CN108147505A - A kind of device and method of Driven by Solar Energy wastewater treatment coupling production hydrogen - Google Patents

A kind of device and method of Driven by Solar Energy wastewater treatment coupling production hydrogen Download PDF

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Publication number
CN108147505A
CN108147505A CN201711375577.0A CN201711375577A CN108147505A CN 108147505 A CN108147505 A CN 108147505A CN 201711375577 A CN201711375577 A CN 201711375577A CN 108147505 A CN108147505 A CN 108147505A
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waste water
water
pipe
cathode
hydrogen
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CN108147505B (en
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汪群慧
倪金
史慧敏
夏德宏
徐元晟
高明
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C02F2201/009—Apparatus with independent power supply, e.g. solar cells, windpower, fuel cells
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses the device and methods that a kind of Driven by Solar Energy wastewater treatment couples production hydrogen.The device includes three-dimensional catalysis electrode reactor and photoelectricity, pipeline, water storage and hydrogen collection, and the solid catalysis electrode reactor includes univalent cation exchange membrane and the anode chamber and the cathode chamber.Cathode-anode plate is respectively equipped in described the anode chamber and the cathode chamber.Described the anode chamber and the cathode chamber respectively fills carried active carbon particle, forms three-dimensional catalysis electrode anode and cathode group.Electro-optical system includes solar energy photovoltaic panel, regulated power supply and single-pole double-throw switch (SPDT).Pipe-line system includes waste water water inlet pipe and water outlet pipe, waste water ingress pipe and pump, return of waste water pipe, wastewater effluent valve；Sig water ingress pipe and pump, high alkali liquid return duct, high alkali liquid outlet pipe and valve.The water retention system includes waste water and lye storage tank.The hydrogen collection includes hydrogen gas tank and gas-guide tube.This method handles waste water using Driven by Solar Energy, and water outlet COD removal rates are 70% 80%, and simultaneous hydrogen production tolerance is 1 2L/h.

Description

A kind of device and method of Driven by Solar Energy wastewater treatment coupling production hydrogen
Technical field
The invention belongs to environmental protection water treatment field/electrochemistry/new energy fields, and in particular to one kind can synchronize place It manages used water difficult to degradate and produces the Driven by Solar Energy electro-chemical systems of hydrogen.
Background technology
In recent years, it with the rapid development of the industries such as petrochemical industry, plastics, synthetic fibers, coking, printing and dyeing, generates therewith A large amount of used water difficult to degradate includes dyeing waste water, acrylic fiber wastewater, coking wastewater etc., such water have organic pollution content it is high, The features such as coloration is high, acid-base property is big, complex in composition, change of water quality is big, biodegradability poor (B/C is less than 0.3).Therefore, it often needs Want high-level oxidation technology, such as ozone, Fenton and electrolysis tech carry out the pretreatment of used water difficult to degradate, though however ozone have it is extremely strong Oxidation, but ozone molecule is selectively oxidized, and oxidability and effect promote thus not as good as hydroxyl radical free radical Ozone decomposed generates method for oxidation such as ozone/ultraviolet, ozone/H of more hydroxyl radical free radicals2O2Technique is researched and developed, but Be ozone preparation energy consumption is higher, mass-transfer efficiency is relatively low, the ozone tail gas of effusion not only pollutes ambient atmosphere environment, but also can be right Operator brings serious acute or chronic health hazards.H in Fenton technology2O2In Fe3+Under the action of catalyst, production Raw a large amount of hydroxyl radical free radical, it is preferable to used water difficult to degradate degradation effect, but the technology needs to use a large amount of H2O2, waste water Processing cost it is higher.In traditional two-dimentional electrolysis tech, the impedance between pole plate is big, so voltage or electricity between needing pole plate Current density is sufficiently large, can be only achieved preferable treatment effect, therefore energy consumption is excessive.
