CN110386711B - Tubular free radical oxidation treatment method for landfill leachate - Google Patents
Tubular free radical oxidation treatment method for landfill leachate Download PDFInfo
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- CN110386711B CN110386711B CN201910687191.6A CN201910687191A CN110386711B CN 110386711 B CN110386711 B CN 110386711B CN 201910687191 A CN201910687191 A CN 201910687191A CN 110386711 B CN110386711 B CN 110386711B
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for tubular free radical oxidation treatment of landfill leachate, which adopts air as an oxidant, has small occupied area of equipment, low long-term operation cost and safe and controllable process; the composite oxide carrier with LaMnxCo1-xO3 type perovskite characteristics and the heterogeneous catalyst of nano-silver active metal are used, the catalyst is high in reaction activity and can thoroughly remove pollutants, no toxic and harmful gas, no sludge and no secondary pollution are generated in the sewage treatment process, the CODcr removal rate can reach more than 92% at most, and the NH3-N removal rate is more than 91%.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for tubular free radical oxidation treatment of landfill leachate.
Background
Landfill is a main disposal method of garbage, but the landfill process and the sealing of a landfill site are accompanied by the generation of landfill leachate. Researches show that the leachate contains various toxic substances and carcinogenic substances, if the leachate is degraded under natural conditions, the COD (chemical oxygen demand) and BOD (biochemical oxygen demand) values of the leachate can reach the national discharge standard within 15 years, and the ammonia nitrogen can reach the national discharge standard within 24-26 years. Leachate, if discharged without treatment, would severely contaminate ground water, surface water and the surrounding environment, so proper treatment of the leachate is essential.
The pollutants in the leachate mainly come from the following three sources: a large amount of soluble organic matters and inorganic matters contained in the garbage are dissolved in the entering process of rainwater and surface water and underground water to enter leachate; the garbage enters the percolate through soluble substances generated by biological and chemical physical actions; covering soil and soluble substances entering percolate in surrounding soil. The composition of the leachate is influenced by factors such as garbage composition, climate, hydrogeology, garbage landfill time and landfill mode.
The tubular radical oxidation process was developed on the basis of the wet air oxidation process. The wet air oxidation method was developed by Zimmer to man in the united states in 1994, and is also called the WAO method. The treatment method of adding the catalyst in the WAO method is called a tubular free radical oxidation method, which is called a WACO method for short. The method is characterized in that under the conditions of high temperature (200-280 ℃) and high pressure (2-8 MPa), oxygen-enriched gas or oxygen is used as an oxidant, the catalytic action of a catalyst is utilized to accelerate the respiratory reaction between organic matters in the wastewater and the oxidant, so that the organic matters in the wastewater and poisons containing N, S and the like are oxidized into CO2、N2、SO2、H2O, achieving the purpose of purification. For various industrial organic wastewater with high chemical oxygen content or containing compounds which can not be degraded by a biochemical method, the COD removal rate reaches more than 99 percent, no post-treatment is needed, and the emission standard can be reached only by one-time treatment.
The catalyst is added into the traditional wet oxidation treatment system, and the activation energy of the reaction is reduced, so that the temperature and the pressure of the reaction are reduced under the condition of not reducing the treatment effect, the oxidative decomposition capacity is improved, the reaction time is shortened, the reaction efficiency is improved, the corrosion of equipment is reduced, and the cost is reduced; the perovskite with the wet oxidation effect seriously depending on the catalyst performance of the catalyst refers to a ceramic oxide, and the molecular general formula of the perovskite is ABO 3; such oxides were first discovered and are the calcium titanate (CaTiO3) compound present in perovskite ore and are therefore named. Because of the many characteristics of the structure of the compound, the application and research are wide in condensed physical aspect, so the ratio (1:1:3) of each compound in the molecular formula is abbreviated as "113 structure" for physicist and chemical family. In a cubic crystal form. The formation of the poly-lamellar twins occurs when the high temperature modification is converted to the low temperature modification, in which the cubic crystal often has parallel-edged striations.
