CN112374583A - 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 111
- 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 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 239000000149 chemical water pollutant Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 29
- 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 14
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 239000000843 powder Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000011282 treatment 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
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010813 municipal solid waste Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 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
- 230000015556 catabolic process Effects 0.000 description 1
- 229940061631 citric acid acetate Drugs 0.000 description 1
- 239000011248 coating agent Substances 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
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 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
- 239000005416 organic matter Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis 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
Images
Classifications
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- 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
Abstract
The invention discloses a preparation method and application of a functionalized sludge-based carbon three-dimensional particle electrode, which are characterized in that residual sludge is prepared into hydrothermal carbonized sludge particles with a certain size by a hydrothermal method, the hydrothermal carbonized sludge particles are subjected to heat treatment for 2 hours at 900 ℃ under nitrogen atmosphere to obtain sludge-based carbon particles, the sludge-based carbon particles are soaked in a solution containing a certain proportion of ferric salt and manganese salt, the solution is shaken in a constant-temperature shaking table at 40 ℃ until the solution is completely evaporated to dryness, and the solution is taken out and then placed in a muffle furnace for heat treatment at 400 ℃ to obtain a sludge-carbon-loaded ferro-manganese bimetallic oxide composite material. Under normal temperature and normal pressure, in a single-chamber double-electrode system, the sludge carbon-supported iron-manganese double-metal oxide composite material prepared by the method is used as a three-dimensional particle electrode, titanium nets 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 external application voltage of 2.0V, the TOC concentration of catalytic air oxidation is 200mg·L‑1The mineralization rate of the landfill leachate can reach more than 98 percent within 2 hours.
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 of a novel electrode material in an electrically-assisted catalytic wet air oxidation reaction system, and application of the electrode material in organic pollutant wastewater treatment.
Background
The excess sludge is a solid waste containing a large amount of organic matters, a plurality of metal elements and pathogenic substances generated in the urban sewage treatment process. With the gradual increase of the sewage treatment amount every year in China, the sludge yield is also continuously increased. The reasonable disposal of municipal sludge has become an urgent problem to be solved in the development of socioeconomic industry. Traditional sludge disposal relies primarily on landfilling, composting and incineration. However, as environmental awareness increases, these methods of sludge disposal are increasingly limited, and the failure to properly dispose of the increasing amount of excess sludge will cause serious secondary pollution. Therefore, the development of new technologies for resource treatment and utilization of excess sludge is receiving more and more attention from all social circles, and among them, the method for preparing activated carbon by pyrolysis and carbonization of sludge is widely accepted.
The catalytic wet air oxidation is to accelerate the respiration reaction between organic matters in the wastewater and an oxidant by using oxygen-enriched gas or oxygen as the oxidant and utilizing the catalytic action of a catalyst under certain temperature and pressure so as to decompose organic pollutants in the wastewater into CO2And H2O, etc. or small molecular organic matter. Compared with the traditional wet air oxidation, the catalytic wet air oxidation reaction has lower temperature and pressure, shorter time and higher efficiency due to the adoption of the oxidation catalyst, thereby greatly reducing the investment and operation cost and being considered as a new wastewater treatment technology with wide industrial application prospect. The method can be applied to the treatment of high-concentration industrial wastewater generated in the coking, chemical, petroleum and synthetic industries, in particular to organic pesticides, dyes, synthetic fibers, flammable and explosive substances and high-concentration industrial organic wastewater which is difficult to biodegrade. Although milder than the reaction conditions of wet air oxidation, catalytic wet air oxidation still requires an operating temperature of 80 ℃ or higher and an operating pressure of 0.5MPa or higher. The key problem to be solved in the technical development process is to further reduce the temperature and pressure of the catalytic wet air oxidation reaction, improve the stability of the catalyst and prolong the service life of the catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method and application of a functionalized sludge-based carbon three-dimensional particle electrode. The method takes the excess sludge as a raw material, obtains magnetic sludge carbon particles with a certain size after hydrothermal, carbonization, impregnation and heat treatment, takes the magnetic sludge carbon particles as particle electrodes, and drives a sludge carbon surface catalyst to catalyze air under the action of an external electric field at normal temperature and normal pressure to oxidize and degrade organic pollutants in the wastewater.
