CN115893777B - Landfill leachate treatment method - Google Patents
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Abstract
The invention provides a landfill leachate treatment method, and belongs to the technical field of sewage treatment. Comprising the following steps: (1) Mixing the landfill leachate with limestone, and settling to obtain solid slag and settling liquid; (2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate; (3) Mixing the aerated effluent with a landfill leachate treatment agent, reacting under an aerobic condition, reacting under an anaerobic condition, adding dilute acid solution, performing hydrolysis pre-acidification treatment, introducing ozone for reaction, and then performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank. The garbage leachate treatment method disclosed by the invention is simple in flow, short in treatment time and excellent in purification effect, and the prepared garbage leachate treatment agent has the effect of high-efficiency reaction through biological, catalytic oxidation, photocatalytic oxidation and adsorption fixation, so that the garbage leachate treatment speed is increased, and the treatment efficiency and effect are improved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a landfill leachate treatment method.
Background
The treatment of landfill leachate is a problem recognized at home and abroad, and particularly, the implementation of a new standard of "pollution control Standard of domestic landfill" in GB16889-2008 puts higher demands on the treatment of landfill leachate. The technology for treating landfill leachate has been developed for many years, and currently, the main stream treatment technology accepted in the industry is that the front section adopts 'biochemical+MBR', and the rear section adopts 'nanofiltration or reverse osmosis'. The front biochemical process mainly adopts A/O, and MBR is in most cases in the form of an external membrane in recent years; the back end "nanofiltration or reverse osmosis" basically employs DTRO membranes or roll membranes.
The domestic existing landfill leachate treatment technology mainly has the following problems:
(1) The energy consumption is high: the garbage percolate is characterized in that TN and NH3-N are high, and the A/O biochemical treatment denitrification technology and theory are based on low concentration TN and NH3-N, and are used for high concentration TN and NH 3 N adopts A to denitrify the O system, lacks mature system theory, and is more engineering to reference low-concentration TN and NH 3 -N theory. Because TN and NH3-N concentration in the landfill leachate are high, in order to improve the treatment efficiency, oxygen supply and sludge concentration are required to be increased, and mud and water are difficult to separate when the sludge concentration of the aerobic sludge by the traditional activated sludge method reaches more than 6000 mg/L. In order to effectively improve the sludge concentration, membrane filtration is adopted to replace a biochemical secondary sedimentation tank, and the treatment is necessary in the biochemical treatment section of the landfill leachate. Meanwhile, more than 3g of oxygen is needed for removing 1g of nitrogen according to the traditional theory, so that the energy consumption of a biochemical system is extremely high.
(2) The operation difficulty is large: in the A/O technology, the operation conditions of the A (anaerobic denitrification) unit and the O (aerobic nitrification) unit are far different. The traditional denitrification theory considers that the A unit is mainly heterotrophic bacteria and has shorter mud age, and the O unit is mainly autotrophic bacteria and has longer mud age. As the A/O technology has no sludge sedimentation tank, in actual operation, microorganisms in the A section can enter the O section along with sewage, and microorganisms in the O section, which are trapped by MBR (Membrane Bio-Reactor), enter the A section through backflow, so that the high-efficiency operation of each section of the existing system is difficult. In addition, in the A/O technology, the temperature, alkalinity, organic carbon concentration and dissolved oxygen concentration of sewage can all influence the stable operation and treatment effect of the system. Therefore, the stable operation of the biochemical system is realized in actual engineering, and the difficulty is extremely high.
(3) Carbon source is needed to be supplemented: landfill leachate is generally maladjusted in carbon-nitrogen ratio. The A/O is adopted to realize denitrification, and the ratio of the carbon source to the total nitrogen is required to be generally 6-8. Such a high carbon-nitrogen ratio is generally only marginally required at the initial stage of use in a landfill, and for most garbage leachate treatment projects, a carbon source must be fed from the outside to achieve an ideal denitrification effect.
(4) Pollution transfer: nanofiltration or reverse osmosis is a process of concentrating pollutants, most of the pollutants trapped by nanofiltration or reverse osmosis are treated by spraying the concentrated solution back to a landfill, and in theory, the residual pollutants are not effectively decomposed. Although the technicians search the technology of thoroughly treating the concentrated solution at present, certain problems still exist in the cost and the operation mode in the practical application process.
(5) The membrane replacement cost is high: as a membrane separation technique, replacement of the membrane after a period of use is necessary. From the current actual engineering running condition in China, the membrane needs to be replaced once in 2-3 years. According to statistics of actual running conditions of landfill leachate treatment facilities in China, the adoption of a biochemical treatment process, an MBR process, a nanofiltration process or a reverse osmosis process is really lower than 50% of continuous and stable running, and the treated effluent reaches the standard of GB16889-2008 and is extremely small in quantity.
Chinese patent CN100398470C discloses a landfill leachate treatment method, which comprises six steps of flocculation tank pre-precipitation treatment, partial denitrification treatment, anaerobic treatment, aerobic treatment, membrane biological treatment and nanofiltration treatment, thereby realizing the purification effect on the landfill leachate. Chinese patent CN101234836B discloses a landfill leachate treatment method, which comprises five parts, namely pretreatment, up-flow sludge bed reaction (entity is UASB anaerobic reactor), nitrification-denitrification reaction (entity is a/O facultative aerobic aeration tank), mud-water separation (entity is sedimentation tank), membrane treatment (entity is ceramic ultrafiltration membrane+ro reverse osmosis system), to realize purification of landfill leachate. In the anaerobic treatment step of the landfill leachate, an integrated anaerobic reactor such as a UASB reactor is mainly adopted, however, in the integrated anaerobic reactor, due to unstable biodegradation load, acid-producing bacteria excessively produce VFA (volatile fatty acid), so that the PH value of an anaerobic system is reduced, the activity of methanogenic bacteria is influenced, and the removal efficiency of the whole anaerobic system is influenced; in addition, the oxidation-reduction potential (ORP) in the anaerobic reaction treatment process in the prior art is relatively high, so that the effect of the anaerobic reaction, namely the effect of hydrolyzing and degrading organic matters in landfill leachate is not ideal, and particularly when macromolecular organic matters which are difficult to degrade and hydrolyze are encountered, the effect of the anaerobic reaction is poorer, so that the subsequent treatment effect cannot be well ensured.