Perovskites are named under the name presvik, russian geology, and their structures typically have simple, double, and layered perovskite structures. The chemical general formula of the simple Perovskite compound is that X is generally smaller in radius or a Double Perovskite structure (Double-Perovskite) has a composition general formula, the composition of a layered Perovskite structure is more complex, and the general formula and the superconducting and tripartite layered Perovskite structure are more researched. The most studied are perovskite structure type compounds of composition.
The perovskite structure type compound mainly comprises orthorhombic, cubic, rhombohedral, tetragonal, monoclinic and triclinic crystal systems, A-site ions are usually rare earth or metal elements with larger ion radius of alkaline earth, and are coordinated with 12 oxygen atoms to form densest cubic accumulation, and mainly play a role in stabilizing the perovskite structure; the B site is generally an element with a small ionic radius (generally a transition metal element such as Mn, Co, Fe, etc.), which coordinates with 6 oxygens and occupies the octahedral center in cubic close packing, and due to the variability of its valence state, it is generally a major component determining many properties of perovskite structure type materials. Compared to simple oxides, perovskite structures can allow some elements to exist in unusual valence states, have non-stoichiometric ratios of oxygen, or allow reactive metals to exist in mixed valence states, giving the solid certain special properties. Because the nature of the solid is closely related to the catalytic activity of the solid, the specificity of the perovskite structure enables the solid to be widely applied to catalysis.
The perovskite type composite oxide ABO3 is a novel inorganic non-metallic material with unique physical and chemical properties, the A site is generally rare earth or alkaline earth element ions, the B site is transition element ions, and the A site and the B site can be partially replaced by other metal ions with similar radiuses to keep the crystal structure of the A site and the B site basically unchanged, so that the A site and the B site are theoretically ideal samples for researching the surface and catalytic properties of the catalyst. As the compound has stable crystal structure, unique electromagnetic property and high activities of oxidation reduction, hydrogenolysis, isomerization, electrocatalysis and the like, the compound has great development potential in the fields of environmental protection, industrial catalysis and the like as a novel functional material.
A site or B site in the standard perovskite is substituted by other metal ions or partially substituted, and then various composite oxides can be synthesized to form anion defects or B site ions with different valence states, so that the perovskite type composite material is a novel functional material with excellent performance and wide application.
The composition of landfill leachate is complex, and generally, the organic matters in the leachate can be divided into three: although the concentration of a certain specific pollutant in the percolate is very low, the traditional treatment method has complex process flow, large equipment floor area, large equipment investment and maintenance cost, long design-production-installation period and difficult comprehensive popularization, and therefore, the process equipment needs to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a tubular free radical oxidation treatment method for landfill leachate, which has high catalytic activity, can be effectively suitable for the treatment of landfill leachate with complex components, has CODcr removal rate of over 90 percent, and can reach the standard discharge after advanced treatment
In order to realize the aim, the invention provides a method for tubular free radical oxidation treatment of landfill leachate, which is characterized in that a tubular continuous reaction device is adopted in the method, and the device comprises a filter, an evaporator, a sewage buffer tank, a sewage pump, a free radical generator, a condenser, an air compressor, a high-pressure buffer tank and a high-pressure separation tank; the outlet of the filter is connected with the inlet of the evaporator, the inlet of the sewage buffer tank is connected with the outlet of the evaporator, and the outlet is connected with the sewage inlet of the free radical generator through a sewage pump; the air compressor is connected with an inlet of the high-pressure buffer tank, an outlet of the high-pressure buffer tank 8 is connected with the free radical generator, a condenser is arranged at an outlet of the free radical generator, a condensation outlet is connected with the high-pressure separation tank, an exhaust hole is formed in the top end of the high-pressure separation tank, and a collection hole is formed in the bottom of the high-pressure separation tank; the catalyst is a composite oxide carrier with LaMnxCo1-xO3 type perovskite characteristics, and a nano-silver active metal multiphase catalyst is used, so that the catalytic activity of the perovskite composite oxide can be further improved through nano-silver loading, and the catalyst is more suitable for catalytic oxidation reaction of landfill leachate with complex components; said has LaMnxCo1-xO3A composite oxide characterized by perovskite, wherein the doping amount (x value) is in the range of 0 to 0.2.