Therefore it finds a kind of not only free from environmental pollution but also Health cost will not be brought to operator, while low energy consumption and has The wastewater treatment method having an economic benefit is extremely urgent.Solar energy is the inexhaustible energy, and hydrogen is also can be again The raw energy, and its unit mass calorific value highest, belong to cleaning green energy resource.Apparatus of the present invention utilize Driven by Solar Energy, will too Sun can be converted into direct current and supply electricity to electrolyzer with electricity, and the active carbon particle electrode of supported catalyst is filled between two-plate, be formed Three-dimensional catalysis electrode substantially reduces the hindrance function between two-plate, improves the degradation efficiency and hydrogen of used water difficult to degradate Yield.The anode chamber and the cathode chamber is separated by univalent cation exchange membrane, and anode chamber carries out the degradation of waste water, reduces the COD of waste water；Cathode chamber Coupling production hydrogen simultaneously concentrates lye.
Invention content
The present invention provides a kind of devices for integrating refractory wastewater, hydrogen producing, are Driven by Solar Energy, can be most The utilization of limits and generation clean energy resource, while handle waste water.The device has the characteristics that green, environmentally friendly, energy saving.
The technical scheme is that：A kind of device of Driven by Solar Energy wastewater treatment coupling production hydrogen, described device include Three-dimensional catalysis electrode reactor, electro-optical system, pipe-line system, water retention system and hydrogen collection, the three-dimensional catalysis electricity Pole reactor includes univalent cation exchange membrane, anode chamber and cathode chamber；Sun is respectively arranged in the anode chamber and cathode chamber Pole electrode plate and cathode electrode plate；The anode chamber and cathode chamber respectively fill carried active carbon mosaic electrode, are formed three-dimensional Catalysis electrode anode clusters and cathode group；The electro-optical system includes solar energy photovoltaic panel 7, voltage stabilizing emergency power supply 8 and single-pole double throw Switch；The pipe-line system include wastewater inlet pipe, waste water ingress pipe, waste water import pump, return of waste water pipe, wastewater effluent valve, Waste water outlet pipe；Sig water ingress pipe, sig water import pump, high alkali liquid return duct, high alkali liquid outlet valve, high alkali liquid outlet pipe； The water retention system includes waste water tank, lye storage tank；The hydrogen collection includes gas-guide tube and hydrogen gas tank.
It is preferable over, active carbon particle electrode surface can load gamma MnO2。
Be preferable over, active carbon particle can be blocky-shaped particle, grain size 2-4mm；Active carbon particle can be cylindrical particle, Grain size is 2mm, 4mm and 6mm；The raw material of active carbon particle is prepared as a kind of or both composition in coconut husk and shell.
It is preferable over, anode electrode plate material is：Ti/RuO2One kind of electrode plate and Pt electrode plates；Cathode electrode plate material For：One kind in stainless steel fibre felt electrode plate, glassy carbon electrode plate, Cu electrode plates and graphite electrode plate, between medium between anodic-cathodic plate Away from 3-10cm.
It is preferable over, solar energy is converted into direct current energy by solar energy photovoltaic panel, is powered for three-dimensional catalysis electrode；Pass through Single-pole double-throw switch (SPDT) can make the device power in fine day using solar energy photovoltaic panel, without can be used voltage stabilizing should during sunlight Urgent telegram source works on.
It is preferable over, the device of production hydrogen is coupled using Driven by Solar Energy wastewater treatment, is included the following steps：
Step 1：Fill a certain amount of area load gamma MnO respectively in anode chamber and cathode chamber2Activated carbon Grain；
Step 2：Pending waste water is injected into waste water tank, then import pump through anolyte and pass through sun by wastewater inlet pipe Pole liquid ingress pipe enters anode chamber；Sig water imports pump by catholyte and enters cathode chamber by catholyte ingress pipe, connects electricity Source, the organic pollution of anolyte are degraded and decolourize in anode chamber；H in cathode chamber+It obtains being electronically generated hydrogen on cathode, OH-Accumulation increases catholyte basicity, and above-mentioned sig water is the waste water that the concentrated base that cathode chamber of the present invention obtains is obtained with anode chamber Water outlet is configured；
Step 3：Meanwhile anolyte is back to waste water tank；Catholyte is back to lye storage tank, H2Pass through gas-guide tube again Into hydrogen gas tank；
Step 4：After cyclic electrolysis after a period of time, the alkali after being concentrated is discharged from high alkali liquid outlet pipe, is cleaned Waste water afterwards is discharged from waste water outlet pipe, and which part high alkali liquid and purified water are configured to the sig water that concentration is less than 0.4g/L, It is used for next batch refractory wastewater.
