CN108275811B - Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling - Google Patents
Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling Download PDFInfo
- Publication number
- CN108275811B CN108275811B CN201810023280.6A CN201810023280A CN108275811B CN 108275811 B CN108275811 B CN 108275811B CN 201810023280 A CN201810023280 A CN 201810023280A CN 108275811 B CN108275811 B CN 108275811B
- Authority
- CN
- China
- Prior art keywords
- solar
- organic wastewater
- energy
- wastewater
- degradation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000010168 coupling process Methods 0.000 title claims abstract description 22
- 230000008878 coupling Effects 0.000 title claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 20
- 230000000593 degrading effect Effects 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 66
- 230000015556 catabolic process Effects 0.000 claims abstract description 55
- 239000002071 nanotube Substances 0.000 claims abstract description 37
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 230000005611 electricity Effects 0.000 claims abstract description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 68
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000010840 domestic wastewater Substances 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- 230000005684 electric field Effects 0.000 abstract description 15
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- 230000001699 photocatalysis Effects 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000001808 coupling effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- VHMNUXJPZWEOCB-UHFFFAOYSA-N 1-nitro-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound [N+](=O)([O-])C12C(C=CC=C1)O2 VHMNUXJPZWEOCB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 101150001463 sunA gene Proteins 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/46165—Special power supply, e.g. solar energy or batteries
-
- 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
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for degrading organic wastewater by utilizing solar energy through three-field coupling of light, electricity and heat, wherein the method adopts a solar cell to provide electric energy, adopts a solar heat collection device to provide heat energy, and adopts carbon nano tubes/secondary anode to oxidize TiO2The nanotube is used as a working electrode, the platinum electrode is used as a counter electrode, the working electrode is electrically conducted with the anode of the solar cell, and the counter electrode is electrically conducted with the cathode of the solar cell; before degradation, a working electrode and a counter electrode are placed in organic wastewater, the organic wastewater is heated by using the solar heat collection device, and then the organic wastewater is kept stand in a dark environment without power; when in degradation, the solar heat collection device is utilized to heat the organic wastewater, the solar cell is utilized to electrify the wastewater, and the electrolysis is carried out under the condition that the working electrode is irradiated by sunlight. The method couples three fields of solar energy: the thermal field, the optical field and the electric field energy improve the degradation efficiency and the utilization rate of solar energy.
Description
Technical Field
The invention relates to the technical field of organic wastewater degradation, in particular to a method for degrading organic wastewater by utilizing solar energy through three fields of photo-electricity-heat coupling.
Background
The traditional organic wastewater treatment method comprises physical methods such as foam separation technology, adsorption and membrane separation technology and the like, chemical methods such as flocculation precipitation method, coagulation precipitation method, advanced oxidation technology and the like, photocatalytic degradation, photo-assisted Fenton oxidation, biological degradation and the like. However, no satisfactory method has been widely used for the efficient degradation of organic wastewater, and the efficient wastewater treatment method should take into consideration economic rationality (e.g., no or low consumption of chemicals) and environmental friendliness ("green remediation route"). Therefore, developing new technologies, efficient and environmentally friendly methods for degrading organic wastewater have become an urgent challenge.
Solar energy is a clean, safe and inexhaustible green energy. At present, the application technologies of solar energy-thermal energy and solar energy electric energy are mature, such as solar heat collection, solar water heating systems, solar greenhouses, solar power generation, solar cells and the like. However, since both solar energy-thermal energy utilization and solar energy-electric energy utilization require energy conversion application by means of intermediate equipment, a great energy loss is accompanied in the conversion process. Moreover, although the solar energy-light energy utilization is direct utilization, the ultraviolet energy accounts for only a small part of the solar spectrum energy, so that the utilization rate of the solar energy cannot be fundamentally improved. If the energy of each part of the solar spectrum can be combined and coupled and applied to the same chemical reaction, the coupling application of the solar light, electricity and heat energy is realized, sufficient energy is provided for the chemical reaction, additional energy input is not needed in the whole process, and other chemical agents are not needed to be added, so that the technology has great research significance and wide application prospect.
Disclosure of Invention
Technical problem to be solved
Aiming at the defect of lack of a method for efficiently and environmentally degrading organic wastewater by using solar energy in the prior art, the invention provides an experimental mode for applying solar energy light-electricity-heat three-field coupling to oxidation treatment of organic wastewater, simultaneously seeks a high-efficiency coupling mode for solar energy utilization by allocating three fields, and firstly loads and modifies TiO modified by carbon nano tubes2The nanotube electrode is used as a central electrode in the degradation process of organic wastewater, and solar energy is utilized to the maximum extent to degrade the organic wastewater.