When in use, the catalyst is loaded in the free radical generator in advance, the landfill leachate firstly removes large solid particles through the filter, then the landfill leachate is filtered and then is led into the evaporator to be concentrated and then is led into the sewage buffer tank because of low concentration, the sewage to be treated in the sewage pool is pumped into the free radical generator through the sewage pump, meanwhile, high-pressure air is conveyed into the high-pressure buffer tank through the air compressor, after the pressure is stable and reaches a preset value, the high-pressure air is conveyed into the free radical generator, the sewage to be treated in the free radical generator 5 and the air from the high-pressure buffer tank generate wet oxidation reaction under the action of the catalyst, macromolecular organic matters in the sewage in the free radical generator are oxidized and decomposed by the strong oxidant under certain pressure and temperature conditions, double bonds in the organic matter structure are broken and are oxidized into small molecules by the macromolecules, the small molecules are further oxidized into carbon dioxide and water, the purified sewage flows into a condenser through a water outlet of a free radical generator and enters a high-pressure separation tank after being cooled, uncondensed gas is discharged through an exhaust hole, and liquid is collected through a collection port.
Preferably, the reaction temperature is 130-210 ℃, the reaction pressure is 2.2-3.5 MPa, and the liquid space velocity is 0.7-3.6 h-1And the flow rate of oxygen or air is 50-400 ml/min.
The preparation method of the catalyst comprises the following steps:
the preparation method of the catalyst comprises the following steps:
1) weighing lanthanum soluble salt, manganese soluble salt and cobalt soluble salt according to a stoichiometric ratio, dissolving the lanthanum soluble salt, the manganese soluble salt and the cobalt soluble salt in a certain amount of deionized water to prepare a mixed metal salt solution, adding a certain amount of citric acid, and stirring until the mixed metal salt solution is completely dissolved to form sol;
2) drying the sol, cooling to room temperature, fully grinding and sieving;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere to obtain a composite oxide carrier with LaMnxCo1-xO3 type perovskite characteristics;
4) weighing a certain amount of soluble silver salt, dissolving the soluble silver salt in a certain amount of deionized water, and preparing a silver salt solution; weighing a certain amount of polyvinylpyrrolidone, dissolving in deionized water to prepare PVP solution;
5) dropwise adding a PVP solution into an anion solution under the stirring condition to obtain a mixed solution, then adding the LaMnxCo1-xO3 type perovskite-characteristic composite oxide carrier prepared in the step 3), carrying out ultrasonic treatment for 10-20 minutes, adding a sodium borohydride solution, reacting for 1-3 hours, filtering, washing with deionized water to be neutral, and drying to obtain the composite catalyst.
Preferably, the molar ratio of the citric acid to the metal ions in the mixed metal salt solution in step 1) is 2-3: 1.
Preferably, the drying temperature in the step 2) is 80-110 ℃, and the sieving is 80-mesh sieving.
Preferably, in the step 3), the power of the microwave is 1500 w-2000 w, the heating temperature is 900-1100 ℃, and the heating time is 2-5 minutes.
Preferably, the concentration of silver ions in the step 4) is 0.02-0.1 mol/L, the concentration of PVP solution is 0.01-0.05 g/mL, and the addition amount of PVP is 1-2% of the mass of the carrier.
Preferably, the amount of sodium borohydride added in step 5) is 1.1 to 1.5 times the molar amount of silver ions.