It is preferable over, pending waste water is less than the waste water of 0.3 difficult for biological degradation for B/C ratios.
It is preferable over, one or two kinds of combinations of the lye that cathode chamber adds in for dilute NaOH solution and dilute KOH solution, concentration is low In 0.4g/L.
It is preferable over, waste water enters in three-dimensional catalysis electrode reactor, hydraulic detention time 3-20min, current density 100- 200mA/cm2, processing time 1-3h.
It is preferable over, sig water and active carbon particle only need to disposably be put into, and lye constantly generates during electrolysis cycle And it is concentrated；The organic matter adsorbed on active carbon particle by electrochemical decomposition, therefore can Reusability, without needing to change.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
(1) electronics transfer and conservation principle are rationally utilized, while handling waste water, coupling prepares calorific value height and to clean energy Source-hydrogen, and the processing for used water difficult to degradate provides a new thinking.
(2) compared with traditional electrolysis, the electrode surface area of unit sump volume is increased, also makes virtual electrode spacing It greatly shortens, increases mass transfer rate, electrolytic efficiency improves 2 to 3 times；Due to the inhomogeneities of active carbon particle in itself, cause It locally generates larger current density (point effect), and the larger molecular organics in waste water can be degraded rapidly.
(3) active carbon particle electrode is once put into, can multiple Reusability, greatly reduce processing waste water consumables cost.
(4) cation in anode chamber (predominantly hydrogen ion and alkali metal) moves to the moon through univalent cation exchange membrane Pole room, the H of migration+With water power from H+It obtains being electronically generated hydrogen (2H on cathode++2e-=H2), and OH-Accumulation and and alkali Metal ion combines, so as to recyclable concentrated base.Energy saving, emission reduction, production capacity, the multipurpose for recycling alkali are realized, this method utilizes Driven by Solar Energy handles waste water, and water outlet COD removal rates are 70%-80%, and simultaneous hydrogen production tolerance is 1-2L/h.
Description of the drawings
Fig. 1 is a kind of structure diagram of the device of Driven by Solar Energy wastewater treatment coupling production hydrogen of the present invention.
Fig. 2 (a) is the chroma removal rate curve synoptic diagram of present invention processing dyeing waste water.
Fig. 2 (b) is the COD removal rate curve synoptic diagrams of present invention processing dyeing waste water.
Fig. 2 (c) couples hydrogen output curve synoptic diagram for present invention processing dyeing waste water.
In figure：
1. univalent cation exchange membrane, 2. anode chambers, 3. cathode chambers, 4. anode electrode plates, 5. cathode electrode plates, 6, work Property charcoal mosaic electrode, 7. solar energy photovoltaic panels, 8. voltage stabilizing emergency power supplies, 9. single-pole double-throw switch (SPDT)s, 10. wastewater inlet pipes, 11a. Waste water ingress pipe, 11b. sig waters ingress pipe, 12a. waste water import pump, 12b. sig waters import pump, 13a. return of waste waters Guan Shui Valve, 13b. sig waters return duct, 14a. wastewater effluents valve, 14b. high alkali liquids outlet valve, 15a. waste water outlet pipes, 15b. concentrated bases Liquid outlet pipe, 16. waste water tanks, 17. lye storage tanks, 18. gas-guide tubes, 19. hydrogen gas tanks.
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end Same or similar label represents same or similar element or the element with identical similar functions.Below with reference to additional The embodiment of figure description is exemplary, and is only used for explaining the present invention, and cannot be construed to the limitation of the present invention.
With reference to following description and attached drawing, it will be clear that these and other aspects of the embodiment of the present invention.In these descriptions In attached drawing, some specific embodiments in the embodiment of the present invention are specifically disclosed, to represent to implement the reality of the present invention Some modes of the principle of example are applied, it is to be understood that, the scope of embodiments of the invention is not limited.On the contrary, the present invention Embodiment includes falling into all changes, modification and the equivalent in the range of the spirit and intension of attached claims.
