CN108275811A - A method of passing through the hot THM coupling degradation of organic waste water of optical-electronic-using solar energy - Google Patents
A method of passing through the hot THM coupling degradation of organic waste water of optical-electronic-using solar energy Download PDFInfo
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- 238000010168 coupling process Methods 0.000 title claims abstract description 27
- 230000008878 coupling Effects 0.000 title claims abstract description 25
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 25
- 239000010815 organic waste Substances 0.000 title claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002071 nanotube Substances 0.000 claims abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002048 anodisation reaction Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 62
- 238000005868 electrolysis reaction Methods 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 23
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- 239000010936 titanium Substances 0.000 claims description 14
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- 229910052719 titanium Inorganic materials 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- 239000010865 sewage Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 23
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- 238000000926 separation method Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
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- 238000000354 decomposition reaction Methods 0.000 description 5
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- 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
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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- 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 present invention relates to a kind of using solar energy by the method for photoelectric heat THM coupling degradation of organic waste water, and the method provides electric energy using solar cell, thermal energy is provided using solar energy heat collector, with carbon nanotube/two-step anodization TiO2Nanotube is conducted as working electrode using platinum electrode as the anode to electrode, working electrode and the solar cell, is conducted to the negative electrode of electrode and the solar cell；It before degradation, is put into organic wastewater by working electrode and to electrode, heats organic wastewater using the solar energy heat collector, then stood in dark surrounds and under the conditions of cold；When degradation, organic wastewater is heated using the solar energy heat collector, is powered to waste water using solar cell, is electrolysed under conditions of sunlight irradiates working electrode.Three field energy of solar energy is coupled by this method present invention：Thermal field, light field and electric field energy improve the utilization rate of degradation efficiency and solar energy.
Description
Technical field
The present invention relates to organic wastewater degraded technical fields more particularly to a kind of utilization solar energy to pass through optical-electronic-Re Sanchang
The method for coupling degradation of organic waste water.
Background technology
Traditional method for processing organic wastewater includes the physical methods such as foam separating technology, absorption and membrane separation technique, wadding
The chemical methodes such as the solidifying precipitation method, coagulant sedimentation, high-level oxidation technology and photocatalytic degradation and light help Fenton oxidation and life
Object degradation etc..However, there are no a kind of satisfactory methods can be widely applied for the efficient of organic wastewater so far
In degradation, efficient wastewater treatment method should fully take into account economic rationality (such as：No or low consumed chemical drugs
Agent) and the feature of environmental protection (" green repair path ").Therefore, new technology is developed, efficient and environmental-friendly degradation of organic waste water
Method has become a urgent challenge.
Solar energy be it is a kind of cleaning, safe, inexhaustible green energy resource.Currently, solar energy-thermal energy and too
The application technology of positive energy electric energy is more mature, such as solar energy heating, solar water heating system, solar heated green house, solar energy hair
Electricity, solar cell etc..But since solar energy-heat energy utilization and solar-electrical energy are using being required for carrying out by intermediate equipment
The Transformation Application of energy, just along with prodigious energy loss in conversion process.Moreover, although solar energy-light-use is straight
Utilization is connect, but since ultraviolet portion energy only accounts for the ratio of very small part in solar spectrum energy, so can not be from basic
The upper utilization rate for promoting solar energy.If can combine each section energy of solar spectral, coupling is applied to sameization
It learns in reaction, realizes the coupling application of sunlight-electric-thermal energy, provide the sufficient energy for chemical reaction, whole process does not need
Additional input energy, while other chemical agents need not be added, such technology will be with great research significance and extensively
Wealthy application prospect.
Invention content
(1) technical problems to be solved
For a kind of biodegrading process carrying out efficient environmental protection to organic wastewater using solar energy is lacked in the prior art, originally
Invention proposes to be applied to solar energy-electric-thermal THM coupling in the experiment model of oxidation processes organic wastewater, passes through simultaneously
Allotment three, seeks the efficient coupling pattern of Solar use, and for the first time by the TiO of carbon nanotube loaded modification2Nanotube electricity
Application of electrode maximally utilises solar energy and carries out organic wastewater in the degradation process of organic wastewater centered on pole
Degradation.