Preferably, the drying operation in the step 5) is drying for 3-5 hours in a vacuum drying oven at 100-120 ℃.
The effect of tubular free radical oxidation mainly depends on the activity of the catalyst, and for the activity of the calcium-titanium composite oxide catalyst, the important influence factors of the synthesis process are provided, the catalyst prepared by different preparation methods usually has different structures, forms, granularities, specific surface areas and catalytic activities, while the perovskite catalyst prepared by the method has smaller particle size, more uniform dispersion, larger specific surface area and more stable performance, and the catalytic activity is further improved after the nano silver is loaded, so that the catalyst prepared by the method has better catalytic activity for the landfill leachate with complex components, and the wet oxidation of the landfill leachate with complex components can be realized under the conditions of lower temperature and lower oxygen partial pressure.
Compared with the prior art, the invention has the beneficial effects that:
1) the process of the invention adopts air as the oxidant, the equipment occupies small area, the long-term operation cost is low, and the process is safe and controllable; convenient and practical, the catalyst reaction activity is high, and thorough to getting rid of the pollutant, do not produce poisonous and harmful gas among the sewage treatment process, do not produce mud, do not have secondary pollution.
2) In the preparation process of the composite catalyst, the composite oxide with LaMnxCo1-xO3 type perovskite characteristics prepared by microwave sintering is used as a carrier catalyst, the particle size is smaller, the dispersion is more uniform, the specific surface area is larger, the performance is more stable, and the catalytic performance is greatly improved by the synergistic effect of the loaded nano silver ions and the carrier. The high-efficiency and stable catalyst changes the process of wet oxidation reaction, greatly reduces the temperature and pressure required by the oxidation reaction, improves the treatment effect, and improves the oxidation efficiency, the CODcr removal rate of the landfill leachate is more than 90%, and the NH3-N removal rate is more than 91%.
Drawings
FIG. 1 shows a tubular continuous reaction apparatus according to the present invention
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As shown in fig. 1, the tubular free radical oxidation treatment device of the present invention comprises a filter 1, an evaporator 2, a sewage buffer tank 3, a sewage pump 4, a free radical generator 5, a condenser 6, an air compressor 7, a high pressure buffer tank 8, and a high pressure separation tank 9; the outlet of the filter 1 is connected with the inlet of the evaporator 2, the inlet of the sewage buffer tank 4 is connected with the outlet of the evaporator 2, and the outlet is connected with the sewage inlet of the free radical generator 5 through the sewage pump 4; the air compressor machine 7 links to each other with high-pressure buffer tank 8's entry, high-pressure buffer tank 8 export links to each other with free radical generator 5, free radical generator 5 exit set up condenser 6, the condensation export is connected with high-pressure knockout drum 9, 9 tops of high-pressure knockout drum are equipped with the exhaust hole, and the bottom is equipped with collects the mouth.
When in use, the catalyst is loaded in the free radical generator 5 in advance, the landfill leachate firstly removes large solid particles through the filter, the filtered landfill leachate is guided into the evaporator 2 to be concentrated and then is guided into the sewage buffer tank 3, the sewage to be treated in the sewage pool is pumped into the free radical generator 5 through the sewage pump 4, meanwhile, high-pressure air is conveyed into the high-pressure buffer tank 8 through the air compressor, after the pressure is stable and reaches a preset value, the high-pressure air is conveyed into the free radical generator 5, the sewage to be treated in the free radical generator 5 and the air from the high-pressure buffer tank 8 generate wet oxidation reaction under the action of the catalyst, macromolecular organic matters in the sewage in the free radical generator 1 are oxidized and decomposed by the strong oxidant under certain pressure and temperature conditions, double bonds in the organic matter structure are broken, the macromolecules are oxidized into micromolecules, and the micromolecules are further oxidized into carbon dioxide and water, the COD is greatly reduced, the BOD/COD value is improved, the purified sewage flows into a condenser 6 through a water outlet of a free radical generator 5 and enters a high-pressure separation tank 7 after being cooled, uncondensed gas is discharged through an exhaust hole, and liquid is collected through a collection port.