The ammonia nitrogen removal method mentioned in the method of Chinese patent CN100398470C is a physical treatment method, partial denitrification is carried out through a circulating stripping tank and a stripping tower after the garbage leachate is alkalized, and the stripping method adopting the stripping tower has higher ammonia nitrogen removal efficiency, but the ammonia nitrogen stripping tower has large investment, and when the method is operated, a large amount of alkaline agent is needed to be added to adjust the PH value of the leachate to 9-11, and the circulating stripping tower also needs higher gas-liquid ratio (generally more than 2000:1); in addition, the physical stripping of ammonia nitrogen has extremely high requirements on water temperature, especially in winter, if the circulating water is not subjected to heating treatment, the removal efficiency of the circulating water cannot be guaranteed, so that the ammonia nitrogen stripping method has the defects of high investment operation cost and complex control mode, and secondary pollution is easy to cause because the tail gas containing a large amount of ammonia after deamination is difficult to treat, and if the stripped ammonia is subjected to absorption treatment, the investment and the operation cost are also relatively high.
The ammonia nitrogen removal method proposed in chinese patent CN101234836B is a nitrification-denitrification process, which is a biological treatment method, and although the biological treatment method can overcome some defects existing in the stripping method, the ammonia nitrogen removal rate and the energy consumption of the biological treatment method still do not reach the optimal state.
Disclosure of Invention
The invention aims to provide a landfill leachate treatment method, which has the advantages of simple flow, short treatment time and excellent purification effect, and the prepared landfill leachate treatment agent is fixed by biological, catalytic oxidation, photocatalytic oxidation and adsorption, and has the effect of purifying the landfill leachate in multiple ways and high-efficiency reaction, so that the landfill leachate treatment speed is accelerated, the treatment efficiency and effect are improved, and the landfill leachate treatment agent has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a landfill leachate treatment agent, which comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving a pore-forming agent and a hydrophilic emulsifier in water to obtain a water phase; dissolving aluminum isopropoxide, tetrabutyl titanate and an oleophylic emulsifier in an organic solvent to obtain an oil phase; adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing, and calcining to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
preferably, the hydrophilic emulsifier is selected from at least one of tween-20, tween-40, tween-60, tween-80; the lipophilic emulsifier is at least one selected from span-20, span-40, span-60 and span-80; the organic solvent is at least one selected from dichloromethane, chloroform, toluene, xylene, petroleum ether, ethyl acetate, methyl acetate, butyl acetate, cyclohexane and n-hexane.
S2, preparing magnetic microspheres: dissolving ferric chloride and ferrous chloride in water, adding Al prepared in step S1 2 O 3 /TiO 2 Dropwise adding ammonia water into the composite porous hollow microspheres for reaction, separating by using a magnet, washing and drying to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed solutions obtained after the aerobic microbial agent and the anaerobic microbial agent are respectively activated to obtain a microbial agent;
s4, preparing the microorganism-rich magnetic microsphere: adding the magnetic microsphere prepared in the step S2 into the microbial agent prepared in the step S3, stirring and mixing, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microsphere;
s5, deposition of polydopamine: adding the microorganism-rich magnetic microsphere prepared in the step S4 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating by a magnet, washing and drying to obtain the polydopamine modified microorganism-rich magnetic microsphere;
s6, pretreatment of activated carbon and fly ash: uniformly mixing the activated carbon and the fly ash, adding the mixture into an acid solution, and carrying out soaking treatment to obtain a pretreated mixture of the activated carbon and the fly ash;
s7, preparing a landfill leachate treating agent: adding the pretreated activated carbon and fly ash mixture prepared in the step S6 into water, adding the polydopamine modified microorganism-rich magnetic microsphere prepared in the step S5, stirring and mixing, separating by a magnet, washing and drying to obtain the landfill leachate treating agent.
As a further improvement of the invention, the porogen in step S1 comprises a mesoporous porogen and a macroporous porogen, wherein the mesoporous porogen is at least one selected from cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO106, the macroporous porogen is at least one selected from polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether, preferably at least one selected from cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, the mass ratio is 3-5:7, the mass ratio of the porogen, hydrophilic emulsifier and water is 3-5:1-2:100, the mass ratio of the aluminum isopropoxide, tetrabutyl titanate, lipophilic emulsifier and organic solvent is 7-12:10-15:2-3:100, the mass ratio of the aqueous phase and the oil phase is 3-5:6-8, the emulsifying condition is 12000-15000r/min, the stirring reaction time is 0.5-1h, and the calcining time is 2-300 h; the ferric chloride, ferrous chloride and Al in the step S2 2 O 3 /TiO 2 The mass ratio of the composite porous hollow microspheres is 27:13:100-150, wherein the concentration of the ammonia water is 15-20wt%, and the reaction time is 1-2h.
As a further improvement of the present invention, in the step S3, an aerobic microbial agent and an anaerobic agent are used as the microbial agent The mass ratio of the oxygen microbial agent is 5-10:7, and the aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 2-4:5-7; the anaerobic microbial agent comprises denitrifying bacteria, and the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in Gao's culture medium, and performing activation culture for 12-18h under the conditions of oxygen volume fraction of 25-30%, temperature of 25-30deg.C, and rotation speed of 50-70r/min to obtain aerobic microorganism strain seed liquid with bacterial content of 10 8 -10 9 cfu/mL, the activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in Gao's culture medium, and performing activation culture for 12-18h under oxygen-free condition at 25-30deg.C and rotation speed of 50-70r/min to obtain aerobic microorganism strain seed solution with bacterial content of 10 8 -10 9 The mass ratio of the microbial agent to the magnetic microspheres in the step S4 is 50:12-15, and the stirring and mixing time is 30-50min.
As a further improvement of the invention, the mass ratio of the microorganism-rich magnetic microsphere, the dopamine hydrochloride and the catalyst in the step S5 is 20:22-25:0.5-1, and the catalyst contains 3-5wt% of CoCl 2 The pH=5-6 Tris-HCl solution, the temperature of the heating and stirring reaction is 45-50 ℃, the time is 2-3h, the mass ratio of the activated carbon to the fly ash to the acid solution in the step S6 is 10-15:17-20:100, the acid solution is nitric acid solution with the concentration of 1-2mol/L, the soaking treatment time is 20-40min, the mass ratio of the pretreated mixture of the activated carbon and the fly ash to the polydopamine modified microorganism-rich magnetic microsphere in the step S7 is 3-5:7-10, and the stirring and mixing time is 15-30min.
The invention further protects the landfill leachate treatment agent prepared by the preparation method.
The invention further protects application of the landfill leachate treatment agent in landfill leachate treatment.