(2) technical solution
In order to solve the above technical problem, the present invention provides following technical solutions：
A method of using solar energy by the hot THM coupling degradation of organic waste water of optical-electronic-, the method uses the sun
Energy battery provides electric energy, thermal energy is provided using solar energy heat collector, with carbon nanotube/two-step anodization TiO2Nanotube is made
It for working electrode, is conducted using platinum electrode as the anode to electrode, working electrode and the solar cell, to electrode and institute
The negative electrode for stating solar cell conducts；
It before degradation, is put into organic wastewater by working electrode and to electrode, has using solar energy heat collector heating
Then machine waste water is stood in dark surrounds and under the conditions of cold；
When degradation, using the solar energy heat collector continue heat organic wastewater, using solar cell to waste water into
Row is powered, and is electrolysed under conditions of sunlight irradiates working electrode.
Preferably, before degradation and when degradation, organic wastewater is heated to 60~90 DEG C using the solar energy heat collector；
With
When degradation, the voltage of 1.2~1.8V is provided using the solar cell.
Preferably, the carbon nanotube/two-step anodization TiO2Nanotube is prepared with the following method：
(1) using titanium sheet as anode, platinized platinum as cathode, using the mixed solution that ammonium fluoride, ethylene glycol and water form as
Electrolyte is electrolysed；Titanium sheet after electrolysis is kept the temperature into 40~50min at 460~500 DEG C, obtains an anodic oxidation
TiO2Nanotube；
(2) with an anodic oxidation TiO2Nanotube is as anode, and platinized platinum is as cathode, with ammonium fluoride, ethylene glycol and water
The mixed solution of composition is electrolysed again as electrolyte；Anode material after electrolysis is kept the temperature 50 at 450~460 DEG C
~60min obtains two-step anodization TiO2Nanotube；
(3) using fused carbonate as electrolyte, two-step anodization TiO2Nanotube is as cathode, and nickel electrode is as sun
Pole is electrolysed, and the cathode after electrolysis is carried out ultrasonic wave pickling and drying successively, to obtain carbon nanotube/secondary anode
Aoxidize TiO2Nanotube.
It is further preferred that the carbonate be lithium carbonate, sodium carbonate and potassium carbonate according to (60~65)：(20~25)：
The mixture of (15~20) mass ratio composition.It is highly preferred that the carbonate be lithium carbonate, sodium carbonate and potassium carbonate according to 61：
22：The mixture of 17 mass ratioes composition.
It is further preferred that in step (3), the process conditions of the electrolysis are：Electrolysis temperature is 500~750 DEG C, electric current
Density is 100~150mA, and electrolysis time is 10~50s.
Preferably, the solar cell is silica-based solar cell.
Preferably, the solar energy heat collector is selected from flat-plate solar collector, trough type solar heat-collector, vacuum tube
Any one of solar thermal collector.
Preferably, it before degradation, is put into organic wastewater by working electrode and to electrode, utilizes the solar energy heat collector
Waste water temperature is warming up to 60~90 DEG C, 10~20min is then stood in dark surrounds and under the conditions of cold.
Preferably, the organic wastewater is the trade effluent containing neopelex and/or nitrobenzene or life
Sewage.
(3) advantageous effect
The above-mentioned technical proposal of the present invention has the following advantages that：
The present invention gets up the energy synthesis of solar energy-electric-thermal three, enables its effective Distribution utilization, the sun
Heat not only contributes to the reduction of oxidation-reduction potential to the increase of reaction, and is conducive to the enhancing of kinetics.Solar energy
Battery provides stable potential, can promote the transfer of electronics, and the ultraviolet portion in sunlight provides photic electricity for photocatalysis
The separation of son and hole, therefore, the photo-thermal electrochemical pattern of the matching of solar energy multi- scenarios method and coordinated drive can be organic waste
The degradation of water (the especially organic wastewater of nitrobenzene-containing and/or neopelex) provides effective way of Solar use
Diameter.
The present invention has investigated a kind of full spectrum solar energy coupling matching and acts on the side in organic wastewater degraded
Method, this method react sunlight ultraviolet portion energy applied to photochemical catalyst, it is seen that light portion of energy is applied to solar-electricity
Pond generates electricity, and infrared portions energy is applied to solar thermal collector heat, and one is coupling in when three kinds of portion of energy utilize simultaneously
In a reaction, the efficient thorough degradation of organic wastewater may be implemented.