(II) technical scheme
In order to solve the technical problems, the invention provides the following technical scheme:
a method for degrading organic wastewater by solar energy through three-field coupling of light, electricity and heat comprises the steps of providing electric energy by a solar cell, providing heat energy by a solar heat collection device, and oxidizing TiO by a carbon nano tube/secondary anode2The nanotube is used as a working electrode, the platinum electrode is used as a counter electrode, the working electrode is electrically conducted with the anode of the solar cell, and the counter electrode is electrically conducted with the cathode of the solar cell;
before degradation, a working electrode and a counter electrode are placed in organic wastewater, the organic wastewater is heated by using the solar heat collection device, and then the organic wastewater is kept stand in a dark environment without power;
and during degradation, continuously heating the organic wastewater by using the solar heat collection device, electrifying the wastewater by using the solar cell, and electrolyzing under the condition that the working electrode is irradiated by sunlight.
Preferably, before and during degradation, the solar heat collection device is used for heating the organic wastewater to 60-90 ℃; and
and during degradation, the solar cell is utilized to provide 1.2-1.8V voltage.
Preferably, the carbon nanotube/twice anodized TiO2The nanotubes were prepared as follows:
(1) electrolyzing by taking a titanium sheet as an anode, a platinum sheet as a cathode and a mixed solution of ammonium fluoride, ethylene glycol and water as an electrolyte; the electrolyzed titanium sheet is subjected to heat preservation at 460-500 ℃ for 40-50 min to obtain primary anodic oxidation TiO2A nanotube;
(2) by primary anodic oxidation of TiO2The nanotube is used as an anode, a platinum sheet is used as a cathode, and a mixed solution consisting of ammonium fluoride, ethylene glycol and water is used as electrolyte for electrolysis again; the electrolyzed anode material is subjected to heat preservation for 50-60 min at the temperature of 450-460 ℃, and secondary anodic oxidation TiO is obtained2A nanotube;
(3) by melting carbonatesAs electrolyte, secondary anodic oxidation of TiO2The nanotube is used as a cathode, a nickel electrode is used as an anode, electrolysis is carried out, and the cathode after electrolysis is sequentially subjected to ultrasonic pickling and drying, so that the carbon nanotube/secondary anode oxidized TiO is obtained2A nanotube.
Further preferably, the carbonate is lithium carbonate, sodium carbonate and potassium carbonate according to the ratio of (60-65): (20-25): (15-20) by mass. More preferably, the carbonate salt is lithium carbonate, sodium carbonate and potassium carbonate in a ratio of 61:22:17 mass ratio.
Further preferably, in the step (3), the process conditions of the electrolysis are as follows: the electrolysis temperature is 500-750 ℃, the current density is 100-150 mA, and the electrolysis time is 10-50 s.
Preferably, the solar cell is a silicon-based solar cell.
Preferably, the solar thermal collector is selected from any one of flat plate solar collector, trough solar collector, vacuum tube solar collector.
Preferably, before degradation, the working electrode and the counter electrode are placed in organic wastewater, the temperature of the wastewater is raised to 60-90 ℃ by using the solar heat collection device, and then the wastewater is kept stand for 10-20 min in a dark environment without power supply.
Preferably, the organic wastewater is industrial wastewater or domestic wastewater containing sodium dodecyl benzene sulfonate and/or nitrobenzene.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
the invention integrates the energy of the solar energy, the electricity and the heat, so that the energy can be effectively distributed and utilized, and the increase of the solar heat to the reaction is not only beneficial to the reduction of the oxidation-reduction potential, but also beneficial to the enhancement of the reaction kinetics. The solar cell provides a stable potential and can promote electron transfer, and the ultraviolet part in sunlight provides separation of photoinduced electrons and holes for photocatalysis, so that the solar multi-field coupling matching and synergistically driven photothermal electrochemical mode can provide an effective way for solar energy utilization for degradation of organic wastewater (especially organic wastewater containing nitrobenzene and/or sodium dodecyl benzene sulfonate).
The invention provides a method for coupling and matching full-spectrum solar energy to act on organic wastewater degradation, which applies partial energy of sunlight ultraviolet to photocatalyst reaction, partial energy of visible light to solar cell power generation, partial energy of infrared light to solar heat collector heat generation, and can realize efficient and thorough degradation of organic wastewater when three partial energies are coupled in one reaction.
Drawings
FIG. 1 is an ultraviolet-visible light absorption spectrum of nitrobenzene degraded by the solar photo-thermal-electric three-field coupling method provided in example 1;
FIG. 2 is a UV-VIS absorption spectrum of nitrobenzene oxide using solar-electric field alone;
FIG. 3 is a UV-VIS absorption spectrum of a solar-optical field alone oxidized nitrobenzene;
FIG. 4 is a current curve for nitrobenzene degradation using the solar photo-thermal-electric three-field coupling method provided in example 1;
FIG. 5 is a current curve for degrading nitrobenzene under the coupling condition of a solar energy photoelectric two-field.
Fig. 6 shows energy level analysis under solar STEP light-thermal-electric three-field coupling conditions.
Fig. 7 shows the mechanism of multi-field driven photothermal electrochemical degradation of nitrobenzene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few 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.
