CN112374583B - Preparation and application of functionalized sludge-based carbon three-dimensional particle electrode - Google Patents
Preparation and application of functionalized sludge-based carbon three-dimensional particle electrode Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 110
- 239000002245 particle Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000010813 municipal solid waste Substances 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000000149 chemical water pollutant Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229940061631 citric acid acetate Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses preparation and application of a functionalized sludge-based carbon three-dimensional particle electrode, which are characterized in that excess sludge is prepared into hydrothermal carbonized sludge particles with a certain size by a hydrothermal method, the hydrothermal carbonized sludge particles are obtained after being subjected to heat treatment for 2 hours in a nitrogen atmosphere at 900 ℃, then the sludge-based carbon particles are immersed in a solution containing ferric salt and manganese salt with a certain proportion, the solution is placed in a constant-temperature shaking table at 40 ℃ to shake until the solution is completely evaporated, and the solution is taken out and placed in a muffle furnace to be subjected to heat treatment at 400 ℃ to obtain a sludge carbon-loaded ferrum-manganese double-metal oxide composite material. In a single-chamber double-electrode system at normal temperature and normal pressure, the sludge carbon-supported iron-manganese bimetallic oxide composite material prepared by the invention is used as a three-dimensional particle electrode, titanium meshes with the same size are respectively used as anodes and cathodes, air is blown from the bottom of a reactor, and under the additional voltage of 2.0V, the TOC concentration of the catalytic air is 200 mg.L ‑1 garbage leachate, so that the mineralization rate of the garbage leachate can reach more than 98% in 2 h.
Description
Technical Field
The invention relates to preparation and application of a functionalized sludge-based carbon three-dimensional particle electrode, in particular to treatment of excess sludge, preparation and application of the excess sludge as a novel electrode material in an electro-catalysis wet-type air oxidation reaction system in organic pollutant wastewater treatment.
Background
The surplus sludge is a solid waste which is produced in the urban sewage treatment process and contains a large amount of organic matters, a plurality of metal elements and pathogenic substances. Along with the gradual increase of the annual sewage treatment capacity of China, the sludge yield is also continuously increased. Reasonable disposal of municipal sludge has become a problem to be solved in the development of socioeconomic performance. Traditional sludge disposal mainly relies on landfill, composting and incineration. However, with the increasing awareness of environmental protection, these methods for disposing of sludge are increasingly limited, and if the excessive sludge is not properly disposed of, serious secondary pollution is caused. Therefore, the development of new technology for recycling the surplus sludge is receiving more and more attention from the society, and the method for preparing the activated carbon by pyrolysis and carbonization of the sludge is widely accepted.
The catalytic wet air oxidation is a chemical process of using oxygen-enriched gas or oxygen as an oxidant at a certain temperature and pressure, and accelerating the respiration reaction between organic matters in the wastewater and the oxidant by utilizing the catalytic action of a catalyst, so that organic pollutants in the wastewater are decomposed into inorganic matters such as CO 2 and H 2 O or micromolecular organic matters. Compared with the traditional wet air oxidation, the catalytic wet air oxidation reaction temperature and pressure are lower, the time is shorter and the efficiency is higher, so that the investment and the operation cost are greatly reduced, and the catalytic wet air oxidation reaction technology is considered to be a novel wastewater treatment technology with wide industrial application prospect. The method can be applied to the treatment of high-concentration industrial wastewater produced in coking, chemical industry, petroleum and synthetic industry, in particular to high-concentration industrial organic wastewater which is difficult to biodegrade and contains organic pesticides, dyes, synthetic fibers, inflammable and explosive substances. Although milder than the reaction conditions of wet air oxidation, catalytic wet air oxidation still requires operating temperatures above 80 ℃ and operating pressures above 0.5 MPa. Further reducing the temperature and pressure of the catalytic wet air oxidation reaction, improving the stability of the catalyst and prolonging the service life of the catalyst is a key problem to be solved in the technical development process.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the preparation and application of the functionalized sludge-based carbon three-dimensional particle electrode. According to the invention, excess sludge is used as a raw material, and magnetic sludge carbon particles with a certain size are obtained after hydrothermal treatment, carbonization, impregnation and heat treatment and are used as particle electrodes, and under the action of an external electric field, a sludge carbon surface catalyst is driven to catalyze air oxidation to degrade organic pollutants in wastewater.