[ example 1 ]
1) Weighing 1mol of lanthanum nitrate, 0.2mol of manganese nitrate and 0.8mol of cobalt nitrate according to a stoichiometric ratio, dissolving the lanthanum nitrate, the manganese nitrate and the cobalt nitrate in 5L of deionized water to prepare a mixed metal salt solution, adding 2.5mol of citric acid, and stirring until the citric acid is completely dissolved to form sol;
2) drying the sol at 100 ℃, cooling to room temperature, fully grinding and sieving with a 80-mesh sieve;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere, wherein the microwave power is 1500ww, the heating temperature is 900 ℃, and the heating time is 5 minutes, so as to obtain a composite oxide carrier with the characteristics of LaMn0.2Co0.8O3 type perovskite;
4) weighing 0.1mol of nitric acid, and dissolving the nitric acid in 500mL of deionized water to prepare a silver salt solution; weighing 0.5g of polyvinylpyrrolidone, and dissolving in 10mL of deionized water to prepare a PVP solution;
5) dropwise adding PVP solution into an anion solution under the stirring condition to obtain a mixed solution, then adding 50g of the composite oxide carrier with the LaMn0.2Co0.8O3 type perovskite characteristics prepared in the step 3), carrying out ultrasonic treatment for 10 minutes, adding 0.12mol of sodium borohydride, reacting for 2 hours, filtering, washing with deionized water to be neutral, then placing into a vacuum drying oven, and drying for 5 hours at 120 ℃ to obtain the composite catalyst A1.
[ example 2 ]
1) Weighing 1mol of lanthanum nitrate, 0.1mol of manganese nitrate and 0.9mol of cobalt nitrate according to the stoichiometric ratio, dissolving the lanthanum nitrate, the manganese nitrate and the cobalt nitrate in 5L of deionized water to prepare a mixed metal salt solution, adding 2.2mol of citric acid, and stirring until the citric acid is completely dissolved to form sol;
2) drying the sol at 100 ℃, cooling to room temperature, fully grinding and sieving with a 80-mesh sieve;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under the air atmosphere, wherein the microwave power is 2000ww, the heating temperature is 1100 ℃, and the heating time is 3 minutes, so as to obtain the composite oxide carrier with the LaMn0.1Co0.9O3 type perovskite characteristics;
4) weighing 0.1mol of nitric acid, and dissolving the nitric acid in 500mL of deionized water to prepare a silver salt solution; weighing 1.0g of polyvinylpyrrolidone, dissolving in 15mL of deionized water, and preparing into a PVP solution;
5) dropwise adding PVP solution into an anion solution under the stirring condition to obtain a mixed solution, then adding 50g of the LaMn0.1Co0.9O3 type perovskite composite oxide carrier prepared in the step 3), carrying out ultrasonic treatment for 15 minutes, adding 0.15mol of sodium borohydride, reacting for 2 hours, filtering, washing with deionized water to be neutral, then placing into a vacuum drying oven, and drying for 3 hours at 120 ℃ to obtain the composite catalyst A2.
