CN108147505B - Device and method for producing hydrogen by coupling solar-driven wastewater treatment - Google Patents

Device and method for producing hydrogen by coupling solar-driven wastewater treatment Download PDF

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CN108147505B
CN108147505B CN201711375577.0A CN201711375577A CN108147505B CN 108147505 B CN108147505 B CN 108147505B CN 201711375577 A CN201711375577 A CN 201711375577A CN 108147505 B CN108147505 B CN 108147505B
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wastewater
alkali liquor
cathode
pipe
hydrogen
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CN108147505A (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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    • 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

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Abstract

The invention discloses a device and a method for producing hydrogen by coupling solar-driven wastewater treatment. The device comprises a three-dimensional catalytic electrode reactor and a photoelectric, pipeline, water storage and hydrogen collection system, wherein the three-dimensional catalytic electrode reactor comprises a monovalent cation exchange membrane and an anode chamber and a cathode chamber. And the cathode and anode chambers are respectively provided with a cathode plate and an anode plate. And the cathode and anode chambers are respectively filled with loaded activated carbon particles to form a three-dimensional catalytic electrode cathode and anode group. The photoelectric system comprises a solar photovoltaic panel, a stabilized voltage power supply and a single-pole double-throw switch. The pipeline system comprises a wastewater inlet and outlet pipe, a wastewater inlet pipe, a wastewater outlet pipe, a pump, a wastewater return pipe and a wastewater outlet valve; a dilute alkali liquor leading-in pipe and a pump, a concentrated alkali liquor return pipe, a concentrated alkali liquor outlet pipe and a valve. The water storage system comprises a waste water and alkali liquor storage tank. The hydrogen collecting system comprises a hydrogen tank and an air guide pipe. The method utilizes solar energy to drive and treat the wastewater, the COD removal rate of the effluent is 70-80%, and the hydrogen production amount is 1-2L/h.

Description

Device and method for producing hydrogen by coupling solar-driven wastewater treatment
Technical Field
The invention belongs to the field of environmental protection water treatment/electrochemistry/new energy, and particularly relates to a solar-driven electrochemical system capable of synchronously treating refractory wastewater and producing hydrogen.
Background
In recent years, with the rapid development of petrochemical industry, plastics, synthetic fibers, coking, printing and dyeing and the like, a large amount of non-degradable wastewater including printing and dyeing wastewater, acrylic fiber wastewater, coking wastewater and the like is generated, and the water has the characteristics of high organic pollutant content, high chromaticity, high acidity and alkalinity, complex components, large water quality change, poor biodegradability (B/C is less than 0.3) and the like. Therefore, advanced oxidation technologies such as ozone, fenton and electrolysis are often required to pretreat the wastewater difficult to degrade, but ozone has a strong oxidation effect, but the ozone molecule is selectively oxidized, and the oxidation capability and effect are not as good as that of hydroxyl radicals, so that the oxidation method for promoting the ozone decomposition to generate more hydroxyl radicals such as ozone/ultraviolet, ozone/H2O2The process is researched and developed, but the preparation of ozone canThe consumption is high, the mass transfer efficiency is low, and the escaped ozone tail gas not only pollutes the surrounding atmospheric environment, but also brings serious acute or chronic health injury to operators. Fenton technique H2O2In Fe3+Under the action of the catalyst, a large amount of hydroxyl free radicals are generated, the degradation effect on the difficultly degraded wastewater is good, but the technology needs to use a large amount of H2O2The treatment cost of the waste water is high. In the traditional two-dimensional electrolysis technology, the impedance between the polar plates is large, so that the voltage or current density between the polar plates is required to be large enough to achieve a better treatment effect, and the energy consumption is overlarge.
Therefore, it is urgent to find a method for treating wastewater which does not pollute the environment, does not cause health damage to operators, and has low energy consumption and economic benefits. Solar energy is inexhaustible energy, hydrogen is renewable energy, and the heat value per unit mass is highest, so that the solar energy belongs to clean green energy. The device of the invention utilizes solar energy to drive, converts the solar energy into direct current to supply power to the electrolytic cell, and fills the activated carbon particle electrode loaded with the catalyst between the two polar plates to form a three-dimensional catalytic electrode, thereby greatly reducing the impedance effect between the two polar plates and improving the degradation efficiency of the waste water difficult to degrade and the yield of hydrogen. The anode chamber and the cathode chamber are separated by a monovalent cation exchange membrane, and the anode chamber is used for degrading the wastewater and reducing the COD of the wastewater; the cathode chamber is coupled to produce hydrogen and concentrate alkali liquor.