Description of the drawings
Fig. 1 is the ultraviolet-visible of the solar energy-thermo-electrically THM coupling method degrading nitrobenzene provided using embodiment 1
Optical absorption spectra；
Fig. 2 is to utilize the uv-visible absorption spectroscopy that nitrobenzene is aoxidized under solar energy-electric field independent role；
Fig. 3 is the uv-visible absorption spectroscopy of solar energy-light field independent role oxidation nitrobenzene；
Fig. 4 is the current curve of the solar energy-thermo-electrically THM coupling method degrading nitrobenzene provided using embodiment 1；
Fig. 5 is the current curve of degrading nitrobenzene under two field coupling conditions of solar energy optical-electronic.
Fig. 6 shows the level analysis under the conditions of solar energy STEP optical and thermals-electricity THM coupling.
Fig. 7 shows the mechanism of the photo-thermal electrochemical degrading nitrobenzene of more drivings.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiment of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of using solar energy by the method for the hot THM coupling degradation of organic waste water of optical-electronic-, described
Method provides electric energy using solar cell, thermal energy is provided using solar energy heat collector, with carbon nanotube/two-step anodization
TiO2Nanotube is as working electrode, using platinum electrode as to electrode, the positive electrode conductance of working electrode and the solar cell
It is logical, the negative electrode of electrode and the solar cell is conducted.Solar cell used is capable of providing stable voltage, uses
To provide electric energy to electrode.Preferably, the solar cell is silica-based solar cell.Solar energy heat collector used
It can select any one of flat-plate solar collector, trough type solar heat-collector, vacuum tube solar heating element.The present invention
Working electrode material used is carbon nanotube/two-step anodization TiO2Nanotube.Carbon nanotube/two-step anodization TiO2
Nanotube realizes the utilization of solar energy-luminous energy as photochemical catalyst.This photocatalyst material can carry out as follows
It prepares：(1) using titanium sheet as anode, platinized platinum is as cathode, using the mixed solution that ammonium fluoride, ethylene glycol and water form as electrolysis
Liquid is electrolysed；Titanium sheet after electrolysis is kept the temperature into 40~50min at 460~500 DEG C, obtains an anodic oxidation TiO2It receives
Mitron；(2) with an anodic oxidation TiO2Nanotube is formed as cathode with ammonium fluoride, ethylene glycol and water as anode, platinized platinum
Mixed solution as electrolyte, be electrolysed again；Anode material after electrolysis keeps the temperature at 450~460 DEG C to 50~
60min obtains two-step anodization TiO2Nanotube；(3) using fused carbonate as electrolyte, two-step anodization TiO2It receives
Mitron is electrolysed as cathode, nickel electrode as anode, and the cathode after electrolysis is carried out ultrasonic wave pickling and drying successively,
To obtain carbon nanotube/two-step anodization TiO2Nanotube.Carbonate used is preferably lithium carbonate, sodium carbonate and carbonic acid
Potassium is according to (60~65)：(20~25)：The mixture of (15~20) mass ratio composition, more preferably according to 61：22：17 mass ratioes
The mixture of composition.In step (3), the process conditions of the electrolysis are preferably：Electrolysis temperature is 500~750 DEG C, current density
For 100~150mA, electrolysis time is 10~50s.
It before degradation, is put into organic wastewater by working electrode and to electrode, has using solar energy heat collector heating
Then machine waste water is stood in dark surrounds and under the conditions of cold, time of repose can select 10~20 minutes, preferably
10~15 minutes.Heating temperature can be identical with temperature when being degraded, preferably 60 DEG C, it is ensured that reach under degradation temperature
The equilibrium state of absorption-desorption between electrode (as catalyst) and solution (organic wastewater).
When degradation, organic wastewater is heated using the solar energy heat collector, heating temperature is preferably 60~90 DEG C, simultaneously
It is powered to waste water using solar cell, the applied voltage of 1.2~1.8V is provided, irradiate the item of working electrode in sunlight
It is electrolysed under part.