The invention relates to preparation of a functionalized sludge-based carbon three-dimensional particle electrode, which takes surplus sludge as a raw material, and obtains magnetic sludge carbon particles with a certain size after hydrothermal treatment, carbonization, impregnation and heat treatment, and the preparation method specifically comprises the following steps:
Step 1: preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 5-20wt%, regulating the pH value to 1-3 by using HCl, transferring into a reaction kettle, and carrying out hydrothermal carbonization for 8-24 h at 160-220 ℃; cooling, filtering, washing the hydrothermal sludge to be neutral, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving with a 80-mesh sieve, and mixing the crushed and dried hydrothermal sludge according to a mud-water mass ratio of 3:2, gradually adding water in proportion, uniformly stirring, filling into a grinding tool, and freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of 5+/-0.2 mm;
Step 2: carrying out heat treatment on the obtained hydrothermal carbonized sludge particles for 2 hours in a nitrogen atmosphere at 900 ℃ to obtain sludge-based carbon particles; and soaking the sludge-based carbon particles in a salt solution containing ferric salt and manganese salt, shaking in a shaking table at a constant temperature of 40 ℃ until the solution is completely evaporated, taking out, and then placing in a muffle furnace for heat treatment at 400 ℃ to obtain the sludge carbon-loaded ferrum-manganese bimetallic oxide composite material.
The ferric salt is ferric nitrate, and the manganese salt is one of manganese acetate, manganese nitrate, manganese chloride or manganese sulfate; the molar ratio of iron to manganese is 0.5-5: 1, the total mass of the ferric salt and the manganese salt is 20-100 wt% of the dry sludge.
In addition, in order to prevent ferric hydroxide precipitate from forming during the drying process, citric acid, EDTA or nitrilotriacetic acid with the same molar ratio or more is added as a complexing agent.
The application of the functionalized sludge-based carbon three-dimensional particle electrode prepared by the method is that the functionalized sludge-based carbon particle electrode is used as a three-dimensional electrode to be applied to a catalytic wet air oxidation system, so that organic pollutants in wastewater can be effectively removed. The method specifically comprises the following steps:
In a 200mL single-chamber double-electrode system at normal temperature and normal pressure, the sludge carbon-supported iron-manganese bimetallic oxide composite material prepared by the invention is used as a three-dimensional particle electrode, titanium meshes with the same size are respectively used as anodes and cathodes, air is blown in from the bottom of a reactor at the flow rate of 20mL min -1, and under the external voltage of 2.0V, the TOC concentration of catalytic air is 200mg L -1 garbage leachate, so that the mineralization rate of the garbage leachate in 2h can reach more than 98%.
The dosage of the three-dimensional particle electrode is 1/3-2/3 of the volume of the reactor, the anode and the cathode are respectively titanium meshes wrapped with sheet-mounted magnets with the area of 10cm 2, wherein the surfaces of the magnets are coated with insulating polymer coatings, and the interval between the anode and the cathode is 2cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the functionalized sludge-based carbon particle electrode by using the surplus sludge and applies a catalytic wet air oxidation system, which is a novel method for disposing the surplus sludge, and simultaneously effectively reduces the production cost of electrode materials.
2. According to the invention, the ferro-manganese bimetallic oxide is loaded on the surface of the sludge particles by a simple dipping and heat treatment method, so that the synergistic catalysis effect of the bimetallic oxide is brought into play.
3. The sludge-based carbon three-dimensional particle electrode prepared by the method has good magnetism, is favorable for close contact between particles and between the particles and the electrode, and realizes normal-temperature and normal-pressure catalytic wet air oxidation reaction of landfill leachate under low voltage.