The invention discloses a preparation method of a functionalized sludge-based carbon three-dimensional particle electrode, which takes excess sludge as a raw material and obtains magnetic sludge carbon particles with a certain size after hydrothermal, carbonization, impregnation and heat treatment, and specifically comprises the following steps:
step 1: preparing the municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 5-20 wt%, adjusting the pH value to 1-3 by using HCl, transferring the solution into a reaction kettle, and performing hydrothermal carbonization for 8-24 hours at 160-220 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, and sieving the crushed sludge with a 80-mesh sieve according to a mass ratio of sludge to water of 3: 2, gradually adding water, 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 2h at 900 ℃ in a nitrogen atmosphere to obtain sludge-based carbon particles; and then soaking the sludge-based carbon particles in a salt solution containing ferric salt and manganese salt, placing the solution in a constant-temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, taking out the solution, placing the solution in a muffle furnace, and carrying out heat treatment at 400 ℃ to obtain the sludge-carbon-supported ferro-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 mass of the dry sludge.
In addition, citric acid, EDTA or nitrilotriacetic acid with the molar ratio more than equal to that of the ferric salt is added as a complexing agent in order to prevent ferric hydroxide precipitation formed in the drying process of the ferric salt.
The functionalized sludge-based carbon three-dimensional particle electrode prepared by the method is applied to a catalytic wet air oxidation system as a three-dimensional electrode, and can effectively remove organic pollutants in wastewater. The method specifically comprises the following steps:
under normal temperature and normal pressure and in a 200mL single-chamber double-electrode system, the sludge carbon-supported ferro-manganese double-metal oxide composite material prepared by the method is used as a three-dimensional particle electrode, titanium nets with the same size are respectively used as a cathode and an anode, and 20 mL/min is carried out from the bottom of a reactor-1The TOC concentration of the catalytic air is 200 mg.L under the external voltage of 2.0V-1The mineralization rate of the landfill leachate can reach more than 98 percent within 2 hours.
The using amount of the three-dimensional particle electrodes accounts for 1/3-2/3 of the volume of the reactor, and the cathode and the anode are respectively coated with an area of 10cm2The titanium mesh with the magnet, wherein the surface of the magnet is coated with an insulating polymer coating, and the distance between the cathode and the anode is 2 cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the excess sludge to prepare the functionalized sludge-based carbon particle electrode and applies the catalytic wet air oxidation system, thereby being a new method for disposing the excess sludge and effectively reducing the production cost of electrode materials.
2. The invention loads the ferro-manganese bimetallic oxide on the surface of the sludge particles by a simple dipping and heat treatment method, which is beneficial to exerting the synergistic catalytic effect of the bimetallic oxide.
3. The sludge-based carbon three-dimensional particle electrode prepared by the invention has good magnetism, is beneficial to the close contact between particles and electrodes, and realizes the normal-temperature normal-pressure catalytic wet air oxidation reaction of the landfill leachate under low voltage.
Drawings
FIG. 1 is a schematic diagram of a catalytic wet air oxidation reaction apparatus of example 1 using a functionalized sludge-based carbon-supported ferro-manganese bimetallic oxide as a particle electrode.
FIG. 2 is an XRD (X-ray diffraction) pattern of sludge-based carbon-supported ferro-manganese bimetallic oxide composite materials prepared by different ferro-manganese ratios. From the figureIt can be seen that the iron-manganese ratio is within the range of 1: 2-2: 1, and the bimetallic oxide loaded on the surface of the sludge carbon is mainly Fe3O4And Mn3O4The mixed metal oxide is present.
FIG. 3 is a graph showing the variation of the TOC removal rate of the catalytic wet air oxidation landfill leachate with sludge-based carbon carrying different metal oxides as particle electrodes after 5 continuous cycles with the cycle number under the conditions of example 1. As can be seen from the figure, the increase of the iron content is beneficial to the enhancement of the cycling stability of the particle electrode.
Fig. 4 is a graph showing the change of the TOC removal rate with time in the 5 th cycle degradation process of catalytic wet air oxidation landfill leachate with sludge-based carbon carrying different metal oxides as particle electrodes under the conditions of example 1. As can be seen from the figure, Fe and Mn are present in a molar ratio of 1: 1, the degradation performance of the particulate electrode material is optimal.