Comparative example 1
1) Weighing 1mol of lanthanum nitrate and 1mol of cobalt nitrate according to a stoichiometric ratio, dissolving the lanthanum nitrate and the cobalt nitrate in 5L of deionized water to prepare a mixed metal salt solution, adding 2.5mol of citric acid, and stirring until the lanthanum nitrate and the cobalt nitrate are completely dissolved to form sol;
2) drying the sol at 100 ℃, cooling to room temperature, fully grinding and sieving with a 80-mesh sieve;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under the air atmosphere, wherein the microwave power is 1500ww, the heating temperature is 900 ℃, and the heating time is 5 minutes, so as to obtain the composite oxide carrier with LaCoO3 type perovskite characteristics;
4) weighing 0.1mol of nitric acid, and dissolving the nitric acid in 500mL of deionized water to prepare a silver salt solution; weighing 0.5g of polyvinylpyrrolidone, and dissolving in 10mL of deionized water to prepare a PVP solution;
5) dropwise adding PVP solution into an anion solution under the stirring condition to obtain a mixed solution, then adding 50g of the LaCoO3 type perovskite-characteristic composite oxide carrier prepared in the step 3), carrying out ultrasonic treatment for 10 minutes, adding 0.12mol of sodium borohydride, reacting for 2 hours, filtering, washing with deionized water to be neutral, then placing into a vacuum drying oven, and drying for 5 hours at 120 ℃ to obtain the composite catalyst B1.
Comparative example 2
1) Weighing 1mol of lanthanum nitrate and 1mol of cobalt nitrate according to a stoichiometric ratio, dissolving the lanthanum nitrate and the cobalt nitrate in 5L of deionized water to prepare a mixed metal salt solution, adding 2.5mol of citric acid, and stirring until the lanthanum nitrate and the cobalt nitrate are completely dissolved to form sol;
2) drying the sol at 100 ℃, cooling to room temperature, fully grinding and sieving with a 80-mesh sieve;
3) and adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere, wherein the microwave power is 1500ww, the heating temperature is 900 ℃, and the heating time is 5 minutes, so as to obtain the composite oxide C1 with LaCoO3 type perovskite characteristics.
[ example 3 ]
And (3) treating sample sewage:
the sample sewage is landfill leachate of a refuse landfill, and the main indexes are as follows through detection:
color: black; the pH value is 4.2; the main component of COD is piperidone compounds, and CODcr is 45220 mg/L; 9000 times of chroma; organic acid 2120 mg/L; NH3-N was 4320 mg/L.
According to the apparatus shown in FIG. 1, the granular catalysts prepared in examples 1 to 2 and comparative examples 1 to 2 were loaded into the catalyst bed in the radical generator 1, the pressure of the air compressor and the high-pressure buffer tank was adjusted to a set pressure of 3.5MPa, the radical generator was heated to 250 ℃ and air was fed into the radical generator together with the sample sewage, and after 3 hours, COD test analysis was carried out from the reaction solution, and the removal rate of COD was shown in Table 1.
TABLE 1
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (8)
1. A method for tubular free radical oxidation treatment of landfill leachate is characterized in that a tubular continuous reaction device is adopted in the method, and the device comprises a filter, an evaporator, a sewage buffer tank, a sewage pump, a free radical generator, a condenser, an air compressor, a high-pressure buffer tank and a high-pressure separation tank; the outlet of the filter is connected with the inlet of the evaporator, the inlet of the sewage buffer tank is connected with the outlet of the evaporator, and the outlet is connected with the sewage inlet of the free radical generator through a sewage pump; the air compressor is connected with an inlet of a high-pressure buffer tank, an outlet of the high-pressure buffer tank is connected with a free radical generator, an outlet of the free radical generator is provided with a condenser, a condensation outlet is connected with a high-pressure separation tank, the top end of the high-pressure separation tank is provided with an exhaust hole, and the bottom of the high-pressure separation tank is provided with a collection port; the catalyst loaded in the free radical generator is LaMnxCo1-xO3The composite oxide with perovskite characteristic is a carrier, the nano-silver is used as a heterogeneous catalyst of active metal, the catalytic activity of the perovskite composite oxide can be further improved through nano-silver loading, and the perovskite composite oxide is more suitable for catalytic oxidation reaction of landfill leachate with complex components, wherein the value of x is in the range of 0-0.2.