The invention further provides a landfill leachate treatment method, which comprises the following steps:
(1) Mixing the landfill leachate with limestone, and settling to obtain solid slag and settling liquid;
(2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate;
(3) Mixing the aerated effluent with the landfill leachate treatment agent, performing a first reaction under aerobic conditions, performing a second reaction under anaerobic conditions, adding dilute acid solution, performing hydrolysis pre-acidification treatment, introducing ozone, performing a third reaction, performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank.
As a further improvement of the invention, the mass ratio of the landfill leachate to the limestone in the step (1) is 1000:25-55, and the sedimentation time is 12-18h.
As a further improvement of the invention, the mass ratio of the aerated effluent to the landfill leachate treatment agent in the step (3) is 100:3-5, the first reaction time is 4-6h, the second reaction time is 2-4h, the third reaction time is 2-3h, and the hydrolysis pre-acidification treatment time is 15-20min.
As a further improvement of the invention, in the step (3), the volume fraction of oxygen is 25-30%, the volume fraction of carbon dioxide is 5-10%, the balance is nitrogen, the anaerobic condition is 5-10%, the balance is nitrogen, the dilute acid solution is 0.1-0.2mol/L dilute sulfuric acid or dilute hydrochloric acid, the addition amount is 10-15g/L, and the ozone inlet amount is 8-10 mg/(L.min).
The invention has the following beneficial effects:
the high ammonia nitrogen content in the landfill leachate is one of the most prominent problems existing in the current landfill leachate treatment process, and is also a main factor affecting water quality. The ammonia nitrogen is formed by biodegradation of nitrogenous substances in proteins and the like in kitchen waste, the content of the converted ammonia nitrogen is rapidly increased along with the increase of time, the emitted peculiar smell is increased, the toxicity is improved, the environment is polluted, and the physical health of people is influenced.
In the garbage leachate treatment method, because the ammonia nitrogen concentration in the leachate can inhibit the activity of microorganisms when the concentration is too high, firstly, limestone is added to pretreat the leachate to remove local ammonia nitrogen, so that the microbial agent can have good reactivity after the garbage leachate treatment agent is added subsequently, and then the pre-aeration is carried out to remove hydrogen sulfide poison in the garbage leachate.
Furthermore, the garbage leachate treatment method is added with the garbage leachate treatment agent, and organic matters in the garbage leachate are decomposed into carbon dioxide and sludge by the aerobic microbial agent under the aerobic condition, so that the metal content in the garbage leachate can be effectively reduced, the efficiency is high, and the running cost is low. Further, under anaerobic conditions, the organic matter therein is decomposed into biogas (CO) 2 And CH (CH) 4 Is a mixed gas of (c) and (d). Low cost, less residual mud and less needed nutrient substances.
Microorganisms are immobilized in the pore channels of the microspheres to proliferate in a large amount to form micro-ecology, glycoprotein, lipopolysaccharide and the like secreted by the microorganisms, and the negatively charged groups adsorb heavy metals, flocculate, coordinate complex, ion exchange, electrostatic interaction, redox or generate inorganic microprecipitation and the like, so that a large amount of heavy metal ions are immobilized through the surface microorganisms, thereby realizing efficient treatment of sewage, and simultaneously, the microbial agent also provides effective and rapid degradation for organic pollutants such as persistent organic pollutants, phenolic compounds, nitro compounds, dyes and the like.
In most of the old garbage percolate, the old garbage percolate contains more humic acid, fulvic acid and the like, so that the old garbage percolate is difficult to biodegrade, and the effluent after microbial treatment also contains organic matters which are difficult to degrade, so that the emission standard is difficult to reach, and further advanced treatment is required. And oxidation treatment this can treat these refractory organics.
O 3 The degradation-resistant substances can be converted into easily-decomposable substances, such as complex long-chain humic acid can be decomposed into short-chain organic acid, etc. At the same time, the method can decolorize the percolate with high decolorizing speed because most of the chromogenic organic matters in the garbage percolate contain chromophoric groups such as vinyl, azoxy, azo, carbonyl, thioketone and the like, the bond energy is weak, and the organic matters can be rapidly decolorized by O 3 Or OH damage. Pair B after ozone treatmentOD 5 The removal rate of the waste leachate is obviously improved, and the biodegradability of the waste leachate is improved.
Catalytic ozonation is a catalyst promoting O 3 The reaction is quick and has no selectivity, and the removal rate of TOC and COD and the biodegradability of landfill leachate can be obviously improved. The landfill leachate treatment agent contains abundant ferroferric oxide, and under the condition of a small amount of acid, the oxide can be decomposed to generate a small amount of Fe 2+ And Fe (Fe) 3+ Ions initiate ozone to generate OH, thereby promoting the decomposition of organic matters. Meanwhile, metal oxide TiO in garbage leachate treatment agent 2 、Al 2 O 3 Also has high activity on the catalytic decomposition of ozone, tiO 2 、Al 2 O 3 And the catalytic activity of the ozone is obviously improved under the synergistic effect of the ferroferric oxide.
OH is capable of oxidizing all organics including olefinic, lipidic, aromatic and aliphatic organics, while also oxidizing inorganics including anions and cations. OH can oxidize refractory organic matters in the organic matters into small molecules which are easy to biochemically and can even oxidize the refractory organic matters into CO 2 And H 2 O, thereby improving the biodegradability of the landfill leachate.
According to the invention, after the treatment agent for landfill leachate is subjected to polydopamine deposition modification, a polydopamine thin layer is formed on the surface, a large amount of heavy metal ion pollutants can be fixed through coordination, so that the effect of purifying heavy metal ions is achieved, meanwhile, the groups have good adhesion, on one hand, impurities are removed through acid-treated activated carbon and fly ash, on the other hand, after acid treatment, the contents of surface carboxyl, lactone and phenolic hydroxyl are increased through magnesium, silicon and other ions combined with oxygen-containing functional groups, so that stable adsorption and fixation are achieved through hydrogen bond formation with polydopamine, in addition, COD, ammonia nitrogen and the like in landfill leachate are reduced through adsorption through the addition of porous solid matters such as activated carbon and fly ash, and the addition of the two has a synergistic effect.
In addition, due to TiO 2 Has good photocatalytic oxidation activity, further improves oxidation effect, further purifies landfill leachate, and obtains effluent which reaches the discharge standard after precipitation after purification treatment.
In the landfill leachate treatment agent, the magnetic ferroferric oxide exists, so that the prepared landfill leachate treatment agent has magnetism, is convenient for magnet separation in the treatment process, and simultaneously, reacts in the presence of trace acid to generate a small amount of catalyst Fe in the ozone oxidation process 2+ And Fe (Fe) 3+ Ions catalyze ozone to carry out oxidation reaction.