Detailed Description
Example 1:
preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 5 wt%, adjusting the pH to 1 by using HCl, transferring the solution into a reaction kettle, and performing 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 sludge with a 80-mesh sieve, and mixing the crushed sludge with water according to a 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 at 900 ℃ under nitrogen atmosphere for 2 hours to obtain sludge-based carbon particles. Soaking sludge-based carbon particles in a solution containing equimolar amounts of ferric nitrate, citric acid and manganese acetate, wherein the molar ratio of ferric nitrate to manganese acetate is 1: 1, the total mass of ferric salt and manganese salt is 60 wt% of the mass of the dry sludge, then the sludge is placed into a constant-temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, and the solution is taken out and then placed into a muffle furnace to be thermally treated at 400 ℃ for 4 hours to obtain the sludge carbon-loaded ferro-manganese bimetallic oxide composite material.
Referring to fig. 1, the prepared sludge carbon-supported ferro-manganese bimetallic oxide composite material is used as a particle electrode in a 200mL single-chamber double-electrode system at normal temperature and normal pressure, and the dosage of the prepared sludge carbon-supported ferro-manganese bimetallic oxide composite material accounts for 2/3 and 150 percent of the volume of a reactor200mol per liter of mL of TOC-1The landfill leachate is the target pollutant. The same size of the bag has an area of 10cm2The titanium net with the 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 distance between the cathode and the anode is 2 cm. From the bottom of the reactor at a flow rate of 20 mL/min-1The air is continuously blown in at the flow speed, the direct current power supply is adjusted to 2.0V, the garbage percolate is degraded by catalyzing air oxidation, and the TOC removal rate is 98.8% within 2 h. The above operation was repeated, and the TOC removal rate after 5 cycles was 95.9%.
Example 2:
preparing 20 wt% solution from municipal sludge dry powder dried at 80 ℃, adjusting pH to 3 with HCl, transferring into a reaction kettle, and performing 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 sludge with a 80-mesh sieve, and mixing the crushed sludge with water according to a 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 at 900 ℃ in nitrogen atmosphere for 2 hours 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 ferric nitrate to manganese chloride is 0.5: 1, the total mass of the ferric salt and the manganese salt is 20 wt% of the mass of the dry sludge. And then the mixture is put into a constant temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, and the mixture is taken out and then put into a muffle furnace to be thermally treated for 4 hours at 400 ℃ to obtain the sludge carbon-supported ferro-manganese bimetallic oxide composite material.
Under normal temperature and normal pressure and in a 200mL single-chamber double-electrode system, the prepared sludge carbon-supported ferro-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material accounts for 1/3 of the volume of a reactor, 150mL of TOC is 200 mol.L-1The landfill leachate is the target pollutant. The same size of the bag has an area of 10cm2The titanium net with the 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 distance between the cathode and the anode is 2 cm. From the bottom of the reactor at a flow rate of 20 mL/min-1The air is continuously blown in at the flow speed, the direct current power supply is adjusted to 2.0V, the garbage percolate is degraded by catalyzing air oxidation, and the TOC removal rate is 98.2% within 2 h. Repeating the above operation for 5 cyclesThe TOC removal was 79.4%.
Example 3:
preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 15 wt%, adjusting the pH to 2 by using HCl, transferring the solution 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 sludge with a 80-mesh sieve, and mixing the crushed sludge with water according to a 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 at 900 ℃ in nitrogen atmosphere for 2 hours to obtain sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing iron nitrate, citric acid and manganese nitrate in an equimolar ratio, wherein the molar ratio of iron nitrate to manganese nitrate is 2:1, the total mass of the ferric salt and the manganese salt is 100 wt% of the mass of the dry sludge. And then the mixture is put into a constant temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, and the mixture is taken out and then put into a muffle furnace to be thermally treated for 4 hours at 400 ℃ to obtain the sludge carbon-supported ferro-manganese bimetallic oxide composite material.
Under normal temperature and normal pressure and in a 200mL single-chamber double-electrode system, the prepared sludge carbon-supported ferro-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material accounts for 2/3 of the volume of a reactor, 150mL of TOC is 200 mol.L-1The landfill leachate is the target pollutant. The same size of the bag has an area of 10cm2The titanium net with the 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 distance between the cathode and the anode is 2 cm. From the bottom of the reactor at a flow rate of 20 mL/min-1The air is continuously blown in at the flow speed, the direct current power supply is adjusted to 2.0V, the garbage percolate is degraded by catalyzing air oxidation, and the TOC removal rate is 96.4% within 2 h. The above operation was repeated, and the TOC removal rate after 5 cycles was 93.4%.