Disclosure of Invention
The invention provides a device integrating treatment of refractory wastewater and hydrogen production, which is driven by solar energy, can utilize and generate clean energy to the maximum extent and treat wastewater simultaneously. The device has the characteristics of green, environmental protection and energy conservation.
The technical scheme of the invention is as follows: a device for producing hydrogen by coupling solar-driven wastewater treatment comprises a three-dimensional catalytic electrode reactor, a photoelectric system, a pipeline system, a water storage system and a hydrogen collecting system, wherein the three-dimensional catalytic electrode reactor comprises a monovalent cation exchange membrane, an anode chamber and a cathode chamber; an anode electrode plate and a cathode electrode plate are respectively arranged in the anode chamber and the cathode chamber; the anode chamber and the cathode chamber are respectively filled with loaded activated carbon particle electrodes to form a three-dimensional catalytic electrode anode group and a three-dimensional catalytic electrode cathode group; the photovoltaic system comprises a solar photovoltaic panel 7, a voltage-stabilizing emergency power supply 8 and a single-pole double-throw switch; the pipeline system comprises a wastewater inlet pipe, a wastewater inlet pump, a wastewater return pipe, a wastewater outlet valve and a wastewater outlet pipe; a dilute alkali liquid lead-in pipe, a dilute alkali liquid lead-in pump, a concentrated alkali liquid return pipe, a concentrated alkali liquid outlet valve and a concentrated alkali liquid outlet pipe; the water storage system comprises a waste water storage tank and an alkali liquor storage tank; the hydrogen collecting system comprises a gas guide pipe and a hydrogen tank.
Preferably, the surface of the activated carbon particle electrode can be loaded with gamma MnO2。
Preferably, the activated carbon particles can be blocky particles with the particle size of 2-4 mm; the activated carbon particles can be columnar particles with the particle sizes of 2mm, 4mm and 6 mm; the raw material for preparing the activated carbon particles is one or a combination of coconut shells and fruit shells.
Preferably, the anode electrode plate is made of: Ti/RuO2One of an electrode plate and a Pt electrode plate; the cathode electrode plate is made of the following materials: one of a stainless steel fibrofelt electrode plate, a glass carbon electrode plate, a Cu electrode plate and a graphite electrode plate, wherein the distance between the positive electrode plate and the negative electrode plate is 3-10 cm.
Preferably, the solar photovoltaic panel directly converts solar energy into direct current electric energy to supply power for the three-dimensional catalytic electrode; through the single-pole double-throw switch, the device can use the solar photovoltaic panel to supply power in sunny days, and can use the voltage-stabilizing emergency power supply to continue working when no sunlight exists.
Preferably, the device for producing hydrogen by coupling solar-driven wastewater treatment comprises the following steps:
the method comprises the following steps: respectively filling a certain amount of surface-loaded gamma MnO in the anode chamber and the cathode chamber2The activated carbon particles of (1);
step two: injecting wastewater to be treated into a wastewater storage tank through a wastewater inlet pipe, and then entering an anode chamber through an anode fluid inlet pipe through an anode fluid inlet pump; the dilute alkali liquor enters the cathode chamber through the catholyte lead-in pump and the catholyte lead-in pipe, and then the power is switched on and the anode is connectedOrganic pollutants of the polar liquid are degraded and decolored in the anode chamber; in the cathode chamber H+Obtaining electrons at the cathode to form hydrogen, OH-Accumulating to raise the alkalinity of the catholyte, wherein the dilute alkali solution is prepared by the concentrated alkali obtained from the cathode chamber and the wastewater effluent obtained from the anode chamber;
step three: meanwhile, the anolyte flows back to the waste water storage tank; the catholyte flows back to the alkali liquor storage tank, H2Then enters a hydrogen tank through a gas guide pipe;
step four: after a period of circulating electrolysis, the concentrated alkali is discharged from the concentrated alkali liquor outlet pipe, the purified wastewater is discharged from the wastewater outlet pipe, wherein part of the concentrated alkali liquor and the purified water are prepared into dilute alkali liquor with the concentration of less than 0.4g/L for the treatment of the refractory wastewater of the next batch.
Preferably, the wastewater to be treated is a nonbiodegradable wastewater having a B/C ratio of less than 0.3.