The garbage leachate treatment method disclosed by the invention is simple in flow, short in treatment time and excellent in purification effect, and the prepared garbage leachate treatment agent is immobilized through biological, catalytic oxidation, photocatalytic oxidation and adsorption, and the garbage leachate is purified in multiple ways, so that the effect of efficient reaction is achieved, the garbage leachate treatment speed is accelerated, the treatment efficiency and effect are improved, and the garbage leachate treatment agent has a wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 shows Al obtained in example 1 of the present invention 2 O 3 /TiO 2 TEM image of composite porous hollow microspheres;
FIG. 2 is an SEM image of magnetic microspheres prepared according to example 1 of the invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The landfill leachate is derived from a certain landfill site in Nanjing, and the water quality conditions are shown in Table 1.
TABLE 1
Bacillus subtilis and nitrifying bacillus with the content of more than 98 percent and 25 kg/bag are purchased from the environmental protection materials factory of the aviation body in Beijing. Denitrifying bacteria, content >99%,25 kg/bag, purchased from western security biosciences, inc. Activated carbon, industrial grade, pH 7-9, caramel decolorization >90%, total iron content <0.10%, purchased from Henan Linsen activated carbon Co. Fly ash, first grade, 50 kg/bag, 200 mesh, purchased from the mineral product processing plant of Yumei in the Ministry of life.
Example 1
The embodiment provides a preparation method of a landfill leachate treatment agent, which comprises the following steps:
S1.Al 2 O 3 /TiO 2 Preparing composite porous hollow microspheres: 3 parts by weight of a pore-forming agent and 1 part by weight of tween-20 are dissolved in 100 parts by weight of water to obtain a water phase; dissolving 7 parts by weight of aluminum isopropoxide, 10 parts by weight of tetrabutyl titanate and 2 parts by weight of span-20 in 100 parts by weight of butyl acetate to obtain an oil phase; adding 30 parts by weight of water phase into 60 parts by weight of oil phase, emulsifying for 3min at 12000r/min, stirring for reacting for 0.5h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 300 ℃ for 2h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres; FIG. 1 shows the prepared Al 2 O 3 /TiO 2 TEM image of composite porous hollow microsphere, it can be seen that the microsphere has a hollow structure.
The pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 3:7;
s2, preparing magnetic microspheres: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 100 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 Composite porous hollow microBall, adding 15wt% ammonia water dropwise to adjust pH value to 8, stirring and reacting for 1h, separating by magnet, washing by clean water, drying at 105 ℃ for 2h to obtain magnetic microsphere; FIG. 2 is an SEM image of the magnetic microspheres produced, which shows that the particle size of the magnetic microspheres is between 400 and 600 nm.
S3, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 5 parts by weight of an aerobic microbial agent and 7 parts by weight of an anaerobic microbial agent to obtain a microbial agent;
The aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 2:5;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 12 hours under the conditions that the volume fraction of oxygen is 25%, the temperature is 25 ℃ and the rotating speed is 50r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 8 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in Gao's culture medium, and performing activation culture for 12h under the condition of no oxygen, temperature of 25deg.C and rotation speed of 50r/min to obtain aerobic microorganism strain seed liquid with bacterial content of 10 8 cfu/mL；
S4, preparing the microorganism-rich magnetic microsphere: adding 12 parts by weight of the magnetic microspheres prepared in the step S2 into 50 parts by weight of the microbial agent prepared in the step S3, stirring and mixing for 30min, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microspheres;
s5, deposition of polydopamine: adding 20 parts by weight of the microorganism-rich magnetic microsphere prepared in the step S4 into 100 parts by weight of water, adding 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of catalyst, heating to 45 ℃, stirring and reacting for 2 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine-modified microorganism-rich magnetic microsphere;
The catalyst was a catalyst containing 3wt% CoCl 2 Tris-HCl solution at ph=5;
s6, pretreatment of activated carbon and fly ash: uniformly mixing 10 parts by weight of activated carbon and 17 parts by weight of fly ash, adding into 100 parts by weight of 1mol/L nitric acid solution, and soaking for 20min to obtain a pretreated activated carbon and fly ash mixture;
s7, preparing a landfill leachate treating agent: adding 30 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S6 into 500 parts by weight of water, adding 70 parts by weight of the polydopamine modified microorganism-rich magnetic microspheres prepared in the step S5, stirring and mixing for 15min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treatment agent.
Example 2
The embodiment provides a preparation method of a landfill leachate treatment agent, which comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving 5 parts by weight of a pore-forming agent and 2 parts by weight of tween-40 in 100 parts by weight of water to obtain a water phase; 12 parts by weight of aluminum isopropoxide, 15 parts by weight of tetrabutyl titanate and 3 parts by weight of span-40 are dissolved in 100 parts by weight of ethyl acetate to obtain an oil phase; adding 50 parts by weight of water phase into 80 parts by weight of oil phase, emulsifying for 5min at 15000r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 500 ℃ for 4h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 5:7;
s2, preparing magnetic microspheres: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 150 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 Dropwise adding 20wt% ammonia water into the composite porous hollow microspheres to adjust the pH value to 9, stirring and reacting for 2 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 10 parts by weight of an aerobic microbial agent and 7 parts by weight of an anaerobic microbial agent to obtain a microbial agent;
the aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 4:7;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and performing activation culture for 18h under the conditions that the volume fraction of oxygen is 30%, the temperature is 30 ℃ and the rotating speed is 70r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium, and performing activation culture for 18h under the condition of no oxygen, the temperature is 30 ℃ and the rotating speed is 70r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
S4, preparing the microorganism-rich magnetic microsphere: adding 15 parts by weight of the magnetic microspheres prepared in the step S2 into 50 parts by weight of the microbial agent prepared in the step S3, stirring and mixing for 50 minutes, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microspheres;
s5, deposition of polydopamine: adding 20 parts by weight of the microorganism-rich magnetic microsphere prepared in the step S4 into 100 parts by weight of water, adding 25 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 50 ℃, stirring for reaction for 3 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine-modified microorganism-rich magnetic microsphere;
the catalyst was a catalyst containing 5wt% CoCl 2 Tris-HCl solution at ph=6;
s6, pretreatment of activated carbon and fly ash: uniformly mixing 15 parts by weight of activated carbon and 20 parts by weight of fly ash, adding into 100 parts by weight of 2mol/L nitric acid solution, and soaking for 40min to obtain a pretreated activated carbon and fly ash mixture;
s7, preparing a landfill leachate treating agent: adding 50 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S6 into 500 parts by weight of water, adding 100 parts by weight of the polydopamine modified microorganism-rich magnetic microspheres prepared in the step S5, stirring and mixing for 30min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treatment agent.