The invention provides a method for utilizing the sunA method for degrading organic wastewater by coupling light, electricity and heat, wherein a solar battery is used for providing electric energy, a solar heat collection device is used for providing heat energy, and carbon nano tubes/secondary anode TiO oxide are used for degrading2The nanotube is used as a working electrode, the platinum electrode is used as a counter electrode, the working electrode is electrically conducted with the anode of the solar cell, and the counter electrode is electrically conducted with the cathode of the solar cell. The solar cell used can provide stable voltage for providing electric energy to the electrode. Preferably, the solar cell is a silicon-based solar cell. The solar heat collector can be any one of a flat-plate solar heat collector, a trough type solar heat collector and a vacuum tube solar heat collector. The working electrode material used in the invention is carbon nano tube/TiO (TiO) by secondary anode oxidation2A nanotube. Carbon nanotube/TiO 2 by secondary anode oxidation2The nanotube is used as a photocatalyst to realize the utilization of solar energy and light energy. This photocatalyst material can be prepared as follows: (1) electrolyzing by taking a titanium sheet as an anode, a platinum sheet as a cathode and a mixed solution of ammonium fluoride, ethylene glycol and water as an electrolyte; the electrolyzed titanium sheet is subjected to heat preservation at 460-500 ℃ for 40-50 min to obtain primary anodic oxidation TiO2A nanotube; (2) by primary anodic oxidation of TiO2The nanotube is used as an anode, a platinum sheet is used as a cathode, and a mixed solution consisting of ammonium fluoride, ethylene glycol and water is used as electrolyte for electrolysis again; the electrolyzed anode material is subjected to heat preservation for 50-60 min at the temperature of 450-460 ℃, and secondary anodic oxidation TiO is obtained2A nanotube; (3) using molten carbonate as electrolyte to make secondary anode oxidation of TiO2The nanotube is used as a cathode, a nickel electrode is used as an anode, electrolysis is carried out, and the cathode after electrolysis is sequentially subjected to ultrasonic pickling and drying, so that the carbon nanotube/secondary anode oxidized TiO is obtained2A nanotube. The carbonate is preferably lithium carbonate, sodium carbonate and potassium carbonate according to the proportion of (60-65): (20-25): (15-20), and more preferably, the mass ratio of the mixture is 61:22:17 mass ratio. In the step (3), the electrolysis process conditions are preferably as follows: the electrolysis temperature is 500-750 ℃, the current density is 100-150 mA, and the electrolysis time is 10 ℃50s。
Before degradation, a working electrode and a counter electrode are placed in organic wastewater, the solar heat collection device is utilized to heat the organic wastewater, and then the organic wastewater is kept stand in a dark environment without power supply, wherein the standing time can be 10-20 minutes, and preferably 10-15 minutes. The heating temperature may be the same as the temperature at which the degradation is carried out, and is preferably 60 ℃, ensuring that an equilibrium state of adsorption-desorption between the electrode (as a catalyst) and the solution (organic wastewater) is achieved at the degradation temperature.
And during degradation, the solar heat collection device is used for heating the organic wastewater, the heating temperature is preferably 60-90 ℃, meanwhile, the solar cell is used for electrifying the wastewater, an external voltage of 1.2-1.8V is provided, and electrolysis is carried out under the condition that sunlight irradiates the working electrode.
Oxidative degradation reactions of organic wastewater, such as electrochemical and photocatalytic oxidation reactions, are high-energy barrier reactions, and in order to cross the barrier, a large amount of energy is required to make the reactant molecules reach a transition state, and the energy is called activation energy required by the reaction. When the reaction temperature increases, the potential at the initial stage of the reaction increases, making the potential barrier more likely to cross. Thus, increasing the temperature of the reaction solution can accelerate the electrochemical and photocatalytic oxidation processes. However, since the external medium heating causes additional energy consumption, there are many drawbacks and limitations in relying on fossil energy sources to provide thermal energy to facilitate electrochemical and photocatalytic oxidation of organic pollutants. The solar energy has the advantages of richness, low cost, low carbon emission and the like, and can be widely applied to the oxidation of organic wastewater. Through the conversion mode, the photo-thermal electrochemical process can fully utilize the full-spectrum energy of solar energy to degrade the organic wastewater, and the three-field energy of solar energy, namely the thermal field, the optical field and the electric field, is coupled and matched to be applied to the degradation reaction of the organic wastewater, so that the solar energy utilization rate and the degradation rate of the organic wastewater are improved fundamentally. If the oxidation reaction of organic pollutants relies on single field energy as the entire source, a large amount of energy is required to sustain the reaction and at the same time the effectiveness of this way of using solar energy is clearly relatively low due to the limitations of the conversion rate of solar-thermal/solar-electrical energy itself. The three-field cooperative coupling mode is such that: the coupling of the multi-field driven thermoelectric chemical concept matches the thermal activation effect, the light excitation acts on the electrically driven electron transfer process, the energy of the light-electricity-heat three fields simultaneously acts on the anode (central electrode) of the system, the central electrode plays a decisive role in the system, and the nature of the central electrode determines the utilization rate of solar energy and the efficiency of oxidizing organic pollutants in water. During the oxidation reaction that occurs at the surface of the central electrode, all of the energy comes from the solar energy, with no other energy form input, and the solar thermal, solar electrical and solar (UV) portions of the solar energy are coupled synergistically to increase the oxidation rate. The oxidation reaction is a thermodynamic endothermic reaction, the electrolytic potential is reduced by adding solar heat, and the activation application of light on the central electrode is beneficial to improving the degradation efficiency of solar energy on organic matters.
