, concentrated water is not generated, and activated sludge used in biochemical treatment can be recycled.
The landfill leachate treatment system and the method of the invention use an ozone catalytic oxidation method, are simple and easy to control, can effectively assist an activated sludge method to remove pollutants in the landfill leachate, and reduce the chroma of wastewater; various microorganisms in the activated sludge act synergistically to remove nitrogen-containing pollutants in the landfill leachate; the method has the advantages of reasonable scheme, simple procedure, easy realization and full play of the advantages of biochemistry and ozone catalytic oxidation.
The above-described embodiment is only one of the embodiments that can implement the technical solution of the present invention, and the scope of the present invention to be claimed is not limited to the embodiment, but includes any changes, substitutions and other embodiments that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed.
Claims (10)
1. A preparation method of a biochar catalyst is characterized by comprising the following steps:
obtaining sludge raw materials, and drying to obtain completely dried sludge; wherein the sludge raw material is sludge subjected to dehydration treatment in a sewage treatment plant;
grinding the completely dried sludge to obtain sludge powder;
and calcining the sludge powder under an anaerobic condition, and cooling to obtain the biochar catalyst.
2. The preparation method of the biochar catalyst according to claim 1, characterized in that in the drying process, the sludge raw material is dried at 105-110 ℃; the completely dried sludge is in a hard granular structure, and the water content is less than 10 percent.
3. The method of claim 1, wherein the fineness of the sludge powder is 5-150 mesh.
4. The preparation method of the biochar catalyst as claimed in claim 1, characterized in that the sludge powder is placed in a tubular vacuum muffle furnace in a nitrogen atmosphere, and is subjected to calcination treatment under an anaerobic condition through nitrogen; wherein, in the calcining process, the heating rate is 20-25 ℃/min, the calcining temperature is 600-900 ℃, and the calcining time is 1.9-2.1h.
5. A biocarbon catalyst prepared by the method of any one of claims 1 to 4.
6. A landfill leachate treatment system is characterized by comprising an ozone generator (1), an ozone catalytic reactor (2), an aeration pump (3), a biochemical reactor (4), a first peristaltic pump (6) and a second peristaltic pump (8);
the gas outlet of the ozone generator (1) is connected with the first inlet of the ozone catalytic reactor (2), and the ozone generator (1) is used for intermittently introducing ozone gas into the ozone catalytic reactor (2); the outlet end of the ozone catalytic reactor (2) is connected with the inlet end of the second peristaltic pump (8), and the outlet end of the second peristaltic pump (8) is connected with the first inlet of the biochemical reactor (4);
an air outlet of the aeration pump (3) is connected with a second inlet of the biochemical reactor (4), and the aeration pump (3) is used for intermittently aerating the biochemical reactor (4); the outlet end of the biochemical reactor (4) is connected with the inlet end of the first peristaltic pump (6), and the outlet end of the first peristaltic pump (6) is connected with the second inlet of the ozone catalytic reactor (2);
wherein the ozone catalytic reactor (2) is internally added with the biochar catalyst as set forth in claim 5; the biochemical reactor (4) stores the landfill leachate stock solution to be treated.
7. The landfill leachate treatment system according to claim 6, wherein a ceramic filter membrane is disposed at the outlet end of the ozone catalytic reactor (2); and a polyvinylidene fluoride hollow fiber membrane is arranged at the outlet end of the biochemical reactor (4).
8. The landfill leachate treatment system of claim 6, further comprising a first vacuum pressure gauge (5) and a second vacuum pressure gauge (7);
the first vacuum pressure gauge (5) is arranged between the second inlet of the ozone catalytic reactor (2) and the outlet end of the first peristaltic pump (7); and the second vacuum pressure gauge (7) is arranged between the outlet end of the ozone catalytic reactor (2) and the inlet end of the second peristaltic pump (8).
9. A landfill leachate treatment method, characterized in that a landfill leachate treatment system according to any one of claims 6 to 8 is used; the landfill leachate treatment method comprises the following steps:
adding the landfill leachate stock solution to be treated into the biochemical reactor (4), and carrying out intermittent aeration in the biochemical reactor (4) by using the aeration pump (3);
pumping the aerated landfill leachate in the biochemical reactor (4) into the ozone catalytic reactor (2) by using a first peristaltic pump (6);
when the aerated landfill leachate in the ozone catalytic reactor (2) reaches a preset volume, adding the biochar catalyst as in claim (5); then, introducing ozone gas into the ozone catalytic reactor (2) in a gap mode by using the ozone generator (1) to perform catalytic reaction;
wherein, during operation of the ozone generator (1), the first peristaltic pump (6) and the second peristaltic pump (8) work simultaneously; the pump speed of the first peristaltic pump (6) and the second peristaltic pump (8) is adjusted to ensure that the hydraulic retention time of the landfill leachate in the ozone catalytic reactor (2) is 2-2.5h.
10. The landfill leachate treatment method according to claim 9, wherein during the intermittent aeration in the biochemical reactor (4) by the aeration pump (3), the aeration time is 3.5-4h, and the interval time is 2.5-3h;
in the process of introducing ozone gas into the ozone catalytic reactor (2) in a gap mode by using the ozone generator (1), the aeration time is 5-10min, and the interval time is 5-10min.
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