Preferably, the alkali liquor added into the cathode chamber is one or two of dilute NaOH solution and dilute KOH solution, and the concentration is lower than 0.4 g/L.
Preferably, the wastewater enters a three-dimensional catalytic electrode reactor, the hydraulic retention time is 3-20min, and the current density is 100-2The treatment time is 1-3 h.
Preferably, the dilute alkali liquor and the activated carbon particles only need to be added once, and the alkali liquor is continuously generated and concentrated in the electrolytic circulation process; the organic matter adsorbed on the active carbon particles is electrochemically decomposed, so that the active carbon particles can be repeatedly used without replacement.
The technical scheme of the invention has the following beneficial effects:
(1) by reasonably utilizing the electron transfer and conservation principles, the coupling preparation method has high heat value while treating the wastewater, provides a new idea for the treatment of the wastewater difficult to degrade and the hydrogen which is a clean energy.
(2) Compared with the traditional electrode electrolysis, the electrode surface area of unit cell volume is increased, the actual electrode distance is greatly shortened, the mass transfer rate is increased, and the electrolysis efficiency is improved by 2 to 3 times; due to the nonuniformity of the activated carbon particles, larger current density is locally generated (tip effect), and macromolecular organic matters in the wastewater can be rapidly degraded.
(3) The active carbon particle electrode is put into once and can be repeatedly used, so that the cost of waste water treatment consumables is greatly reduced.
(4) Cations (mainly hydrogen ions and alkali metals) in the anode chamber permeate the monovalent cation exchange membrane to migrate to the cathode chamber, and migrated H+And H ionized by water+Obtaining electrons at the cathode to generate hydrogen (2H)++2e-＝H2) And OH-Accumulates and combines with alkali metal ions, so that the concentrated alkali can be recovered. The method realizes multiple purposes of energy conservation, emission reduction, capacity and alkali recovery, and utilizes solar energy to drive the treatment of the wastewater, the COD removal rate of the effluent is 70-80%, and the hydrogen production amount is 1-2L/h.
Drawings
FIG. 1 is a schematic structural diagram of a device for producing hydrogen by coupling solar-driven wastewater treatment.
FIG. 2(a) is a schematic diagram showing a chromaticity removal rate curve for treating printing and dyeing wastewater according to the present invention.
FIG. 2(b) is a diagram showing the COD removal rate curve of the printing and dyeing wastewater treated by the present invention.
FIG. 2(c) is a schematic diagram of a coupling hydrogen production curve for treating printing and dyeing wastewater according to the present invention.
In the figure:
1. the device comprises a monovalent cation exchange membrane, 2 parts of an anode chamber, 3 parts of a cathode chamber, 4 parts of an anode electrode plate, 5 parts of a cathode electrode plate, 6 parts of an activated carbon particle electrode, 7 parts of a solar photovoltaic plate, 8 parts of a voltage-stabilizing emergency power supply, 9 parts of a single-pole double-throw switch, 10 parts of a wastewater inlet pipe, 11a parts of a wastewater inlet pipe, 11b parts of a dilute alkali liquor inlet pipe, 12a parts of a wastewater inlet pump, 12b parts of a dilute alkali liquor inlet pump, 13a parts of a wastewater return pipe water valve, 13b parts of a dilute alkali liquor return pipe, 14a parts of a wastewater outlet valve, 14b parts of a concentrated alkali liquor outlet valve, 15a parts of a wastewater outlet pipe, 15b parts of a concentrated alkali liquor outlet pipe, 16 parts of a wastewater storage tank.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
These and other aspects of embodiments of the invention will be apparent with reference to the following description and attached drawings. In the description and drawings, particular embodiments of the invention have been disclosed in detail as being indicative of some of the ways in which the principles of the embodiments of the invention may be practiced, but it is understood that the scope of the embodiments of the invention is not limited correspondingly. On the contrary, the embodiments of the invention include all changes, modifications and equivalents coming within the spirit and terms of the claims appended hereto.
As shown in FIG. 1, the device for producing hydrogen by coupling solar-driven wastewater treatment comprises a three-dimensional catalytic electrode reactor for treating wastewater and generating hydrogen, a photovoltaic system for supplying power, a pipeline system, a water storage system for storing wastewater and a hydrogen collection system for collecting hydrogen;
the three-dimensional catalytic electrode reactor is respectively connected with the water storage system and the hydrogen collecting system through the pipeline system, and the photoelectric system supplies power to the three-dimensional catalytic electrode reactor.