The oxidative degradation of organic wastewater, such as the oxidation reaction process such as electrochemistry and photocatalysis are that high energy barrier is anti-
It answers, in order to pass through potential barrier, needs a large amount of energy that reactant molecule is made to reach transition state, this energy is known as reacting required activation
Energy.When reaction temperature increases, the potential energy for reacting the starting stage increases, and potential barrier is made to be easier to pass through.Therefore, reaction solution is improved
Temperature can accelerate electrochemistry and Photocatalytic Oxidation.But since external agency heating can cause additional energy to disappear
Consumption, thus by fossil energy provide thermal energy in favor of electrochemistry and photochemical catalytic oxidation organic contamination there is many drawbacks and
Limitation.Solar energy has many advantages, such as rich, inexpensive and low-carbon emission, can be widely used in the oxidation of organic wastewater.It is logical
Such transform mode is crossed, photo-thermal electrochemical process can make full use of the full spectral energy of solar energy to carry out the drop of organic wastewater
Three field energies of solar energy, that is, thermal field, light field and electric field energy are coupled by solution, the present invention, are allowed to collaboration matching and are applied to organic waste
The degradation reaction of water, to fundamentally improve the degradation rate of solar energy utilization ratio and organic wastewater.If organic pollution
Oxidation reaction as whole sources, then needs a large amount of energy to maintain to react dependent on single game energy, and simultaneously because by
The limitation of itself conversion ratio of solar energy-thermal energy/solar-electrical energy, this validity in the way of solar energy are obvious
It is relatively low.Three synergistic effect coupled mode make：The coupling matching thermal activation of the concept of the thermoelectrochemistry of more drivings
Effect, photostimulation in electric drive electronic transfer process, energy that optical-electronic-heat is three at the same act on system anode (in
Heart electrode) on, central electrode has played conclusive effect in system, its property determines the height of solar energy utilized
With the efficiency of oxidation organic pollutants.In the oxidation reaction process that central electrode surface occurs, all energy come
From in solar energy, without the input of other form of energy, solar heat, solar-electricity and the part solar energy (UV) solar energy
By collaboration coupling to improve oxidation rate.Oxidation reaction is the endothermic reaction thermodynamically, and the addition of solar heat reduces electrolysis
Current potential, and activation application of the light on central electrode is conducive to the degradation efficiency for improving solar energy to organic matter.
It, can be dirty to the trade effluent containing neopelex and/or nitrobenzene or life using the above method
Water carries out degradation rapidly and efficiently.
It is the embodiment that the present invention enumerates below.
Embodiment 1
Utilize waste water of the method provided by the invention degradation containing nitrobenzene.
Prepare photocatalyst material：Titanium sheet is cleaned by ultrasonic 15min in acetone, absolute ethyl alcohol and distilled water successively,
It is dry in nitrogen.Using bipolar electrode system：Power supply uses D.C. regulated power supply, and DC power anode is accessed by anode of titanium sheet,
Platinized platinum (2cm × 2cm) is to access power cathode to electrode, in 0.5wt%NH4F+(CH2OH)2+ 2vol%H2The mixed solution of O
In the electrolyte of composition, it is electrolysed under room temperature 50V constant voltages, electrolysis time 30min.After reaction, titanium sheet is used
It after distilled water flushing, is placed in Muffle furnace under air atmosphere, is warming up to 450 DEG C since room temperature with the rate of 5 DEG C/min, perseverance
Warm 1h, an anodic oxidation TiO obtained2Nanotube.
It will long once anodic oxidation TiO2The titanium sheet of nanotube, which is placed in the beaker equipped with distilled water, to be cleaned by ultrasonic, until
Completely remove the titania nanotube film on its surface.There are the cleaning of the titanium sheet of the hexagon pit marking of marshalling is dry for taking-up
Only it and dries, is electrolysed, electrolytic condition is 20V constant voltage 30min, remaining is identical as last time electrolysis.After reaction, by titanium
Piece distilled water flushing, with the remaining electrolyte of removal and the fragment of nanotube nozzle.Then, it is placed in stone Muffle furnace in air
Under atmosphere, 450 DEG C are warming up to the rate of 5 DEG C/min since room temperature, constant temperature 1h makes TiO2Crystal form by it is unformed be converted into it is sharp
Titanium ore type obtains two-step anodization TiO2Nanotube.