Example 3
The embodiment provides a preparation method of a landfill leachate treatment agent, which comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7;
s2, preparing magnetic microspheres: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 125 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 Dropwise adding 17wt% ammonia water into the composite porous hollow microspheres to adjust the pH value to 8.5, stirring and reacting for 1.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 7 parts by weight of aerobic microbial agent and 7 parts by weight of anaerobic microbial agent to obtain a microbial agent;
The aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 3:6;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 16h under the conditions that the volume fraction of oxygen is 27%, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: respectively streaking aerobic microorganism in Gao's culture mediumUnder the condition of no oxygen, the temperature is 27 ℃, the rotating speed is 60r/min, and the activation culture is carried out for 16 hours, thus obtaining the seed liquid of the aerobic microorganism strain, the bacterial content is 10 9 cfu/mL；
S4, preparing the microorganism-rich magnetic microsphere: adding 13 parts by weight of the magnetic microspheres prepared in the step S2 into 50 parts by weight of the microbial agent prepared in the step S3, stirring and mixing for 40min, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microspheres;
s5, deposition of polydopamine: adding 20 parts by weight of the microorganism-rich magnetic microsphere prepared in the step S4 into 100 parts by weight of water, adding 23 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine-modified microorganism-rich magnetic microsphere;
The catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s6, pretreatment of activated carbon and fly ash: uniformly mixing 12 parts by weight of activated carbon and 18.5 parts by weight of fly ash, adding into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain a pretreated activated carbon and fly ash mixture;
s7, preparing a landfill leachate treating agent: adding 40 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S6 into 500 parts by weight of water, adding 85 parts by weight of the polydopamine modified microorganism-rich magnetic microspheres prepared in the step S5, stirring and mixing for 20min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treatment agent.
Example 4
The difference compared to example 3 is that the porogen is a single cetyltrimethylammonium bromide.
Example 5
The difference compared to example 3 is that the porogen is a single polyethylene glycol octyl phenyl ether.
Example 6
The difference from example 3 is that the aerobic microbial agent is a single bacillus subtilis.
Example 7
The difference from example 3 is that the aerobic microbial agent is a single nitrifying bacteria genus.
Comparative example 1
In comparison with example 3, the difference is that aluminum isopropoxide is not added in step S1.
The method comprises the following steps:
S1.TiO 2 preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 22 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7.
Comparative example 2
In comparison with example 3, the difference is that tetrabutyl titanate is not added in step S1.
The method comprises the following steps:
S1.Al 2 O 3 preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 22 parts by weight of aluminum isopropoxide and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7.
Comparative example 3
The difference compared to example 3 is that no porogen is added in step S1.
The method comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparation of composite hollow microspheres: dissolving 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite hollow microspheres;
comparative example 4
In comparison with example 3, the difference is that step S2 is not performed.
S1.Al 2 O 3 /TiO 2 Preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7;
s2, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 7 parts by weight of aerobic microbial agent and 7 parts by weight of anaerobic microbial agent to obtain a microbial agent;
the aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 3:6;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 16h under the conditions that the volume fraction of oxygen is 27%, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium, and performing activation culture for 16h under the condition of no oxygen, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
S3, preparing microorganism-rich microspheres: adding 13 parts by weight of Al prepared in the step S1 into 50 parts by weight of the microbial agent prepared in the step S2 2 O 3 /TiO 2 Mixing the composite porous hollow microspheres for 40min, separating by a magnet, washing and drying to obtain microorganism-rich microspheres;
s4, deposition of polydopamine: adding 20 parts by weight of the microorganism-rich microspheres prepared in the step S3 into 100 parts by weight of water, adding 23 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine-modified microorganism-rich microspheres;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s5, pretreatment of activated carbon and fly ash: uniformly mixing 12 parts by weight of activated carbon and 18.5 parts by weight of fly ash, adding into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain a pretreated activated carbon and fly ash mixture;
s6, preparing a landfill leachate treating agent: adding 40 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S6 into 500 parts by weight of water, adding 85 parts by weight of the polydopamine modified microorganism-rich microspheres prepared in the step S5, stirring and mixing for 20min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treatment agent.
Comparative example 5
The difference from example 3 is that the aerobic microbial agent is not added in step S3.
The method comprises the following steps:
s3, preparing a microbial agent: and activating the anaerobic microbial agent to obtain strain seed liquid, namely the microbial agent.
The anaerobic systemThe method for activating the microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium, and performing activation culture for 16h under the condition of no oxygen, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL。
Comparative example 6
The difference from example 3 is that the anaerobic microbial agent is not added in step S3.
S3, preparing a microbial agent: and activating the aerobic microbial agent to obtain strain seed liquid, namely the microbial agent.
The activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 16h under the conditions that the volume fraction of oxygen is 27%, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL。
Comparative example 7
The difference from example 3 is that steps S3 and S4 are not performed.
The method comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7;
s2, preparing magnetic microspheres: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 125 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 The composite porous hollow microsphere is added with 17wt% ammonia water dropwise to adjust the pH value to 8.5, and stirredMixing and reacting for 1.5h, separating by a magnet, washing by clear water, and drying for 2h at 105 ℃ to obtain the magnetic microsphere;
s3, deposition of polydopamine: adding 20 parts by weight of the magnetic microsphere prepared in the step S2 into 100 parts by weight of water, adding 23 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine modified magnetic microsphere;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
s4, pretreatment of activated carbon and fly ash: uniformly mixing 12 parts by weight of activated carbon and 18.5 parts by weight of fly ash, adding into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain a pretreated activated carbon and fly ash mixture;
s5, preparing a landfill leachate treating agent: adding 40 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S4 into 500 parts by weight of water, adding 85 parts by weight of the polydopamine modified magnetic microspheres prepared in the step S3, stirring and mixing for 20min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treating agent.