By utilizing the method, the industrial sewage or domestic sewage containing the sodium dodecyl benzene sulfonate and/or the nitrobenzene can be quickly and efficiently degraded.
The following are examples of the present invention.
Example 1
The method provided by the invention is used for degrading the wastewater containing nitrobenzene.
Preparing a photocatalyst material: the titanium sheet is ultrasonically cleaned in acetone, absolute ethyl alcohol and distilled water for 15min in sequence and dried in nitrogen. A two-electrode system is adopted: the power supply adopts a direct current stabilized voltage power supply, a titanium sheet is taken as an anode and connected to a positive electrode of the direct current power supply, a platinum sheet (2cm multiplied by 2cm) is taken as a counter electrode and connected to a negative electrode of the power supply, and the content of NH is 0.5wt percent4F+(CH2OH)2+2vol％H2And electrolyzing in electrolyte composed of O mixed solution at room temperature under constant voltage of 50V for 30 min. After the reaction is finished, washing the titanium sheet with distilled water, placing the titanium sheet in a muffle furnace in the air atmosphere, heating the titanium sheet to 450 ℃ from room temperature at the speed of 5 ℃/min, and keeping the temperature for 1h to obtain the primary anodized TiO2A nanotube.
Growing primary anode TiO oxide2Placing the titanium sheet of the nanotube in a beaker filled with distilled water for ultrasonic cleaningAnd washing until the titanium dioxide nanotube film on the surface is completely removed. And taking out the titanium sheet with the hexagonal pit marks arranged in order, cleaning, drying, and electrolyzing under the condition of constant voltage of 20V for 30min, wherein the rest is the same as the last electrolysis. And after the reaction is finished, washing the titanium sheet with distilled water to remove residual electrolyte and fragments at the pipe orifice of the nanotube. Then placing the mixture in a muffle furnace, raising the temperature to 450 ℃ from room temperature at a speed of 5 ℃/min under the air atmosphere, and keeping the temperature for 1h to ensure that the TiO is heated2The crystal form is converted from amorphous form to anatase form to obtain secondary anodic oxidation TiO2A nanotube.
By mixing molten carbonate systems (Li)2CO3，Na2CO3，K2CO3) The electrolyte was used in a weight ratio of 61:22: 17. The prepared secondary anode is oxidized into TiO2The nanotube was used as a cathode, the nickel electrode was used as an anode, and electrolysis was carried out at 500 ℃ with a current density of 100mA and an electrolysis time of 10 s. After the electrolysis is finished, taking the loaded cathode out of the electrolytic bath, and sequentially carrying out ultrasonic pickling and drying to obtain the carbon nano tube/secondary anodic oxidation TiO2A nanotube photocatalyst.
The method comprises the steps of providing stable voltage for degradation by adopting a solar cell, providing heat energy for degradation by adopting a flat-plate solar collector, heating organic wastewater, and preparing the carbon nano tube/secondary anode oxidized TiO by adopting the method2The nanotube is used as a working electrode, the platinum electrode is used as a counter electrode, the working electrode is electrically conducted with the anode of the solar cell, and the counter electrode is electrically conducted with the cathode of the solar cell. Before degradation, the working electrode and the counter electrode were placed in organic wastewater (NB concentration 20 mg. L)-1) In the method, a flat-plate solar collector is used for heating organic wastewater, the water temperature of the wastewater is heated to 60 ℃, and then the wastewater is kept stand for 10 minutes in a dark environment without power supply, so that the equilibrium state of adsorption-desorption between an electrode and a solution is achieved. When in degradation, the flat-plate solar collector is utilized to heat the organic wastewater to 60 ℃, and simultaneously, the solar cell is utilized to electrify the wastewater, so as to provide an external voltage of 1.2V, and the electrolysis is carried out under the condition that the working electrode is irradiated by sunlight.
As can be seen from FIG. 1, the degradation rate of nitrobenzene is 88.1% at 15 minutes of electrolysis. When the electrolysis is carried out for 30 minutes, the degradation rate of nitrobenzene reaches 100 percent.
In addition, the current change during degradation was measured, and the results are shown in FIG. 4.
Comparative example 1: the degradation process used in comparative example 1 is essentially the same as that used in example 1, except that: the external voltage provided by the solar cell is 1.2V, the solar thermal collector heats the wastewater to 30 ℃ (equivalent to normal temperature condition), the working electrode is a platinum electrode, has no photocatalysis function, cannot utilize ultraviolet light for photocatalysis, is equivalent to oxidizing nitrobenzene only under the independent action of the solar energy-electric field, and the ultraviolet-visible light absorption spectrum of the nitrobenzene is shown in figure 2. As can be seen from fig. 2, after 60 minutes of the electrolysis voltage, the characteristic absorption of the ultraviolet spectrum was slightly decreased, and the degradation rate at 30 minutes was 2.2%, and the degradation rate at 60 minutes was 3.6% as calculated from this.