Example 4:
preparing municipal sludge dry powder dried at 80 ℃ into a solution with the concentration of 10 wt%, adjusting the pH value to 3 by using HCl, transferring the solution into a reaction kettle, and carrying out hydrothermal carbonization for 18 hours at 160 ℃; cooling, filtering, washing the hydrothermal sludge to neutrality, and drying at 80 ℃; crushing the dried hydrothermal sludge, sieving the crushed sludge with a 80-mesh sieve, and mixing the crushed sludge with water according to a 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 at 900 ℃ in nitrogen atmosphere for 2 hours to obtain sludge-based carbon particles. Immersing sludge-based carbon particles in a solution containing ferric nitrate, EDTA and manganese sulfate in an equal molar ratio of 3: 1, the total mass of the ferric salt and the manganese salt is 60 wt% of the mass of the dry sludge. And then the mixture is put into a constant temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, and the mixture is taken out and then put into a muffle furnace to be thermally treated for 4 hours at 400 ℃ to obtain the sludge carbon-supported ferro-manganese bimetallic oxide composite material.
Under normal temperature and normal pressure and in a 200mL single-chamber double-electrode system, the prepared sludge carbon-supported ferro-manganese double-metal oxide composite material is used as a particle electrode, the dosage of the composite material accounts for 1/2 of the volume of a reactor, 150mL of TOC is 200 mol.L-1The landfill leachate is the target pollutant. The same size of the bag has an area of 10cm2The titanium net with the 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 distance between the cathode and the anode is 2 cm. From the bottom of the reactor at a flow rate of 20 mL/min-1The air is continuously blown in at the flow speed, the direct current power supply is adjusted to 2.0V, the garbage percolate is degraded by catalyzing air oxidation, and the TOC removal rate is 90.9% within 2 h. The above operation was repeated, and the TOC removal rate after 5 cycles was 90.4%.
Claims (9)
1. A preparation method of functionalized sludge-based carbon three-dimensional particles is characterized by comprising the following steps:
step 1: preparing municipal excess sludge dry powder dried at 80 ℃ into a solution with the concentration of 5-20 wt%, adjusting the pH value to 1-3 by using HCl, transferring the solution into a reaction kettle for hydrothermal carbonization treatment, cooling and filtering, washing the hydrothermal sludge to be neutral, and drying at 80 ℃; crushing the dried hydrothermal sludge, and sieving the crushed sludge with a 80-mesh sieve according to a mass ratio of sludge to water of 3: 2, gradually adding water, 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 in a nitrogen atmosphere to obtain sludge-based carbon particles; and then soaking the sludge-based carbon particles in a salt solution containing ferric salt and manganese salt, placing the solution in a constant-temperature shaking table at 40 ℃ to shake until the solution is completely evaporated to dryness, taking out the solution, placing the solution in a muffle furnace, and carrying out heat treatment at 400 ℃ to obtain the sludge-carbon-supported ferro-manganese bimetallic oxide composite material.
2. The method of claim 1, wherein:
in the step 1, the hydrothermal carbonization is carried out for 8-24 hours at 160-220 ℃.
3. The method of claim 1, wherein:
in the step 2, the obtained hydrothermal carbonized sludge particles are subjected to heat treatment for 2 hours at 900 ℃ in a nitrogen atmosphere to obtain sludge-based carbon particles.
4. The method of claim 1, wherein:
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.
5. The method of claim 4, wherein:
in the salt solution containing ferric salt and manganese salt, 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 mass of the dry sludge.
6. The method of claim 1, wherein:
in order to prevent ferric salt from forming ferric hydroxide precipitate in the solution evaporation process, citric acid, EDTA or nitrilotriacetic acid with equal molar ratio is added as a complexing agent.
7. The use of the functionalized sludge-based carbon three-dimensional particles prepared by any one of the methods of claims 1 to 6, wherein: the functionalized sludge-based carbon particles are 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.
8. Use according to claim 7, characterized in that it comprises the following steps:
under normal temperature and normal pressure and in a 200mL single-chamber double-electrode system, the functionalized sludge-based carbon particles are used as three-dimensional particle electrodes, titanium nets with the same size are respectively used as cathodes and anodes, air is blown in from the bottom of a reactor, and under the external application voltage of 2.0V, the TOC concentration of catalytic air oxidation is 200 mg.L-1The mineralization rate of the landfill leachate can reach more than 98 percent within 2 hours.
9. Use according to claim 8, characterized in that:
the using amount of the three-dimensional particle electrodes accounts for 1/3-2/3 of the volume of the reactor, and the cathode and the anode are respectively coated with an area of 10cm2The piece of the titanium net is provided with the magnet, and the distance between the cathode and the anode is 2 cm.
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