2. The method of tubular free radical oxidation treatment of landfill leachate of claim 1, wherein the catalyst is pre-loaded in the free radical generator, the landfill leachate is first filtered to remove large solid particles, then filtered and then introduced into the evaporator to be concentrated and then introduced into the sewage buffer tank, the sewage to be treated in the sewage tank is pumped into the free radical generator by the sewage pump, meanwhile, the high pressure air is delivered into the high pressure buffer tank by the air compressor, after the pressure is stable and reaches a preset value, the high pressure air is delivered into the free radical generator, the sewage to be treated in the free radical generator and the air from the high pressure buffer tank are subjected to wet oxidation reaction under the action of the catalyst, the macromolecular organic matters in the sewage in the free radical generator are oxidized and decomposed by the strong oxidant under certain pressure and temperature conditions, the double bond fracture in the organic matter structure is by macromolecule oxidation for the micro molecule, and the micro molecule further oxidizes into carbon dioxide and water, and the sewage of purification gets into high-pressure knockout drum after flowing into the condenser cooling through the free radical generator delivery port, and the gas branch of noncondensation is by the exhaust vent blowdown, and liquid is collected by the collection mouth.
3. The method for tubular free radical oxidation treatment of landfill leachate according to claim 1, wherein the reaction temperature is 130-210 ℃, the reaction pressure is 2.2-3.5 MPa, and the liquid space velocity is 0.7-3.6 h-1And the flow rate of oxygen or air is 50-400 ml/min.
4. The method for tubular free radical oxidation treatment of landfill leachate according to claim 1, wherein the method for preparing the catalyst comprises the following steps:
1) weighing lanthanum soluble salt, manganese soluble salt and cobalt soluble salt according to a stoichiometric ratio, dissolving the lanthanum soluble salt, the manganese soluble salt and the cobalt soluble salt in a certain amount of deionized water to prepare a mixed metal salt solution, adding a certain amount of citric acid, and stirring until the mixed metal salt solution is completely dissolved to form sol;
2) drying the sol, cooling to room temperature, fully grinding and sieving;
3) adding the sieved powder into a calcining device, and carrying out microwave heating calcination under an air atmosphere to obtain the powder with LaMnxCo1-xO3A composite oxide support characterized by perovskite;
4) weighing a certain amount of soluble silver salt, dissolving the soluble silver salt in a certain amount of deionized water, and preparing a silver salt solution; weighing a certain amount of polyvinylpyrrolidone, dissolving in deionized water to prepare PVP solution;
5) dropwise adding PVP solution into the silver ion solution under the stirring condition to obtain a mixed solution, and then adding the LaMn prepared in the step 3)xCo1-xO3Carrying out ultrasonic treatment on the composite oxide carrier with the perovskite characteristic for 10-20 minutes, adding a sodium borohydride solution, reacting for 1-3 hours, filtering, washing with deionized water to be neutral, and drying to obtain the composite catalyst.
5. The method for tubular free radical oxidation treatment of landfill leachate according to claim 4, wherein the molar ratio of citric acid to metal ions in the mixed metal salt solution in step 1) is 2-3: 1; the drying temperature in the step 2) is 80-110 ℃, and the sieving is carried out by a 80-mesh sieve.
6. The method for tubular free radical oxidation treatment of landfill leachate according to claim 4, wherein in step 3), the power of the microwave is 1500 w-2000 w, the heating temperature is 900-1100 ℃, and the heating time is 2-5 minutes.
7. The method for tubular free radical oxidation treatment of landfill leachate according to claim 4, wherein the concentration of silver ions in step 4) is 0.02-0.1 mol/L, the concentration of PVP solution is 0.01-0.05 g/mL, and the addition amount of PVP is 1-2% of the mass of the carrier.
8. The method for tubular free radical oxidation treatment of landfill leachate according to claim 4, wherein the amount of sodium borohydride added in step 5) is 1.1 to 1.5 times of the molar amount of silver ions; the drying operation of the step 5) is as follows: drying the mixture for 3 to 5 hours in a vacuum drying oven at the temperature of between 100 and 120 ℃.
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