Comparative example 8
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7;
s2, magnetic microspheresPreparation: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 125 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 Dropwise adding 17wt% ammonia water into the composite porous hollow microspheres to adjust the pH value to 8.5, stirring and reacting for 1.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 7 parts by weight of aerobic microbial agent and 7 parts by weight of anaerobic microbial agent to obtain a microbial agent;
The aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 3:6;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 16h under the conditions that the volume fraction of oxygen is 27%, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium, and performing activation culture for 16h under the condition of no oxygen, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
S4, preparing the microorganism-rich magnetic microsphere: adding 13 parts by weight of the magnetic microspheres prepared in the step S2 into 50 parts by weight of the microbial agent prepared in the step S3, stirring and mixing for 40min, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microspheres;
s5, pretreatment of activated carbon and fly ash: uniformly mixing 12 parts by weight of activated carbon and 18.5 parts by weight of fly ash, adding into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain a pretreated activated carbon and fly ash mixture;
S6, preparing a landfill leachate treating agent: adding 40 parts by weight of the pretreated activated carbon and fly ash mixture prepared in the step S5 into 500 parts by weight of water, adding 85 parts by weight of the microorganism-rich magnetic microspheres prepared in the step S4, stirring and mixing for 20min, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain the landfill leachate treating agent.
Comparative example 9
The difference compared to example 3 is that step S6 is a single activated carbon.
The method comprises the following steps:
s6, pretreatment of activated carbon: adding 30.5 parts by weight of activated carbon into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain pretreated activated carbon.
Comparative example 10
The difference compared to example 3 is that step S6 is a single fly ash.
The method comprises the following steps:
s6, pretreatment of fly ash: adding 30.5 parts by weight of fly ash into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain pretreated fly ash.
Comparative example 11
The difference from example 3 is that steps S6 and S7 are not performed.
S1.Al 2 O 3 /TiO 2 Preparing composite porous hollow microspheres: dissolving 4 parts by weight of a pore-forming agent and 1.5 parts by weight of tween-80 in 100 parts by weight of water to obtain a water phase; dissolving 10 parts by weight of aluminum isopropoxide, 12 parts by weight of tetrabutyl titanate and 2.5 parts by weight of span-80 in 100 parts by weight of methyl acetate to obtain an oil phase; adding 40 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 4min at 13500r/min, stirring for reacting for 1h, centrifuging for 15min at 5000r/min, washing with clear water, and calcining at 400 ℃ for 3h to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 4:7;
s2, preparing magnetic microspheres: 27 parts by weight of ferric chloride and 13 parts by weight of ferrous chloride are dissolved in 100 parts by weight of water, and 125 parts by weight of Al prepared in the step S1 is added 2 O 3 /TiO 2 Composite porous hollow microsphere, 17wt% ammonia water is added dropwise to adjust pH value to 8.5Stirring and reacting for 1.5h, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2h to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed liquid obtained by respectively activating 7 parts by weight of aerobic microbial agent and 7 parts by weight of anaerobic microbial agent to obtain a microbial agent;
the aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus, and the mass ratio is 3:6;
the anaerobic microbial agent comprises denitrifying bacteria;
the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium respectively, and carrying out activation culture for 16h under the conditions that the volume fraction of oxygen is 27%, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
The activation method of the anaerobic microbial agent comprises the following steps: marking off the aerobic microorganism in a Gao's culture medium, and performing activation culture for 16h under the condition of no oxygen, the temperature is 27 ℃ and the rotating speed is 60r/min to obtain an aerobic microorganism strain seed liquid with the bacterial content of 10 9 cfu/mL；
S4, preparing the microorganism-rich magnetic microsphere: adding 13 parts by weight of the magnetic microspheres prepared in the step S2 into 50 parts by weight of the microbial agent prepared in the step S3, stirring and mixing for 40min, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microspheres;
s5, deposition of polydopamine: adding 20 parts by weight of the microorganism-rich magnetic microsphere prepared in the step S4 into 100 parts by weight of water, adding 23 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 2.5 hours, separating by a magnet, washing by clear water, and drying at 105 ℃ for 2 hours to obtain the polydopamine modified microorganism-rich magnetic microsphere, namely a landfill leachate treatment agent;
the catalyst was a catalyst containing 4wt% CoCl 2 Tris-HCl solution at ph=5.5.
Comparative example 12
The difference from example 3 is that only step S6 is included.
The method comprises the following steps:
pretreatment of activated carbon and fly ash: uniformly mixing 12 parts by weight of activated carbon and 18.5 parts by weight of fly ash, adding into 100 parts by weight of 1.5mol/L nitric acid solution, and soaking for 30min to obtain a pretreated mixture of the activated carbon and the fly ash, namely the landfill leachate treating agent.
Test example 1 adsorption and immobilization of heavy Metal ions
The landfill leachate treatment agents prepared in the examples 1-7 and the comparative examples 1-5 and the commercial sewage treatment agent are used for treating serious excessive wastewater of certain heavy metals, ozone is introduced, the ozone introduction amount is 9 mg/(L.min), and all indexes of the effluent after the treatment are shown in the table 2.
TABLE 2
Test example 2 purification effect on antibiotic contaminated wastewater
The landfill leachate treatment agents prepared in examples 1 to 7 and comparative examples 1 to 5 of the present invention and commercial sewage treatment agents were used to treat antibiotic sewage.
(1) Preparing 1g/L of cefalexin solution serving as antibiotic sewage, adjusting the pH value of the sewage to be 7, adding 0.1g/L of treating agent, introducing ozone, stirring for 5min at 200rpm to ensure that the treating agent is fully mixed with the wastewater, and settling for 30min for precipitation. Centrifugation at 5000r/min for 15min, collecting supernatant, detecting absorption peak of the solution at 262nm by ultraviolet-visible spectrophotometer, and calculating clearance rate of cephalexin, and the result is shown in Table 3.
TABLE 3 Table 3
(2) 1g/L ofloxacin solution is prepared as antibiotic sewage, the pH value of the sewage is regulated to be 8, 0.1g/L of treating agent is added, ozone is introduced, the ozone introducing amount is 9 mg/(L.min), stirring is carried out for 5min at 200rpm, so that the sufficient mixing of the treating agent and the wastewater is ensured, and sedimentation is carried out for 30min for precipitation. Centrifugation at 5000r/min for 15min, collecting supernatant, detecting absorption peak of the solution at 294nm with ultraviolet-visible spectrophotometer, and calculating clearance rate of ofloxacin, and the result is shown in Table 4.
TABLE 4 Table 4
As shown in the table above, the landfill leachate treatment agent prepared in the embodiments 1-3 has remarkable advantages compared with the commercial products, and can achieve high-efficiency purification effect on antibiotic pollutants.