With mixed melting carbonate system (Li2CO3, Na2CO3, K2CO3) it is used as electrolyte, weight ratio 61:22:17.It will
The two-step anodization TiO of preparation2Nanotube is electrolysed as anode under conditions of 500 DEG C as cathode, nickel electrode,
Current density is 100mA, electrolysis time 10s.After electrolysis, the cathode after load is taken out from electrolytic cell, successively into
The pickling of row ultrasonic wave and drying obtain carbon nanotube/two-step anodization TiO2Nano pipe light catalyst.
It uses solar cell to provide burning voltage for degradation, flat-plate solar collector is used to provide thermal energy for degradation,
Organic wastewater is heated, with using carbon nanotube/two-step anodization TiO made from the above method2Nanotube is as work
Make electrode, conducted using platinum electrode as the anode to electrode, working electrode and the solar cell, to electrode with it is described too
The negative electrode of positive energy battery conducts.Before degradation, organic wastewater (a concentration of 20mgL of NB are put by working electrode and to electrode-1) in, organic wastewater is heated using flat-plate solar collector, by the water temperature heating of waste water to 60 DEG C, then in dark surrounds
And it is cold under the conditions of stand 10 minutes, make the equilibrium state for reaching absorption-desorption between electrode and solution.When degradation, utilize
Organic wastewater is heated to 60 DEG C by flat-plate solar collector, while being powered to waste water using solar cell, is provided
The applied voltage of 1.2V is electrolysed under conditions of sunlight irradiates working electrode.
As seen from Figure 1, when being electrolysed 15 minutes, the degradation rate of nitrobenzene is 88.1%.When being electrolysed 30 minutes, nitrobenzene
Degradation rate reached 100%.
In addition, the curent change in detection degradation process, the result is shown in Fig. 4.
Comparative example 1：Biodegrading process and embodiment 1 used in comparative example 1 is substantially the same, the difference is that：Solar energy
The applied voltage that battery provides is 1.2V, and waste water temperature is heated to 30 DEG C (being equivalent to normal temperature condition), work by solar thermal collector
It is platinum electrode to make electrode, does not have photo-catalysis function, can not carry out photocatalysis using ultraviolet light, be equivalent to only in solar energy-electricity
Nitrobenzene is aoxidized under the independent role of field, uv-visible absorption spectroscopy is shown in Fig. 2.From figure 2 it can be seen that in electrolysis electricity
After carrying out 60min under the conditions of pressure, the characteristic absorption of ultraviolet spectra is declined slightly, and degradation rate when calculating 30min according to it is
Degradation rate when 2.2%, 60min is 3.6%.
Comparative example 2：Biodegrading process used in comparative example 2 is substantially the same with embodiment 1, the difference is that：It does not use
Waste water temperature is heated to 30 DEG C (being equivalent to normal temperature condition), phase by the applied voltage that solar cell provides, solar thermal collector
When in only aoxidizing nitrobenzene under solar energy-light field independent role, uv-visible absorption spectroscopy is shown in Fig. 3.It can from Fig. 3
To find out, after carrying out 60min under the illumination condition, the characteristic absorption peak of ultraviolet spectra has more apparent decline, root
Degradation rate when according to its calculating 30min is only 64.9%；When degradation time is increased to 60min, degradation efficiency increases to
92.3%.
Comparative example 3：Biodegrading process used in comparative example 3 is substantially the same with embodiment 1, the difference is that：Merely with
Waste water temperature is heated to 60 DEG C by solar thermal collector, is equivalent to solar energy-thermal field and is acted solely on nitrobenzene-containing organic wastewater
Degradation experiment.After carrying out 60min at such a temperature, the characteristic absorption peak (267nm) of uv-visible absorption spectroscopy is not sent out
Raw significant change, two curves of 0min and 60min are completely superposed, i.e. heat effect does not cause additional nitrobenzene to drop
Under solar energy-thermal field energy effect degradation does not occur for solution.
Comparative example 4：Biodegrading process used in comparative example 4 is substantially the same with embodiment 1, the difference is that：Solar energy
Waste water temperature is heated to 30 DEG C (being equivalent to normal temperature condition) by heat collector, is equivalent under two couplings of solar energy optical-electronic
Nitrobenzene is aoxidized, curent change is shown in Fig. 5.