As described in Figure 1, a kind of device of Driven by Solar Energy wastewater treatment coupling production hydrogen of the present invention, described device include being used for Handle waste water, and generate the three-dimensional catalysis electrode reactor of hydrogen, the electro-optical system for power supply, pipe-line system, for storing The water retention system of waste water and the hydrogen collection for collecting hydrogen；
Wherein, the three-dimensional catalysis electrode reactor by the pipe-line system respectively with the water retention system and hydrogen Collection system connects, and the electro-optical system is to the three-dimensional catalysis electrode reactor power supply.
The structure of described device is：
The solid catalysis electrode reactor includes univalent cation exchange membrane 1, anode chamber 2 and cathode chamber 3；
The electro-optical system includes solar energy photovoltaic panel 7, voltage stabilizing emergency power supply 8 and single-pole double-throw switch (SPDT) 9；
The pipe-line system includes wastewater inlet pipe 10, waste water ingress pipe 11a, waste water and imports pump 12a, return of waste water pipe 13a, wastewater effluent valve 14a, waste water outlet pipe 15a；Sig water ingress pipe 11b, sig water import pump 12b, high alkali liquid return duct 13b, high alkali liquid outlet valve 14b, high alkali liquid outlet pipe 15b；
The water retention system includes waste water tank 16, lye storage tank 17；
The hydrogen collection includes gas-guide tube 18 and hydrogen gas tank 19.
Wherein, anode electrode plate 4 and cathode electrode plate 5 are respectively arranged in the anode chamber 2 and cathode chamber 3；The sun Pole room 2 and cathode chamber 3 respectively fill carried active carbon mosaic electrode 6, form three-dimensional catalysis electrode anode clusters and cathode group；Institute It states waste water tank 16 and lye storage tank 17 is separately positioned on 3 both ends of the anode chamber 2 and cathode chamber, the waste water tank 16 passes through Waste water imports pump 12a and waste water ingress pipe 11a and is connect with the bottom of the anode chamber 2, and the anode chamber 2 passes through waste water Return duct 13a is connect with the top of the waste water tank 16, and the wastewater inlet pipe 10 and wastewater effluent valve 14a are arranged on institute State on waste water tank 16, the waste water outlet pipe 15a is arranged on the wastewater effluent valve 14a,
The lye storage tank 17 imports the bottom of pump 12b and sig water ingress pipe 11b and the cathode chamber 3 by sig water Connection, the cathode chamber 3 are connect by high alkali liquid return duct 13b with the top of the lye storage tank 17, the lye storage tank 17 Bottom be equipped with high alkali liquid outlet pipe 15b, the high alkali liquid outlet valve 14b is arranged on the high alkali liquid outlet pipe 15b, described Hydrogen gas tank 19 is connect by the gas-guide tube 18 with the lye storage tank 17；
One end of the solar energy photovoltaic panel 7 connects respectively with the anode electrode plate 4 and 9 one end of the single-pole double-throw switch (SPDT) It connecing, 7 other end of solar energy photovoltaic panel is connect respectively with the voltage stabilizing emergency power supply 8 and 9 one end of the single-pole double-throw switch (SPDT), The connection with the cathode electrode plate 5 and the single-pole double-throw switch (SPDT) 9 respectively of the other end of the voltage stabilizing emergency power supply 8；
4 material of anode electrode plate is：Ti/RuO2One kind of electrode plate and Pt electrode plates；5 material of cathode electrode plate For：One kind in stainless steel fibre felt electrode plate, glassy carbon electrode plate, Cu electrode plates and graphite electrode plate, the anode electrode Spacing between plate 3 and the cathode electrode plate 4 is 3-10cm.
The area load of the active carbon particle electrode 6 has gamma MnO2Particle, the surface of the active carbon particle electrode 6 Load has gamma MnO2The concrete technology of particle is：Step 1：Active carbon particle is filled in anode electrode plate and cathode electricity first Between pole plate, meanwhile, MnSO is added in electrolytic cell4Solution and H2SO4The mixed solution of solution is electrolyte；
Step 2. carries out electrodeposit reaction:Circuit is connected with certain voltage or current density, is passed through certain density oxygen Gas evenly spreads to 7 gap of active carbon particle by even gas distribution plate；
Step 3：Electrolytic cell is in heating water bath state, carries out electro-deposition for a period of time；
Step 4：After electro-deposition, active carbon particle after load is taken out, is rinsed with water, removal activated carbon granule surface is not The MnSO reacted4Solution and H2SO4Solution, and at a suitable temperature dry a period of time to get to load gamma MnO2's Active carbon particle electrode.