Comparative example 2: comparative example 2 the degradation process used was essentially the same as in example 1, except that: the solar thermal collector heats the wastewater to 30 ℃ (equivalent to normal temperature condition) without the external voltage provided by the solar cell, which is equivalent to oxidizing nitrobenzene only under the independent action of solar energy-light field, and the ultraviolet-visible light absorption spectrum is shown in figure 3. As can be seen from fig. 3, after 60min under the illumination condition, the characteristic absorption peak of the ultraviolet spectrum of the material is obviously reduced, and the degradation rate is only 64.9% when 30min is calculated according to the characteristic absorption peak; when the degradation time was increased to 60min, the degradation efficiency increased to 92.3%.
Comparative example 3: comparative example 3 the degradation process used was essentially the same as in example 1, except that: the temperature of the wastewater is heated to 60 ℃ only by using a solar heat collector, which is equivalent to a degradation experiment that a solar energy-thermal field is independently acted on the nitrobenzene-containing organic wastewater. After 60min at the temperature, the characteristic absorption peak (267nm) of the ultraviolet-visible light absorption spectrum is not obviously changed, and the two curves of 0min and 60min are completely superposed, namely, the thermal action does not cause the degradation of additional nitrobenzene, and the degradation of the nitrobenzene does not occur under the action of the energy of the solar energy-thermal field.
Comparative example 4: comparative example 4 the degradation process used was essentially the same as in example 1, except that: the solar heat collector heats the wastewater to 30 ℃ (equivalent to normal temperature), equivalent to oxidizing nitrobenzene under the coupling action of solar energy and two electric fields, and the current change is shown in figure 5.
According to the calculation of figure 4, the energy W (1.2V, 60 ℃ C.) put into the system under the coupling action of the solar energy, the electricity and the heat, the carbon nano tube/the secondary anode oxidation TiO2Nanotube) UIt-1.2V × 1011656.29 × 10-6A · s ═ 1.21J; according to the calculation of figure 5, the energy W (1.2V, 30 ℃ C.) input by the system under the coupling action of the solar energy light-electricity two fields is obtained2Nanotube) UIt-1.2V × 570604.51 × 10-6A·s＝0.69J。
The energy level relation diagram of the light, heat and electric three-field respective action and coupling action related to the invention is shown in fig. 6, when the degradation reaction of organic wastewater is carried out by using the single-field action, a large amount of energy is required to be input across the energy level height required by the reaction, because the degradation reaction of organic substances is generally an endothermic reaction calculated by thermodynamics, and a large amount of activation energy is required to cross the reaction potential barrier in addition to the energy required by theoretical calculation, the total amount of the energy is required to be very large when the energy is provided by a single field. The present inventors have also confirmed through previous experiments that:
(i) after the reaction is carried out for 1 hour under the condition of 60 ℃ under the action of a single thermal field, nitrobenzene in the system is basically unchanged, if the temperature is further increased, when the organic wastewater is degraded in an open system, the nitrobenzene can boil at the temperature of more than 90 ℃ in most plateau areas, on one hand, the volatilization of water and organic matters in the system is very obvious, on the other hand, great practical operation difficulty is brought to industrial operation, and if the organic wastewater is degraded in a closed pressurized system, the reaction can be carried out under the condition that the temperature can be controlled to be more than 100 ℃ by increasing the pressure of the system, but the technical requirement on the whole water treatment device is very high, the operation and transformation of the industrial operation can be difficult to realize in a short time, and meanwhile, the production cost and the technical cost of the later maintenance of the system operation are also very difficult problems.
(2) After 1 hour of the reaction under the condition of 1.2V of the single electric field, the degradation rate of nitrobenzene in the system is less than 5 percent, which is far from reaching the standard of wastewater treatment for practical industrial production, if the voltage of the electric field is further increased, the degradation rate and the degradation rate of various organic matters in the system can be really increased, in the experiment, the voltage value is also increased to 3.0V, but when the reaction is carried out under the condition, a large amount of bubbles can be visually observed on the surface of an electrode, and the reduction of the water amount in the system after 1 hour of the reaction is very obvious, which shows that O is generated along with the decomposition of a large amount of water in the reaction process2And H2. Albeit H2Is a very good clean fuel, but in the conventional sewage treatment process, a gas recovery device is not arranged, and because the composition of the waste water is very complicated, in the actual electrolysis process, a plurality of gases can be generated, if the generated hydrogen is required to be recycled, further purification reaction is required, and the treatment cost is further increased. When organic wastewater treatment is performed using an electrolysis voltage greater than that of water, a part of energy is used for the decomposition reaction of water, and H generated by the decomposition reaction of water2If the recycling is not effective, a large amount of energy is wasted, so that the method is not preferable from the practical viewpoint.
(3) After 1 hour under the condition of a single light field, the improved carbon nano tube/secondary anode oxidized TiO is applied2The nanotube is used for photocatalysis, the degradation rate of nitrobenzene in the system is high, which shows the sensitivity of nitrobenzene which is a substance to the degradation of light field, but from the aspect of energy utilization, the photocatalysis can only utilize the radiation of ultraviolet and a small part of visible light regions in the solar spectrum, and can not utilize most of the solar radiation of visible light and infrared, and the ultraviolet region (the ultraviolet region)<0.4 μm) only accounts for 7 percent of the total energy of the solar radiation on the surface of the earth, so that the photocatalytic method alone is used for degrading the organic wastewater, which can not reach the aim that the organic wastewater is degraded all the timeThe aim of the pursuit of high-efficiency utilization of solar energy is mainly fulfilled.