It is learnt according to Fig. 4 calculating, under the effect of solar energy-electric-thermal THM coupling, the energy W that is put into system (1.2V,
60 DEG C, carbon nanotube/two-step anodization TiO2Nanotube)=UIt=1.2V × 1011656.29 × 10-6As=1.21J；
According to Fig. 5 calculating learn, under two couplings of solar energy optical-electronic, system input energy W (1.2V, 30 DEG C, carbon nanotube/
Two-step anodization TiO2Nanotube)=UIt=1.2V × 570604.51 × 10-6As=0.69J.
Light of the present invention, heat, electricity three respectively the relationship between energy levels figure of effect and coupling as shown in fig. 6, when profit
When carrying out the degradation reaction of organic wastewater with single game effect, a large amount of energy is put into across the energy level needed for reaction is highly desirable,
Since the degradation reaction of organic matter is usually all the endothermic reaction of calculation of thermodynamics, the energy needed is come out except through theoretical calculation
Other than amount, it is also necessary to which a large amount of activation energy crosses over reaction barrier, so when providing energy by single game, the total amount of this energy needs
It is very big.Experiment before the present inventor passes through also demonstrates：
(i) after carrying out reaction under the conditions of independent thermal field acts on 60 DEG C 1 hour, nitrobenzene does not become substantially in system
Change, it is super in most of highlands temperature when carrying out the degradation of organic wastewater in the system of opening wide if further increasing temperature
Crossing 90 DEG C may can boil, and the volatilization of the organic matter in one side water and its system is fairly obvious, on the one hand also give work
Industry operation brings prodigious actual motion difficult, if carry out the degradation of organic wastewater in the system of closing pressurization, passes through
The pressure of promotion system, which can control temperature and reach 100 DEG C or more of condition, is reacted, but in this case to whole water process
The technology requirement of device is very high, may be difficult to realize such industrial operation operation transformation in a short time, simultaneity factor operation
The production cost and technical costs of later maintenance are also prodigious problem.
(2) after being carried out 1 hour under the conditions of independent electric field 1.2V, in system the degradation rate of nitrobenzene less than 5%, this for
It is the standard that wastewater treatment is much not achieved for actual industrial production, if further increasing the voltage of electric field, really
Can in promotion system various organic matters degradation rate and degradation rate, we also attempt to arrive voltage value promotion in experiment
3.0V, but a large amount of bubble can visually be observed by carrying out reacting the just surface in electrode in such a situa-tion, be reacted
The reduction of water after carrying out 1 hour in system is also very apparent, illustrates the decomposition life along with a large amount of water in reaction process
At O2And H2.Although H2It is a kind of extraordinary clean fuel, but in common sewage disposal process, is configured without gas
Body retracting device, and since the ingredient of waste water is extremely complex, in actual electrolytic process, a variety of gas may be will produce
Body, if it is desired to be recycled the hydrogen of generation, it is also necessary to which the cost of further purified reaction, processing also can be into one
Step increases.When carrying out treatment of Organic Wastewater using the decomposition voltage more than water, the decomposition that some energy is used for water is anti-
It answers, and the H that the decomposition reaction of water generates2If it cannot effectively be recycled, the wave of mass energy certainly will be caused
Take, so from the angle of real work, this is also very worthless.
(3) after being carried out 1 hour under the conditions of independent light field, carbon nanotube/two-step anodization TiO after application enhancements2
Nanotube carries out photocatalysis, and the degradation rate of nitrobenzene is higher in system, illustrates the sensitivity that this substance of nitrobenzene degrades to light field
Property, but from the angle of energy utilization for, photocatalysis can only utilize ultraviolet and fraction visible region in solar spectrum
Radiation, can not be used to the solar radiation of most of visible light and infrared part, and ultra-violet (UV) band (<0.4 μm) had
Some energy only account for 7% up to earth surface solar radiation gross energy, so light-catalysed method is used alone to be had
The degradation of machine waste water, it is impossible to which reach that we pursue all the time efficiently utilizes this main purpose of solar energy.
So the target of the degradation rate in order to reach high solar utilization rate and high organic wastewater simultaneously, the present invention
People integrates three field energies, its effective Distribution utilization, solar heat is enable to not only contribute to aoxidize to the increase of reaction
The reduction of reduction potential, and be conducive to the enhancing of kinetics.As can be seen from the above results, solar cell provides
The stable potential of 1.2V can promote the transfer of electronics, ultraviolet portion to provide the separation in photoinduced electron and hole for photocatalysis,
It is matched in solar energy multi- scenarios method, the photo-thermal electrochemical pattern of coordinated drive provides too the degradation of nitrobenzene-containing organic wastewater
The effective way that sun can utilize.