The active carbon particle is a kind of or both composition in coconut husk and shell, and the active carbon particle is block Shape particle, grain size 2-4mm；Or for cylindrical particle, grain size 2mm, 4mm and 6mm；The raw material for preparing active carbon particle is coconut palm A kind of or both composition in shell and shell.
MnSO in the step 14Solution and H2SO4Solution ratio is：MnSO4A concentration of 100-120g/L of solution, H2SO4A concentration of 20-40g/L；Water bath heating temperature in the step 2 is 70-80 DEG C, electrodeposition time 1-2h, is led to The gas entered is high purity oxygen gas, one or two kinds of in air；In step 2 voltage of electrodeposit reaction for 10-20V or Current density is 50-100mA/cm2。
A kind of method using described device processing waste water coupling production hydrogen, which is characterized in that include the following steps：
Step 1：Fill a certain amount of area load gamma MnO respectively in anode chamber 2 and cathode chamber 32Activated carbon Particle；
Step 2：Pending waste water is injected into waste water tank 16, then import pump 12a through anolyte by wastewater inlet pipe 10 Anode chamber 2 is entered by anolyte ingress pipe 11a；Sig water by catholyte import pump 12b by catholyte ingress pipe 11b into Enter cathode chamber 3, power on, the organic pollution of anolyte is degraded and decolourizes in anode chamber 2；H in cathode chamber 3+In cathode On obtain being electronically generated hydrogen, OH-Accumulation increases catholyte basicity；
Step 3：Meanwhile anolyte is back to waste water tank 16；Catholyte is back to lye storage tank 17, H2Again by leading Tracheae 18 enters hydrogen gas tank 19；
Step 4：After cyclic electrolysis after a period of time, the alkali after being concentrated is discharged from high alkali liquid outlet pipe 15b, quilt Purified waste water is discharged from waste water outlet pipe 15a, and which part high alkali liquid and purified water are configured to concentration less than 0.4g/L's Sig water is used for next batch refractory wastewater.
The pending waste water is less than the waste water of 0.3 difficult for biological degradation for B/C ratios；The lye that the cathode chamber adds in is One or two kinds of combinations of dilute NaOH solution and dilute KOH solution, concentration are less than 0.4g/L.
The waste water enters in three-dimensional catalysis electrode reactor, hydraulic detention time 3-20min, current density 100- 200mA/cm2, processing time 1-3h.
Active carbon particle should be filled in anode chamber and cathode chamber, and packed height is flushed with electrode plate.
Comparative example 1
Experiment condition is：Rhodamine B dyeing waste water initial concentration is 100mg/L, processing water 3L, pH=7,2g/L
Na2SO4The waste water is passed through in ordinary two dimensional electrode reactor anode chamber by electrolyte, and photovoltaic panel provides current density 100mA/cm2, hydraulic detention time (HRT) is 10min, and processing time is 3 hours, and cathode chamber lye is NaOH, a concentration of 0.2g/L。
Comparative example 2
Experiment condition is：Rhodamine B dyeing waste water initial concentration is 100mg/L, processing water 3L, pH=7,2g/L
Na2SO4The waste water is passed through in three-dimensional catalysis electrode reactor anode chamber by electrolyte, wherein mosaic electrode for by The active carbon particle (unsupported catalyst) of dyeing waste water adsorption saturation, grain size provide current density in 2-4mm, photovoltaic panel 100mA/cm2, hydraulic detention time (HRT)
For 10min, processing time is 3 hours, and cathode chamber lye is NaOH, a concentration of 0.2g/L.