Therefore, in order to achieve the aims of high solar energy utilization rate and high organic wastewater degradation rate at the same time, the inventor combines three fields of energy to effectively distribute and utilize the three fields of energy, and the increase of solar heat to the reaction is beneficial to not only reducing the oxidation-reduction potential but also enhancing the reaction kinetics. From the above results, the solar cell provides a stable potential of 1.2V, which can promote electron transfer, the ultraviolet part provides separation of photoinduced electrons and holes for photocatalysis, and the photo-thermal electrochemical mode cooperatively driven in solar multi-field coupling matching provides an effective way for solar energy utilization for the degradation of nitrobenzene-containing organic wastewater.
The semiconductor electrode is used as a central electrode, and according to the multi-field driven photo-thermal electrochemical theory, the central electrode of the composite structure simultaneously carries out three different chemical reaction processes of photochemistry, electrochemistry and thermochemistry, and the mechanism is shown in fig. 7. Fig. 7 shows the change in the space charge layer of the center electrode under the effect of multi-field cooperative driving. TiO 22Is an n-type semiconductor, and when a positive electric field is applied on the surface of the semiconductor to act on TiO2When the electrode is of a/Ti type structure, the separation of photoproduction electrons and holes can be facilitated under the action of an electric field, the accelerated conduction of charges is facilitated, and the electrode can positively act on a photocatalytic reaction. In the figure, Es0Is the band position (Es) under dark condition and without applied electric field*Is the energy band position, Es, under the illumination condition when no external electric field is applied*+Is the band position, Es, of a forward electric field applied under illumination conditions*-Is the band position when a negative electric field is applied under illumination conditions. As shown in fig. 7, when an electric field with a forward action is applied to the electrode, the surface photovoltaic voltage significantly increases the separation efficiency and rate of electrons and holes, inhibits the recombination of photo-generated electrons and holes, increases the rate of degrading nitrobenzene by photocatalytic oxidation, and increases the temperature of the system, thereby facilitating the acceleration of mass transfer of nitrobenzene in solution and enabling the degradation rate of nitrobenzene to obtain a rapid increase effect in a short time. Therefore, in the solar STEP light-heat-electricity three fieldsUnder the coupled synergistic effect, the utilization rate of solar energy and the degradation of organic wastewater are simultaneously improved.
The invention utilizes carbon nano tube/secondary anode to oxidize TiO2The nanotube composite electrode is used as the center of the degradation process, so that the solar energy utilization efficiency can be greatly improved. The solar energy-electric energy provides stable potential (1.2V) for reaction, the electron transfer can be promoted under the action of an electric field, and the ultraviolet light of sunlight is TiO2Photocatalysis of the electrode provides energetic radiation, and the synergistic effect of elemental carbon on the surface of the electrode accelerates charge separation and mass transfer. Therefore, the solar energy and the ultraviolet light oxidize the nitrobenzene to provide enough energy through the synergistic effect of the solar energy and the heat. Under the irradiation of solar energy and ultraviolet light, more solar energy is applied for heating, and under the condition, the oxidation rate of nitrobenzene and the utilization rate of solar energy are fundamentally and greatly improved. Therefore, an efficient way is provided for the utilization of solar energy in the application of solar energy light-heat-electricity three-field cooperative matching.
In conclusion, under the coupling action of the solar energy, the electricity and the heat, the degradation of the nitrobenzene is quicker and more thorough, when the voltage of the external electric field is 1.2V, the degradation of the reaction system is only 15min under the condition of 60 ℃, and the degradation efficiency of 88.1 percent is achieved. The solar heat energy reduces the electrolytic voltage of nitrobenzene degradation in the reaction, and an external electric field generated by the photovoltaic cell promotes the separation of photoproduction electron-hole pairs and simultaneously inhibits the recombination of the photogeneration electron-hole pairs, so that TiO is subjected to secondary recombination2The light response range of the light-emitting diode is expanded to a visible light region, and TiO is obviously improved2The photocatalytic activity and the thermal action increase the mass transfer effect of nitrobenzene in a system, and the degradation efficiency of organic wastewater is remarkably increased in the process of a light-electricity-heat three-field coupling system. The solar energy light-electricity-heat three-field coupling plays a synergistic role in the degradation process of nitrobenzene.