The structure of the device is as follows:
the three-dimensional catalytic electrode reactor comprises a monovalent cation exchange membrane 1, an anode chamber 2 and a cathode chamber 3;
the photovoltaic system comprises a solar photovoltaic panel 7, a voltage-stabilizing emergency power supply 8 and a single-pole double-throw switch 9;
the pipeline system comprises a wastewater inlet pipe 10, a wastewater inlet pipe 11a, a wastewater inlet pump 12a, a wastewater return pipe 13a, a wastewater outlet valve 14a and a wastewater outlet pipe 15 a; a dilute alkali liquid lead-in pipe 11b, a dilute alkali liquid lead-in pump 12b, a concentrated alkali liquid return pipe 13b, a concentrated alkali liquid outlet valve 14b and a concentrated alkali liquid outlet pipe 15 b;
the water storage system comprises a waste water storage tank 16 and an alkali liquor storage tank 17;
the hydrogen collection system comprises a gas guide pipe 18 and a hydrogen tank 19.
Wherein, an anode electrode plate 4 and a cathode electrode plate 5 are respectively arranged in the anode chamber 2 and the cathode chamber 3; the anode chamber 2 and the cathode chamber 3 are respectively filled with a loaded activated carbon particle electrode 6 to form a three-dimensional catalytic electrode anode group and a cathode group; the wastewater storage tank 16 and the alkali liquor storage tank 17 are respectively arranged at two ends of the anode chamber 2 and the cathode chamber 3, the wastewater storage tank 16 is connected with the bottom of the anode chamber 2 through a wastewater lead-in pump 12a and a wastewater lead-in pipe 11a, the anode chamber 2 is connected with the top of the wastewater storage tank 16 through a wastewater return pipe 13a, the wastewater inlet pipe 10 and a wastewater outlet valve 14a are arranged on the wastewater storage tank 16, and the wastewater outlet pipe 15a is arranged on the wastewater outlet valve 14a.
The alkali liquor storage tank 17 is connected with the bottom of the cathode chamber 3 through a dilute alkali liquor lead-in pump 12b and a dilute alkali liquor lead-in pipe 11b, the cathode chamber 3 is connected with the top of the alkali liquor storage tank 17 through a concentrated alkali liquor return pipe 13b, a concentrated alkali liquor outlet pipe 15b is arranged at the bottom of the alkali liquor storage tank 17, a concentrated alkali liquor outlet valve 14b is arranged on the concentrated alkali liquor outlet pipe 15b, and the hydrogen tank 19 is connected with the alkali liquor storage tank 17 through the gas guide pipe 18;
one end of the solar photovoltaic panel 7 is respectively connected with the anode plate 4 and one end of the single-pole double-throw switch 9, the other end of the solar photovoltaic panel 7 is respectively connected with the voltage-stabilizing emergency power supply 8 and one end of the single-pole double-throw switch 9, and the other end of the voltage-stabilizing emergency power supply 8 is respectively connected with the cathode plate 5 and the single-pole double-throw switch 9;
the anode electrode plate 4 is made of the following materials: Ti/RuO2One of an electrode plate and a Pt electrode plate; the cathode electrode plate 5 is made of: the cathode plate comprises one of a stainless steel fiber felt electrode plate, a glass carbon electrode plate, a Cu electrode plate and a graphite electrode plate, wherein the distance between the anode electrode plate 3 and the cathode electrode plate 4 is 3-10 cm.
The surface of the active carbon particle electrode 6 is loaded with gamma MnO2Particles, the surface of the active carbon particle electrode 6 is loaded with gamma MnO2The specific process of the particles comprises the following steps: step 1: firstly, filling activated carbon particles in the sunBetween the electrode plate and the cathode electrode plate, and MnSO is added into the electrolytic bath4Solution and H2SO4The mixed solution of the solution is electrolyte;
step 2, carrying out electrodeposition reaction, namely switching on a circuit at a certain voltage or current density, introducing oxygen with a certain concentration, and uniformly dispersing the oxygen to the gaps among the activated carbon particles 7 through a gas uniform distribution plate;
and step 3: the electrolytic bath is in a water bath heating state, and electrodeposition is carried out for a period of time;
and 4, step 4: after the electrodeposition is finished, taking out the loaded activated carbon particles, washing the activated carbon particles with water, and removing unreacted MnSO on the surfaces of the activated carbon particles4Solution and H2SO4Drying the solution at a suitable temperature for a period of time to obtain the gamma-loaded MnO2The activated carbon particle electrode of (1).