Example 8
The embodiment provides a landfill leachate treatment method, which comprises the following steps:
(1) Mixing 1000 parts by weight of landfill leachate with 25 parts by weight of limestone, stirring and reacting for 2 hours, and settling for 12 hours to obtain solid slag and settling liquid;
(2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate;
(3) Mixing 1000 parts by weight of aerated effluent with 30 parts by weight of the landfill leachate treatment agent prepared in the example 1, reacting for 4 hours under aerobic conditions, reacting for 2 hours under anaerobic conditions, adding 0.1mol/L of dilute hydrochloric acid with the addition of 10g/L, performing hydrolytic pre-acidification treatment for 15 minutes, simultaneously introducing ozone with the introduction of 8 mg/(L.min), reacting for 2 hours, and then performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank;
the aerobic condition is that the volume fraction of oxygen is 25%, the volume fraction of carbon dioxide is 5%, and the balance is nitrogen;
the anaerobic condition is that the volume fraction of carbon dioxide is 5 percent, and the balance is nitrogen.
Example 9
The embodiment provides a landfill leachate treatment method, which comprises the following steps:
(1) Mixing 1000 parts by weight of landfill leachate with 55 parts by weight of limestone, stirring and reacting for 2 hours, and settling for 18 hours to obtain solid slag and settling liquid;
(2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate;
(3) Mixing 1000 parts by weight of aerated effluent with 50 parts by weight of the landfill leachate treatment agent prepared in the example 2, reacting for 6 hours under an aerobic condition, reacting for 4 hours under an anaerobic condition, adding 0.2mol/L of dilute hydrochloric acid with the addition amount of 15g/L, performing hydrolytic pre-acidification treatment for 20 minutes, simultaneously introducing ozone with the introduction amount of 10 mg/(L.min), reacting for 3 hours, and then performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank;
the aerobic condition is that the volume fraction of oxygen is 30%, the volume fraction of carbon dioxide is 10%, and the balance is nitrogen;
the anaerobic condition is that the volume fraction of carbon dioxide is 10 percent, and the balance is nitrogen.
Example 10
The embodiment provides a landfill leachate treatment method, which comprises the following steps:
(1) Mixing 1000 parts by weight of landfill leachate with 40 parts by weight of limestone, stirring and reacting for 2 hours, and settling for 16 hours to obtain solid slag and settling liquid;
(2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate;
(3) Mixing 1000 parts by weight of aerated effluent with 40 parts by weight of the landfill leachate treatment agent prepared in the example 3, reacting for 5 hours under an aerobic condition, reacting for 3 hours under an anaerobic condition, adding 0.15mol/L dilute sulfuric acid with the addition amount of 12g/L, performing hydrolytic pre-acidification treatment for 17 minutes, simultaneously introducing ozone with the introduction amount of 9 mg/(L.min), reacting for 2.5 hours, then performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank;
The aerobic condition is that the volume fraction of oxygen is 27%, the volume fraction of carbon dioxide is 7%, and the balance is nitrogen;
the anaerobic condition is that the volume fraction of carbon dioxide is 7 percent, and the balance is nitrogen.
Example 11
In comparison with example 10, a landfill leachate treatment agent was prepared in example 4.
Example 12
In comparison with example 10, a landfill leachate treatment agent was prepared from example 5.
Example 13
In comparison with example 10, a landfill leachate treatment agent was prepared in example 6.
Example 14
In comparison with example 10, the landfill leachate treatment agent was prepared in example 7.
Comparative example 13
In comparison with example 10, the difference is that step (1) was not performed.
Comparative example 14
In comparison with example 10, the difference is that in step (3), dilute sulfuric acid was not added and no hydrolytic pre-acidification treatment was performed.
Comparative example 15
In comparison with example 10, the difference is that the ozone is not supplied in the step (3).
Comparative example 16
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 1.
Comparative example 17
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 2.
Comparative example 18
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 3.
Comparative example 19
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 4.
Comparative example 20
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 5.
Comparative example 21
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 6.
Comparative example 22
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 7.
Comparative example 23
The difference compared to example 10 is that a landfill leachate treatment agent is prepared from comparative example 8.
Comparative example 24
In comparison with example 10, a landfill leachate treatment agent was prepared in comparative example 9.
Comparative example 25
The difference compared to example 10 is that a landfill leachate treatment agent was prepared from comparative example 10.
Comparative example 26
In comparison with example 10, a landfill leachate treatment agent was prepared in comparative example 11.
Comparative example 27
The difference compared to example 10 is that a landfill leachate treatment agent was prepared from comparative example 12.
Test example 3
The effluent water discharged after the treatment by the methods of examples 8 to 14 and comparative examples 13 to 27 of the present invention was examined, and the results are shown in Table 5.
TABLE 5
As shown in the table above, various indexes of effluent discharged after the landfill leachate treatment method in the embodiments 8-10 of the invention are obviously reduced, and the effluent can reach the standard of pollution control Standard of domestic landfill (GB 16889-2008).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the landfill leachate treatment agent is characterized by comprising the following steps of:
S1.Al 2 O 3 /TiO 2 preparing composite porous hollow microspheres: dissolving a pore-forming agent and a hydrophilic emulsifier in water to obtain a water phase; dissolving aluminum isopropoxide, tetrabutyl titanate and an oleophylic emulsifier in an organic solvent to obtain an oil phase; adding the water phase into the oil phase, emulsifying, stirring for reaction, centrifuging, washing, and calcining to obtain Al 2 O 3 /TiO 2 Composite porous hollow microspheres;
the pore-forming agent comprises a mesoporous pore-forming agent and a macroporous pore-forming agent, wherein the mesoporous pore-forming agent is selected from at least one of cetyltrimethylammonium bromide, ethylene oxide-propylene oxide triblock copolymers PEO20-PPO70-PEO20 and PEO106-PPO70-PEO106, and the macroporous pore-forming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether;
S2, preparing magnetic microspheres: dissolving ferric chloride and ferrous chloride in water, adding Al prepared in step S1 2 O 3 /TiO 2 Dropwise adding ammonia water into the composite porous hollow microspheres for reaction, separating by using a magnet, washing and drying to obtain magnetic microspheres;
s3, preparing a microbial agent: uniformly mixing strain seed solutions obtained after the aerobic microbial agent and the anaerobic microbial agent are respectively activated to obtain a microbial agent;
the aerobic microbial agent comprises bacillus subtilis and nitrifying bacillus;
s4, preparing the microorganism-rich magnetic microsphere: adding the magnetic microsphere prepared in the step S2 into the microbial agent prepared in the step S3, stirring and mixing, separating by a magnet, washing and drying to obtain the microbial-enriched magnetic microsphere;
s5, deposition of polydopamine: adding the microorganism-rich magnetic microsphere prepared in the step S4 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating by a magnet, washing and drying to obtain the polydopamine modified microorganism-rich magnetic microsphere;
s6, pretreatment of activated carbon and fly ash: uniformly mixing the activated carbon and the fly ash, adding the mixture into an acid solution, and carrying out soaking treatment to obtain a pretreated mixture of the activated carbon and the fly ash;
s7, preparing a landfill leachate treating agent: adding the pretreated activated carbon and fly ash mixture prepared in the step S6 into water, adding the polydopamine modified microorganism-rich magnetic microsphere prepared in the step S5, stirring and mixing, separating by a magnet, washing and drying to obtain the landfill leachate treating agent.