The invention innovatively allocates three-field energy flux, seeks the most efficient coupling mode for solar energy utilization, and firstly oxidizes the carbon nano tube/TiO by secondary anode2The nanotube is used as a central electrode in the degradation process of organic wastewater to the maximum extentThe organic wastewater is degraded by solar energy. According to the invention, the ultraviolet part energy of sunlight is applied to react with the photocatalyst, the visible part energy is applied to solar cell power generation and the infrared part energy is applied to solar heat collector heat generation, and when the three parts of energy are coupled in a reaction, the organic wastewater is efficiently and thoroughly degraded.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The method for degrading organic wastewater by utilizing solar energy through three-field coupling of light, electricity and heat is characterized in that a solar battery is adopted to provide electric energy, a solar heat collection device is adopted to provide heat energy, and carbon nano tubes/secondary anode TiO oxide are used for oxidizing2The nanotube is used as a working electrode, the platinum electrode is used as a counter electrode, the working electrode is electrically conducted with the anode of the solar cell, and the counter electrode is electrically conducted with the cathode of the solar cell;
before degradation, a working electrode and a counter electrode are placed in organic wastewater, the organic wastewater is heated by using the solar heat collection device, and then the organic wastewater is kept stand in a dark environment without power;
when the organic wastewater is degraded, the solar heat collection device is utilized to continuously heat the organic wastewater, the solar cell is utilized to electrify the wastewater, and the electrolysis is carried out under the condition that the working electrode is irradiated by sunlight; before and during degradation, heating the organic wastewater to 60-90 ℃ by using the solar heat collection device; and
during degradation, the solar cell is utilized to provide 1.2-1.8V voltage;
the carbon nano tube/secondary anode oxidized TiO2The nanotubes were prepared as follows:
(1) electrolyzing by taking a titanium sheet as an anode, a platinum sheet as a cathode and a mixed solution of ammonium fluoride, ethylene glycol and water as an electrolyte; the electrolyzed titanium sheet is subjected to heat preservation at 460-500 ℃ for 40-50 min to obtain primary anodic oxidation TiO2A nanotube;
(2) by primary anodic oxidation of TiO2The nanotube is used as an anode, a platinum sheet is used as a cathode, and a mixed solution consisting of ammonium fluoride, ethylene glycol and water is used as electrolyte for electrolysis again; the anode after electrolysis is subjected to heat preservation for 50-60 min at the temperature of 450-460 ℃, and secondary anodic oxidation TiO is obtained2A nanotube;
(3) using molten carbonate as electrolyte to make secondary anode oxidation of TiO2The nanotube is used as a cathode, a nickel electrode is used as an anode, electrolysis is carried out, and the cathode after electrolysis is sequentially subjected to ultrasonic pickling and drying, so that the carbon nanotube/secondary anode oxidized TiO is obtained2A nanotube; in the step (3), the electrolysis process conditions are as follows: the electrolysis temperature is 500-750 ℃, the current density is 100-150 mA, and the electrolysis time is 10-50 s;
the carbonate is lithium carbonate, sodium carbonate and potassium carbonate according to the proportion of (60-65): (20-25): (15-20) by mass.
2. The method according to claim 1, wherein the carbonate is lithium carbonate, sodium carbonate and potassium carbonate in a ratio of 61:22:17 mass ratio.
3. The method of claim 1, wherein the solar cell is a silicon-based solar cell.
4. The method of claim 1, wherein the solar thermal collector is selected from any one of flat-plate solar collectors, trough solar collectors, and evacuated-tube solar collectors.
5. The method according to claim 1, wherein before degradation, the working electrode and the counter electrode are placed in organic wastewater, the temperature of the wastewater is raised to 60-90 ℃ by using the solar heat collection device, and then the wastewater is kept stand for 10-20 min in a dark environment without power supply.
6. The method according to any one of claims 1 to 5, wherein the organic wastewater is industrial wastewater or domestic wastewater containing sodium dodecylbenzene sulfonate and/or nitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810023280.6A CN108275811B (en) | 2018-01-10 | 2018-01-10 | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810023280.6A CN108275811B (en) | 2018-01-10 | 2018-01-10 | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108275811A CN108275811A (en) | 2018-07-13 |
| CN108275811B true CN108275811B (en) | 2021-02-09 |
Family
ID=62803474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810023280.6A Active CN108275811B (en) | 2018-01-10 | 2018-01-10 | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108275811B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264814B (en) * | 2018-09-13 | 2021-10-12 | 江苏大学 | Device and method for treating organic sewage through photo-thermal concerted catalysis |
| CN109382083B (en) * | 2018-11-30 | 2021-07-20 | 内蒙古工业大学 | Carbon nanotube-doped titanium dioxide nanotube photocatalytic material and preparation method thereof |
| CN109574343A (en) * | 2019-01-21 | 2019-04-05 | 东北石油大学 | The demulsification processing method of oily wastewater solar energy STEP |
| CN110655257B (en) * | 2019-10-15 | 2021-12-21 | 东北石油大学 | Phenol wastewater treatment method |