Electrode centered on semi-conducting electrode, the photo-thermal electrochemical driven according to more is theoretical, the middle electrocardio of composite construction
Pole is carried out at the same time three kinds of photochemistry, electrochemistry and heat chemistry different chemical reaction processes, and mechanism is as shown in Figure 7.Fig. 7 is aobvious
Show under the action of more coordinated drives, in the variation that the space charge layer of central electrode occurs.TiO2It is that a kind of N-shaped is partly led
Body acts on TiO when surface applies positive field2When/Ti type structure electrodes, the effect of electric field can be conducive to light induced electron and
The separation in hole is conducive to the acceleration conduction of charge, can be operated upon by light-catalyzed reaction.Es in the figure0It is dark condition
Under, it is position of energy band when not applying extra electric field, Es*It is under illumination condition, is energy band position when not applying extra electric field
It sets, Es*+It is to apply position of energy band when positive field, Es under illumination condition*-It is to apply negative sense electric field under illumination condition
When position of energy band.As shown in fig. 7, when applying the electric field of positive acting on the electrode, surface photovoltage has significant increase
The separative efficiency and rate of electronics and hole, while inhibiting light induced electron and compound, the increase photocatalytic oxidation degradation nitre in hole
Base benzene rate, while the increase of the temperature of system, are conducive to the acceleration of the effect of mass transmitting of nitrobenzene in the solution, make nitrobenzene
Degradation rate obtains the effect increased sharply in a short time.So in the synergistic effect of solar energy STEP optical and thermals-electricity THM coupling
Under, the utilization rate of solar energy and the degradation of organic wastewater have obtained promotion simultaneously.
The present invention utilizes carbon nanotube/two-step anodization TiO2Center of the nanometer tube combination electrode as degradation process,
The efficiency of solar energy utilization can be greatly improved.Solar-electrical energy provides stable current potential (1.2V), the effect of electric field for reaction
It can promote the transfer of electronics, and the ultraviolet light of sunlight is TiO2The photocatalysis of electrode provides the radiation of energy, electrode table
The transmission of the separation and substance of the charge that the synergistic effect of face simple substance carbon accelerates.Therefore, the synergistic effect of solar heat, solar energy
Electricity and ultraviolet oxidation nitrobenzene provide enough energy.Under the irradiation of solar energy and ultraviolet light, using more sun
It can heat, in this case, the oxygenation efficiency of nitrobenzene and the utilization rate of solar energy have obtained significantly promotion fundamentally.Cause
This, an efficient approach is provided in the utilization that the three collaboration matching applications of solar energy-thermo-electrically are solar energy.
In conclusion under solar energy-electric-thermal THM coupling effect, the degradation of nitrobenzene is more rapid, more thorough
Bottom, when extra electric field voltage is 1.2V, under conditions of reaction system is 60 DEG C, only degrade 15min, has just reached 88.1%
Degradation efficiency.Solar thermal energy reduces the decomposition voltage of nitrobenzene degradation in reaction, and the extra electric field generated by photovoltaic cell promotees
Into the separation of photo-generate electron-hole pair, while also inhibiting the compound again of them so that TiO2Photoresponse range extension
Visible region is arrived, it will be apparent that improve TiO2Photocatalytic activity, and heat effect increase biography of the nitrobenzene in system
Matter acts on, and in the systematic procedure of the hot THM coupling of optical-electronic-, significantly increases the degradation efficiency of organic wastewater.Solar energy
The hot THM coupling of optical-electronic-plays synergistic effect during nitrobenzene degradation.