Embodiment
Experiment condition is：Rhodamine B dyeing waste water initial concentration is 100mg/L, processing water 3L, pH=7,2g/L
Na2SO4The waste water is passed through in three-dimensional catalysis electrode reactor anode chamber by electrolyte, wherein mosaic electrode for by Dyeing waste water adsorption saturation and load gamma MnO2Active carbon particle, grain size provide current density in 2-4mm, photovoltaic panel 100mA/cm2, hydraulic detention time (HRT) is 10min, and processing time is 3 hours, and cathode chamber lye is NaOH, a concentration of 0.2g/L。
By Fig. 2 (a), 2 (b) and 2 (c) is as can be seen that a kind of Driven by Solar Energy wastewater treatment coupling of the present invention The device and method of hydrogen is produced, by filling load gamma MnO in the anode chamber and the cathode chamber2Active carbon particle electrode improves the color of waste water The removal efficiency of degree and COD, meanwhile, the yield of hydrogen also greatly improves.

Claims (10)

1. a kind of device of Driven by Solar Energy wastewater treatment coupling production hydrogen, which is characterized in that described device includes useless for handling Water, and generate the three-dimensional catalysis electrode reactor of hydrogen, the electro-optical system for power supply, pipe-line system, for storing waste water Water retention system and the hydrogen collection for collecting hydrogen；
Wherein, the three-dimensional catalysis electrode reactor by the pipe-line system respectively with the water retention system and Hydrogen collection System connects, and the electro-optical system is to the three-dimensional catalysis electrode reactor power supply.
2. the apparatus according to claim 1, which is characterized in that the structure of described device is：
The solid catalysis electrode reactor includes univalent cation exchange membrane（1）, anode chamber（2）And cathode chamber（3）；
The electro-optical system includes solar energy photovoltaic panel（7）, voltage stabilizing emergency power supply（8）And single-pole double-throw switch (SPDT)（9）；
The pipe-line system includes wastewater inlet pipe（10）, waste water ingress pipe（11a）, waste water import pump（12a）, return of waste water pipe （13a）, wastewater effluent valve（14a）, waste water outlet pipe（15a）；Sig water ingress pipe（11b）, sig water import pump（12b）, it is dense Lye return duct（13b）, high alkali liquid outlet valve（14b）, high alkali liquid outlet pipe（15b）；
The water retention system includes waste water tank（16）, lye storage tank（17）；
The hydrogen collection includes gas-guide tube（18）And hydrogen gas tank（19）；
Wherein, the anode chamber（2）And cathode chamber（3）Inside it is respectively arranged with anode electrode plate（4）And cathode electrode plate（5）；Institute State anode chamber（2）And cathode chamber（3）Respectively filling carried active carbon mosaic electrode（6）, form three-dimensional catalysis electrode anode clusters With cathode group；The waste water tank（16）With lye storage tank（17）It is separately positioned on the anode chamber（2）And cathode chamber（3）Two End, the waste water tank（16）It is imported and pumped by waste water（12a）With waste water ingress pipe（11a）With the anode chamber（2）'s Bottom connects, the anode chamber（2）Pass through return of waste water pipe（13a）With the waste water tank（16）Top connection, it is described useless Water water inlet pipe（10）With wastewater effluent valve（14a）It is arranged on the waste water tank（16）Upper, described waste water outlet pipe（15a）Setting In the wastewater effluent valve（14a）On,
The lye storage tank（17）It is imported and pumped by sig water（12b）With sig water ingress pipe（11b）With the cathode chamber（3）'s Bottom connects, the cathode chamber（3）Pass through high alkali liquid return duct（13b）With the lye storage tank（17）Top connection, it is described Lye storage tank（17）Bottom be equipped with high alkali liquid outlet pipe（15b）, the high alkali liquid outlet valve（14b）It is arranged on the high alkali liquid Outlet pipe（15b）On, the hydrogen gas tank（19）Pass through the gas-guide tube（18）With the lye storage tank（17）Connection；
The solar energy photovoltaic panel（7）One end respectively with the anode electrode plate（4）With the single-pole double-throw switch (SPDT)（9）One end Connection, the solar energy photovoltaic panel（7）The other end respectively with the voltage stabilizing emergency power supply（8）With the single-pole double-throw switch (SPDT)（9） One end connects, the voltage stabilizing emergency power supply（8）The other end respectively with the cathode electrode plate（5）With the single-pole double-throw switch (SPDT) （9）Connection.