Drawings
Fig. 1 is a schematic diagram of a catalytic wet air oxidation reaction apparatus using a functionalized sludge-based carbon-supported iron-manganese bimetallic oxide as a particle electrode in example 1.
FIG. 2 is an XRD pattern of sludge-based carbon-supported iron-manganese double metal oxide composite materials prepared with different iron-manganese ratios. From the graph, the bimetallic oxide loaded on the carbon surface of the sludge mainly exists in the form of mixed metal oxide of Fe 3O4 and Mn 3O4 in the iron-manganese ratio of 1:2-2:1.
FIG. 3 is a graph showing the TOC removal rate of a catalytic wet air oxidation landfill leachate with sludge-based carbon-supported different metal oxides as particle electrodes after 5 consecutive cycles with cycle number under the condition of example 1. As can be seen from the figure, the increase in iron content contributes to the enhancement of the cycling stability of the particle electrode.
FIG. 4 is a graph showing the TOC removal rate over time during the 5 th cycle degradation of a catalytic wet air oxidation landfill leachate with a sludge-based carbon-supported different metal oxides as particle electrodes under the conditions of example 1. As can be seen from the figure, the molar ratio of Fe to Mn is 1:1, the degradation performance of the particle electrode material is optimal.
Detailed Description
Example 1:
Preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 5wt%, regulating the pH to 1 by using HCl, transferring into a reaction kettle, and carrying out hydrothermal carbonization for 8 hours at 160 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving the crushed hydrothermal sludge with a 80-mesh sieve, and mixing the crushed hydrothermal sludge with the 80-mesh sieve according to the mass ratio of 3:2 gradually adding clear water, uniformly stirring, filling into a grinding tool, freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of about 5+/-0.2 mm, and performing heat treatment for 2 hours at 900 ℃ in nitrogen atmosphere to obtain the sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing ferric nitrate, citric acid and manganese acetate in an equimolar ratio of 1:1, the total mass of ferric salt and manganese salt is 60 percent of the dry sludge mass, then the sludge is put into a shaking table with constant temperature of 40 ℃ to shake until the solution is completely evaporated, and the sludge is put into a muffle furnace for heat treatment for 4 hours at 400 ℃ after being taken out, thus obtaining the sludge carbon-loaded ferrum-manganese bimetallic oxide composite material.
Referring to FIG. 1, in a 200mL single-chamber double-electrode system at normal temperature and normal pressure, the prepared sludge carbon-supported iron-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material is 2/3 of the volume of a reactor, and 150mL of landfill leachate with TOC of 200 mol.L -1 is used as a target pollutant. The titanium mesh with the same size and the area of 10cm 2 of the sheet-mounted magnet is used as a cathode and an anode, wherein the surface of the magnet is coated with an insulating polymer pattern layer, and the interval between the cathode and the anode is 2cm. Continuously blowing air from the bottom of the reactor at the flow rate of 20mL min -1, regulating a direct current power supply to 2.0V, and catalyzing the air to oxidize and degrade landfill leachate, wherein the TOC removal rate is 98.8% in 2 hours. The above operation was repeated, and the TOC removal rate after 5 cycles was 95.9%.
Example 2:
Preparing a solution with the concentration of 20wt% from municipal sludge dry powder dried at 80 ℃, regulating the pH to 3 by using HCl, transferring into a reaction kettle, and carrying out hydrothermal carbonization for 12 hours at 220 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving the crushed hydrothermal sludge with a 80-mesh sieve, and mixing the crushed hydrothermal sludge with the 80-mesh sieve according to the mass ratio of 3:2 gradually adding clear water, uniformly stirring, filling into a grinding tool, freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of about 5mm, and performing heat treatment for 2 hours at 900 ℃ under nitrogen atmosphere to obtain sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing ferric nitrate, EDTA and manganese chloride in an equimolar ratio, wherein the molar ratio of the ferric nitrate to the manganese chloride is 0.5:1, the total mass of the ferric salt and the manganese salt is 20wt% of the mass of the dry sludge. And then placing the mixture into a shaking table with constant temperature of 40 ℃ for shaking until the solution is completely evaporated, taking out the mixture, and placing the mixture into a muffle furnace for heat treatment at 400 ℃ for 4 hours to obtain the sludge carbon-loaded ferrum-manganese double-metal oxide composite material.