Three field energy flux of innovative allotment of the invention seek the most efficient coupled mode of Solar use, and for the first time will
Carbon nanotube/two-step anodization TiO2Application of electrode is maximum in the degradation process of organic wastewater centered on nanotube
The degradation reaction that organic wastewater is carried out using solar energy of limit.The present invention by sunlight ultraviolet portion energy apply and photocatalysis
Agent is reacted, it is seen that light portion of energy is applied to solar cell power generation and infrared portions energy is applied to solar energy heating
Device heat obtains the efficient thorough degradation of organic wastewater when three kinds of portion of energy utilize simultaneously to be coupling in a reaction.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of passing through the method for the hot THM coupling degradation of organic waste water of optical-electronic-using solar energy, which is characterized in that the side
Method provides electric energy using solar cell, thermal energy is provided using solar energy heat collector, with carbon nanotube/two-step anodization
TiO2Nanotube is as working electrode, using platinum electrode as to electrode, the positive electrode conductance of working electrode and the solar cell
It is logical, the negative electrode of electrode and the solar cell is conducted；
It before degradation, is put into organic wastewater by working electrode and to electrode, organic waste is heated using the solar energy heat collector
Then water is stood in dark surrounds and under the conditions of cold；
When degradation, continues to heat organic wastewater using the solar energy heat collector, waste water is led to using solar cell
Electricity is electrolysed under conditions of sunlight irradiates working electrode.
2. according to the method described in claim 1, it is characterized in that, before degradation and when degradation, filled using the solar energy heating
It sets and organic wastewater is heated to 60~90 DEG C；With
When degradation, the voltage of 1.2~1.8V is provided using the solar cell.
3. according to the method described in claim 1, it is characterized in that, the carbon nanotube/two-step anodization TiO2Nanotube is adopted
It is prepared with the following method：
(1) using titanium sheet as anode, platinized platinum is as cathode, using the mixed solution that ammonium fluoride, ethylene glycol and water form as electrolysis
Liquid is electrolysed；Titanium sheet after electrolysis is kept the temperature into 40~50min at 460~500 DEG C, obtains an anodic oxidation TiO2It receives
Mitron；
(2) with an anodic oxidation TiO2Nanotube is formed as cathode with ammonium fluoride, ethylene glycol and water as anode, platinized platinum
Mixed solution is electrolysed again as electrolyte；Anode after electrolysis is kept the temperature into 50~60min at 450~460 DEG C, is obtained
To two-step anodization TiO2Nanotube；
(3) using fused carbonate as electrolyte, two-step anodization TiO2Nanotube as cathode, nickel electrode as anode, into
Row electrolysis, carries out ultrasonic wave pickling and drying, to obtain carbon nanotube/two-step anodization successively by the cathode after electrolysis
TiO2Nanotube.
4. according to the method described in claim 3, it is characterized in that, the carbonate is pressed for lithium carbonate, sodium carbonate and potassium carbonate
According to (60~65)：(20~25)：The mixture of (15~20) mass ratio composition.
5. according to the method described in claim 3, it is characterized in that, the carbonate is pressed for lithium carbonate, sodium carbonate and potassium carbonate
According to 61：22：The mixture of 17 mass ratioes composition.
6. according to the method described in claim 3, it is characterized in that, in step (3), the process conditions of the electrolysis are：Electrolysis
Temperature is 500~750 DEG C, and current density is 100~150mA, and electrolysis time is 10~50s.
7. according to the method described in claim 1, it is characterized in that, the solar cell is silica-based solar cell.
8. according to the method described in claim 1, it is characterized in that, the solar energy heat collector is selected from flat panel solar heat collecting
Any one of device, trough type solar heat-collector, vacuum tube solar heating element.
9. according to the method described in claim 1, it is characterized in that, before degradation, organic waste is put by working electrode and to electrode
In water, waste water temperature is warming up to 60~90 DEG C using the solar energy heat collector, then in dark surrounds and no power
Under conditions of stand 10~20min.
10. according to claim 1 to 9 any one of them method, which is characterized in that the organic wastewater is to contain dodecyl
The trade effluent or sanitary sewage of benzene sulfonic acid sodium salt and/or nitrobenzene.
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| CN110655257A (en) * | 2019-10-15 | 2020-01-07 | 东北石油大学 | Phenol wastewater treatment method |
| CN110655257B (en) * | 2019-10-15 | 2021-12-21 | 东北石油大学 | Phenol wastewater treatment method |
| CN113398904A (en) * | 2021-05-06 | 2021-09-17 | 桂林电子科技大学 | Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds) |
| 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 |
| CN113583712A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Multi-energy coupling complementary and sequential conversion system and method |
| CN114590859A (en) * | 2022-03-24 | 2022-06-07 | 东北石油大学 | Method for treating oily sewage by solar STEP light-heat-electric coupling |
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