3. the device of a kind of Driven by Solar Energy wastewater treatment coupling production hydrogen according to claim 2, which is characterized in that described Anode electrode plate（4）Material is：Ti/RuO2One kind of electrode plate and Pt electrode plates；Cathode electrode plate（5）Material is：Stainless steel One kind in fibre felt electrode plate, glassy carbon electrode plate, Cu electrode plates and graphite electrode plate, the anode electrode plate（3）And institute State cathode electrode plate（4）Between spacing be 3-10cm.
4. the apparatus of claim 2, which is characterized in that the active carbon particle electrode（6）Area load have gal Horse MnO2Particle.
5. device according to claim 3, which is characterized in that the active carbon particle electrode（6）Area load have Gamma MnO2The concrete technology of particle is：Step 1：First by active carbon particle be filled in anode electrode plate and cathode electrode plate it Between, meanwhile, MnSO is added in electrolytic cell4Solution and H2SO4The mixed solution of solution is electrolyte；
Step 2. carries out electrodeposit reaction:Circuit is connected with certain voltage or current density, is passed through certain density oxygen, is led to It crosses even gas distribution plate and evenly spreads to active carbon particle gap；
Step 3：Electrolytic cell is in heating water bath state, carries out electro-deposition for a period of time；
Step 4：After electro-deposition, active carbon particle is taken out, is rinsed with water, removal activated carbon granule surface unreacted is complete MnSO4Solution and H2SO4Solution, and at a suitable temperature dry a period of time to get to load gamma MnO2Activated carbon Grain electrode.
6. device according to claim 5, which is characterized in that the active carbon particle be coconut husk and shell in one kind or The composition of both persons, the active carbon particle be blocky-shaped particle, grain size 2-4mm；Or for cylindrical particle, grain size 2mm, 4mm and 6mm；The raw material of active carbon particle is prepared as a kind of or both composition in coconut husk and shell.
7. device according to claim 5, which is characterized in that MnSO in the step 14Solution and H2SO4Solution ratio For：MnSO4A concentration of 100-120g/L, H of solution2SO4A concentration of 20-40g/L；Water bath heating temperature in the step 3 It it is 70-80 DEG C, electrodeposition time 1-2h, the gas being passed through is high purity oxygen gas, one or two kinds of in air；In step 2 The voltage of electrodeposit reaction is 10-20V or current density is 50-100mA/cm2。
8. a kind of method of device processing waste water coupling production hydrogen using as described in claim 1-7 any one, feature exist In including the following steps：
Step 1：In anode chamber（2）And cathode chamber（3）It is middle to fill a certain amount of area load gamma MnO respectively2Activated carbon Grain；
Step 2：Pending waste water is passed through into wastewater inlet pipe（10）Inject waste water tank（16）, then import and pump through anolyte （12a）Pass through anolyte ingress pipe（11a）Into anode chamber（2）；Sig water is imported by catholyte and pumped（12b）Pass through catholyte Ingress pipe（11b）Into cathode chamber（3）, power on, the organic pollution of anolyte is in anode chamber（2）It is degraded and decolourizes； Cathode chamber（3）Middle H+It obtains being electronically generated hydrogen, OH on cathode-Accumulation increases catholyte basicity, and above-mentioned sig water is this hair The wastewater effluent that the concentrated base that bright cathode chamber obtains is obtained with anode chamber is configured；
Step 3：Meanwhile anolyte is back to waste water tank（16）；Catholyte is back to lye storage tank（17）, H2Pass through air guide again Pipe（18）Into hydrogen gas tank（19）；
Step 4：After cyclic electrolysis after a period of time, alkali after being concentrated is from high alkali liquid outlet pipe（15b）Discharge, it is net Waste water after change is from waste water outlet pipe（15a）Discharge, the sig water which part high alkali liquid and purified water are configured to, for next group Secondary refractory wastewater uses.
9. according to the method described in claim 8, it is characterized in that：The pending waste water is less than 0.3 hardly possible biology for B/C ratios The waste water of degradation；One or two kinds of combinations of the sig water that the cathode chamber adds in for dilute NaOH solution and dilute KOH solution, concentration Less than 0.4g/L.
10. too method according to claim 8, it is characterised in that：The waste water enters in three-dimensional catalysis electrode reactor, Hydraulic detention time 3-20min, current density 100-200mA/cm2, processing time 1-3h.
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