In 200mL of single-chamber double-electrode system at normal temperature and normal pressure, the prepared sludge carbon-supported iron-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material is 1/3 of the volume of the reactor, and 150mL of landfill leachate with TOC of 200 mol.L -1 is used as a target pollutant. The titanium mesh with the same size and the area of 10cm 2 of the sheet-mounted magnet is used as a cathode and an anode, wherein the surface of the magnet is coated with an insulating polymer pattern layer, and the interval between the cathode and the anode is 2cm. Continuously blowing air from the bottom of the reactor at the flow rate of 20mL min -1, regulating a direct current power supply to 2.0V, and catalyzing the air to oxidize and degrade landfill leachate, wherein the TOC removal rate is 98.2% within 2 hours. The above operation was repeated, and the TOC removal rate after 5 cycles was 79.4%.
Example 3:
Preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 15wt%, regulating the pH value to 2 by using HCl, transferring into a reaction kettle, and carrying out hydrothermal carbonization for 24 hours at 180 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving the crushed hydrothermal sludge with a 80-mesh sieve, and mixing the crushed hydrothermal sludge with the 80-mesh sieve according to the mass ratio of 3:2 gradually adding clear water, uniformly stirring, filling into a grinding tool, freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of about 5mm, and performing heat treatment for 2 hours at 900 ℃ under nitrogen atmosphere to obtain sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing ferric nitrate, citric acid and manganese nitrate in an equimolar ratio, wherein the molar ratio of the ferric nitrate to the manganese nitrate is 2:1, the total mass of the ferric salt and the manganese salt is 100wt% of the dry sludge mass. And then placing the mixture into a shaking table with constant temperature of 40 ℃ for shaking until the solution is completely evaporated, taking out the mixture, and placing the mixture into a muffle furnace for heat treatment at 400 ℃ for 4 hours to obtain the sludge carbon-loaded ferrum-manganese double-metal oxide composite material.
In 200mL of single-chamber double-electrode system at normal temperature and normal pressure, the prepared sludge carbon-supported iron-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material is 2/3 of the volume of the reactor, and 150mL of landfill leachate with TOC of 200 mol.L -1 is used as a target pollutant. The titanium mesh with the same size and the area of 10cm 2 of the sheet-mounted magnet is used as a cathode and an anode, wherein the surface of the magnet is coated with an insulating polymer pattern layer, and the interval between the cathode and the anode is 2cm. Continuously blowing air from the bottom of the reactor at the flow rate of 20mL min -1, regulating a direct current power supply to 2.0V, and catalyzing the air to oxidize and degrade landfill leachate, wherein the TOC removal rate is 96.4% within 2 hours. The above operation was repeated, and the TOC removal rate after 5 cycles was 93.4%.
Example 4:
Preparing a solution with the concentration of 10wt% from municipal sludge dry powder dried at 80 ℃, regulating the pH to 3 by using HCl, transferring into a reaction kettle, and carrying out hydrothermal carbonization for 18h at 160 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving the crushed hydrothermal sludge with a 80-mesh sieve, and mixing the crushed hydrothermal sludge with the 80-mesh sieve according to the mass ratio of 3:2 gradually adding clear water, uniformly stirring, filling into a grinding tool, freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of about 5mm, and performing heat treatment for 2 hours at 900 ℃ under nitrogen atmosphere to obtain sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing ferric nitrate and EDTA and manganese sulfate in an equimolar ratio, wherein the molar ratio of ferric nitrate to manganese sulfate is 3:1, the total mass of the ferric salt and the manganese salt is 60wt% of the dry sludge mass. And then placing the mixture into a shaking table with constant temperature of 40 ℃ for shaking until the solution is completely evaporated, taking out the mixture, and placing the mixture into a muffle furnace for heat treatment at 400 ℃ for 4 hours to obtain the sludge carbon-loaded ferrum-manganese double-metal oxide composite material.