| CN113398904B (en) * | 2021-05-06 | 2023-05-02 | 桂林电子科技大学 | Preparation method and application of catalyst for catalytically oxidizing VOCs in synergistic manner by medium-low temperature light and heat |
| CN113583712B (en) * | 2021-07-12 | 2022-05-24 | 浙江大学 | Multi-energy coupling complementary and sequential conversion system and method |
| CN114590859B (en) * | 2022-03-24 | 2023-04-07 | 东北石油大学 | Method for treating oily sewage by solar STEP light-heat-electric coupling |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693560A (en) * | 2009-10-21 | 2010-04-14 | 华北水利水电学院 | Integral solar energy photoelectricity water-treatment device |
| CN102534727A (en) * | 2012-01-13 | 2012-07-04 | 天津大学 | Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device |
| CN102583660A (en) * | 2012-01-19 | 2012-07-18 | 华东理工大学 | Electrolytic process for wastewater treatment by solar photovoltaic generation energy |
| CN104803442A (en) * | 2015-05-05 | 2015-07-29 | 东北石油大学 | Device and method of utilizing solar energy light-heat-electrochemistry to degrade polyacrylamide |
| CN104803441A (en) * | 2015-05-05 | 2015-07-29 | 东北石油大学 | Device and method of utilizing solar energy light-heat-electric coupling to treat acrylonitrile sewage |
| CN106219687A (en) * | 2016-08-15 | 2016-12-14 | 浙江大学 | A kind of method of pollutant in photoelectrocatalysis reduction treatment water body |
-
2018
- 2018-01-10 CN CN201810023280.6A patent/CN108275811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693560A (en) * | 2009-10-21 | 2010-04-14 | 华北水利水电学院 | Integral solar energy photoelectricity water-treatment device |
| CN102534727A (en) * | 2012-01-13 | 2012-07-04 | 天津大学 | Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device |
| CN102583660A (en) * | 2012-01-19 | 2012-07-18 | 华东理工大学 | Electrolytic process for wastewater treatment by solar photovoltaic generation energy |
| CN104803442A (en) * | 2015-05-05 | 2015-07-29 | 东北石油大学 | Device and method of utilizing solar energy light-heat-electrochemistry to degrade polyacrylamide |
| CN104803441A (en) * | 2015-05-05 | 2015-07-29 | 东北石油大学 | Device and method of utilizing solar energy light-heat-electric coupling to treat acrylonitrile sewage |
| CN106219687A (en) * | 2016-08-15 | 2016-12-14 | 浙江大学 | A kind of method of pollutant in photoelectrocatalysis reduction treatment water body |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108275811A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108275811B (en) | Method for degrading organic wastewater by solar energy through photo-electric-thermal three-field coupling | |
| Chen et al. | Hydrogen production on TiO2 nanorod arrays cathode coupling with bio-anode with additional electricity generation | |
| CN103367759B (en) | Visible-light response type photocatalysis wastewater fuel cell, manufacture method thereof and application thereof | |
| CN208471684U (en) | A kind of photocatalysis-microbiological fuel cell sewage treatment set composite | |
| CN103771565B (en) | Preparation method of composite electrode of carbon nitride/titanium dioxide nanotube | |
| CN112125390B (en) | Device for degrading antibiotics by adopting photocatalysis-assisted reinforced biological anode | |
| Joya et al. | Artificial leaf goes simpler and more efficient for solar fuel generation | |
| CN106299418A (en) | The photocatalysis wastewater fuel cell, manufacture of strengthening radical reaction and preparation method and application | |
| Xu et al. | Simultaneous electricity generation and wastewater treatment in a photocatalytic fuel cell integrating electro-Fenton process | |
| CN102306802A (en) | Nanotube array fuel battery of visible light response | |
| Liu et al. | Multi-functional photocatalytic fuel cell for simultaneous removal of organic pollutant and chromium (VI) accompanied with electricity production | |
| CN102583660A (en) | Electrolytic process for wastewater treatment by solar photovoltaic generation energy | |
| CN110783111A (en) | Titanium dioxide film electrode and preparation method and application thereof | |
| CN104817190B (en) | A kind of Bioelectrochemical device and the method that utilize solar energy fall dirt to produce hydrogen | |
| CN108273486B (en) | Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof | |
| CN114318384A (en) | Photoelectrocatalysis system and preparation method and application thereof | |
| Tseng et al. | Thermodynamic analysis of a photoelectrochemical hydrogen production system | |
| CN107841763B (en) | A kind of optoelectronic pole and preparation method thereof based on the regulation of surface hydrogen-oxygen shell | |
| CN212198625U (en) | Solar cell-photoelectrochemistry pool integrated device | |
| Xiao et al. | Solar fuel production from CO2 reduction in a self-biased hybrid solar-microbial device | |
| CN209052544U (en) | A kind of coupling device of microbiological fuel cell and photo-electrocatalytic technology | |
| CN111916808A (en) | SmFCs for strengthening electrogenesis decontamination of cobaltosic oxide photocathode and preparation method thereof | |
| CN110451631A (en) | A kind of method of enhanced biological electrochemical in-situ pollution waters restoration | |
| CN214496498U (en) | Light-driven dual-function device for degrading and producing hydrogen | |
| CN113818064B (en) | Needle-shaped nickel black film capable of realizing efficient photo-thermal conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240117 Address after: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Dragon totem Technology (Hefei) Co.,Ltd. Address before: 163318 No. 99 Xuefu Street, Daqing Hi-tech Industrial Development Zone, Heilongjiang Province Patentee before: NORTHEAST PETROLEUM University |
|
| TR01 | Transfer of patent right |