2. The preparation method according to claim 1, wherein the pore-forming agent in the step S1 is cetyl trimethyl ammonium bromide and polyethylene glycol octyl phenyl ether, and the mass ratio is 3-5:7; the mass ratio of the pore-forming agent to the hydrophilic emulsifier to the water is 3-5:1-2:100, the mass ratio of the aluminum isopropoxide to the tetrabutyl titanate to the lipophilic emulsifier to the organic solvent is 7-12:10-15:2-3:100, the mass ratio of the water phase to the oil phase is 3-5:6-8, the emulsification condition is 12000-15000r/min for 3-5min, the stirring reaction time is 0.5-1h, the calcination temperature is 300-500 ℃ and the time is 2-4h; the ferric chloride, ferrous chloride and Al in the step S2 2 O 3 /TiO 2 The mass ratio of the composite porous hollow microspheres is 27:13:100-150, wherein the concentration of the ammonia water is 15-20wt%, and the reaction time is 1-2h.
3. The preparation method of claim 1, wherein in the step S3, the mass ratio of the aerobic microbial agent to the anaerobic microbial agent in the microbial agent is 5-10:7, and the mass ratio of the bacillus subtilis and the nitrifying bacillus in the aerobic microbial agent is 2-4:5-7; the anaerobic microbial agent comprises denitrifying bacteria, and the activation method of the aerobic microbial agent comprises the following steps: marking off the aerobic microorganism in Gao's culture medium, and performing activation culture for 12-18h under the conditions of oxygen volume fraction of 25-30%, temperature of 25-30deg.C, and rotation speed of 50-70r/min to obtain aerobic microorganism strain seed liquid with bacterial content of 10 8 -10 9 cfu/mL, the activation method of the anaerobic microbial agent comprises the following steps: marking off aerobic microorganism in Gao's culture medium, and controlling the temperature to 25 under oxygen-free conditionActivating and culturing at-30deg.C and rotation speed of 50-70r/min for 12-18 hr to obtain aerobic microorganism strain seed liquid with bacterial content of 10 8 -10 9 The mass ratio of the microbial agent to the magnetic microspheres in the step S4 is 50:12-15, and the stirring and mixing time is 30-50min.
4. The preparation method according to claim 1, wherein the mass ratio of the microorganism-rich magnetic microsphere, the dopamine hydrochloride and the catalyst in the step S5 is 20:22-25:0.5-1, and the catalyst is 3-5wt% CoCl 2 The pH=5-6 Tris-HCl solution, the temperature of the heating and stirring reaction is 45-50 ℃, the time is 2-3h, the mass ratio of the activated carbon to the fly ash to the acid solution in the step S6 is 10-15:17-20:100, the acid solution is nitric acid solution with the concentration of 1-2mol/L, the soaking treatment time is 20-40min, the mass ratio of the pretreated mixture of the activated carbon and the fly ash to the polydopamine modified microorganism-rich magnetic microsphere in the step S7 is 3-5:7-10, and the stirring and mixing time is 15-30min.
5. A landfill leachate treatment agent prepared by the preparation method of any one of claims 1 to 4.
6. Use of the landfill leachate treatment agent according to claim 5 in landfill leachate treatment.
7. The garbage leachate treatment method is characterized by comprising the following steps of:
(1) Mixing the landfill leachate with limestone, and settling to obtain solid slag and settling liquid;
(2) Delivering the sedimentation liquid to an equalizing tank for pre-aeration to remove hydrogen sulfide in the landfill leachate;
(3) Mixing the aerated effluent with the landfill leachate treatment agent according to claim 5, performing a first reaction under aerobic conditions, performing a second reaction under anaerobic conditions, adding dilute acid solution, performing hydrolysis pre-acidification treatment, introducing ozone, performing a third reaction, performing magnet adsorption to remove the landfill leachate treatment agent, and discharging after passing through a sedimentation tank.
8. The method for treating landfill leachate according to claim 7, wherein the mass ratio of the landfill leachate to the limestone in the step (1) is 1000:25-55, and the settling time is 12-18h.
9. The method for treating landfill leachate according to claim 7, wherein the mass ratio of the aerated effluent to the landfill leachate treatment agent in the step (3) is 100:3-5, the first reaction time is 4-6 hours, the second reaction time is 2-4 hours, the third reaction time is 2-3 hours, and the hydrolysis pre-acidification treatment time is 15-20 minutes.
10. The method according to claim 7, wherein in the step (3), the aerobic condition is that the volume fraction of oxygen is 25-30%, the volume fraction of carbon dioxide is 5-10%, the balance is nitrogen, the anaerobic condition is that the volume fraction of carbon dioxide is 5-10%, the balance is nitrogen, the dilute acid solution is 0.1-0.2mol/L dilute sulfuric acid or dilute hydrochloric acid, the addition amount is 10-15g/L, and the ozone introducing amount is 8-10 mg/(L.min).
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| JP2003000227A (en) * | 2001-06-21 | 2003-01-07 | Nishihara Environ Sanit Res Corp | New microorganism and organic waste water treating apparatus using the same |
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| CN103408188A (en) * | 2013-07-30 | 2013-11-27 | 杭州天城环境发展有限公司 | GZBS refuse leachate treatment method |
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| JP2003000227A (en) * | 2001-06-21 | 2003-01-07 | Nishihara Environ Sanit Res Corp | New microorganism and organic waste water treating apparatus using the same |
| JP2008049249A (en) * | 2006-08-24 | 2008-03-06 | Fuji Xerox Co Ltd | Water treatment apparatus and method |
| CN101428938A (en) * | 2008-12-04 | 2009-05-13 | 杨青淼 | Treatment process for garbage leachate |
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