In a 200mL single-chamber double-electrode system at normal temperature and normal pressure, the prepared sludge carbon-supported iron-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the particle electrode is 1/2 of the volume of the reactor, and 150mL of garbage leachate with TOC of 200 mol.L -1 is used as a target pollutant. The titanium mesh with the same size and the area of 10cm 2 of the sheet-mounted magnet is used as a cathode and an anode, wherein the surface of the magnet is coated with an insulating polymer pattern layer, and the interval between the cathode and the anode is 2cm. Air is continuously blown in from the bottom of the reactor at the flow rate of 20mL min -1, a direct current power supply is regulated to 2.0V, garbage leachate is degraded by catalytic air oxidation, and the TOC removal rate is 90.9% within 2h. The above operation was repeated, and the TOC removal rate after 5 cycles was 90.4%.
Claims (3)
1. The application of the functionalized sludge-based carbon three-dimensional particles is characterized in that:
The functionalized sludge-based carbon particles are used as three-dimensional electrodes to be applied to a catalytic wet-type air oxidation system to remove organic pollutants in wastewater; specifically, in a 200mL single-chamber double-electrode system at normal temperature and pressure, the functionalized sludge-based carbon particles are used as three-dimensional particle electrodes, titanium meshes with the same size are respectively used as a cathode and an anode, air is blown from the bottom of a reactor, and under the additional voltage of 2.0V, the TOC concentration of the catalytic air is 200 mg.L -1 garbage percolate, so that the mineralization rate of the garbage percolate can reach more than 98% in 2 hours;
The dosage of the three-dimensional particle electrode accounts for 1/3-2/3 of the volume of the reactor, the cathode and the anode are respectively titanium meshes wrapped with sheet-mounted magnets with the area of 10cm 2, and the interval between the cathode and the anode is 2cm;
The preparation method of the functionalized sludge-based carbon particles comprises the following steps:
Step 1: preparing municipal excess sludge dry powder dried at 80 ℃ into a solution with the concentration of 5-20wt%, regulating the pH value to 1-3 by using HCl, transferring into a reaction kettle for hydrothermal carbonization treatment, cooling, filtering, washing the hydrothermal sludge to be neutral, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving with a 80-mesh sieve, and mixing the crushed and dried hydrothermal sludge according to a mud-water mass ratio of 3:2, gradually adding water in proportion, uniformly stirring, filling into a grinding tool, and freeze-drying to obtain hydrothermal carbonized sludge particles with the particle size of 5+/-0.2 mm;
Step 2: carrying out heat treatment on the obtained hydrothermal carbonized sludge particles for 2 hours in a nitrogen atmosphere at 900 ℃ to obtain sludge-based carbon particles; soaking sludge-based carbon particles in a salt solution containing ferric salt and manganese salt, shaking in a shaking table at a constant temperature of 40 ℃ until the solution is completely evaporated, taking out, and then placing in a muffle furnace for heat treatment at 400 ℃ to obtain a sludge carbon-loaded iron-manganese bimetallic oxide composite material;
In the step 2, the ferric salt is ferric nitrate, and the manganese salt is one of manganese acetate, manganese nitrate, manganese chloride or manganese sulfate;
in the salt solution containing ferric salt and manganese salt, the molar ratio of iron to manganese is 0.5-5: 1, wherein the total mass of ferric salt and manganese salt is 20-100 wt% of the mass of the dry sludge.
2. The use according to claim 1, characterized in that:
in the step1, the hydrothermal carbonization is carried out for 8-24 hours at 160-220 ℃.
3. The use according to claim 1, characterized in that:
To prevent ferric salts from forming ferric hydroxide precipitates during solution evaporation, equimolar ratios of citric acid, EDTA or nitrilotriacetic acid are added as complexing agents.
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