The active carbon particles are one or a combination of coconut shells and fruit shells, and are blocky particles with the particle size of 2-4 mm; or columnar particles with particle diameters of 2mm, 4mm and 6 mm; the raw material for preparing the activated carbon particles is one or a combination of coconut shells and fruit shells.
MnSO in the step 14Solution and H2SO4The solution ratio is: MnSO4The concentration of the solution is 100-120g/L, H2SO4The concentration of (A) is 20-40 g/L; the water bath heating temperature in the step 2 is 70-80 ℃, the electrodeposition time is 1-2 hours, and the introduced gas is one or two of high-purity oxygen and air; the voltage of the electrodeposition reaction in the step 2 is 10-20V, or the current density is 50-100mA/cm2。
The method for producing hydrogen by coupling wastewater treatment by using the device is characterized by comprising the following steps:
the method comprises the following steps: a certain amount of surface-loaded gamma MnO is respectively filled in the anode chamber 2 and the cathode chamber 32The activated carbon particles of (1);
step two: injecting wastewater to be treated into a wastewater storage tank 16 through a wastewater inlet pipe 10, and then entering the anode chamber 2 through an anolyte lead-in pipe 11a through an anolyte lead-in pump 12 a; dilute alkali liquorThe cathode solution passing through the cathode solution lead-in pump 12b enters the cathode chamber 3 through the cathode solution lead-in pipe 11b, the power is switched on, and the organic pollutants in the anode solution are degraded and decolored in the anode chamber 2; cathode compartment 3H+Obtaining electrons at the cathode to form hydrogen, OH-The accumulation raises the alkalinity of the catholyte;
step three: meanwhile, the anolyte flows back to the waste water storage tank 16; the catholyte flows back to the alkali liquor storage tank 17, H2Then enters a hydrogen tank 19 through a gas guide pipe 18;
step four: after a period of circulating electrolysis, the concentrated alkali is discharged from the concentrated alkali liquor outlet pipe 15b, the purified wastewater is discharged from the wastewater outlet pipe 15a, wherein part of the concentrated alkali liquor and the purified water are prepared into dilute alkali liquor with the concentration lower than 0.4g/L for the next batch of refractory wastewater treatment.
The wastewater to be treated is wastewater which is difficult to biodegrade and has a B/C ratio of less than 0.3; the alkali liquor added into the cathode chamber is one or the combination of two of dilute NaOH solution and dilute KOH solution, and the concentration is lower than 0.4 g/L.
The wastewater enters a three-dimensional catalytic electrode reactor, the hydraulic retention time is 3-20min, and the current density is 100-2The treatment time is 1-3 h.
The activated carbon granules should be filled in the anode and cathode chambers to a level flush with the electrode plates.
Comparative example 1
The experimental conditions were: the initial concentration of rhodamine B printing and dyeing wastewater is 100mg/L, the treated water amount is 3L, the pH value is 7, and the treated water amount is 2g/L
Na2SO4Electrolyte, the wastewater is led into an anode chamber of a common two-dimensional electrode reactor, and a photovoltaic panel provides current density of 100mA/cm2The Hydraulic Retention Time (HRT) is 10min, the treatment time is 3 hours, and the alkali liquor in the cathode chamber is NaOH, and the concentration is 0.2 g/L.
Comparative example 2
The experimental conditions were: the initial concentration of rhodamine B printing and dyeing wastewater is 100mg/L, the treated water amount is 3L, the pH value is 7, and the treated water amount is 2g/L
Na2SO4Electrolyte, the wastewater is introduced into the anode chamber of the three-dimensional catalytic electrode reactor, wherein particlesThe particle electrode is activated carbon particles (not loaded with a catalyst) which are adsorbed and saturated by printing and dyeing wastewater, the particle diameter is 2-4mm, and the photovoltaic panel provides current density of 100mA/cm2Hydraulic Retention Time (HRT)
The treatment time is 3 hours for 10min, and the alkali liquor in the cathode chamber is NaOH, and the concentration is 0.2 g/L.
Examples
The experimental conditions were: the initial concentration of rhodamine B printing and dyeing wastewater is 100mg/L, the treated water amount is 3L, the pH value is 7, and the treated water amount is 2g/L
Na2SO4Electrolyte, the wastewater is led into the anode chamber of the three-dimensional catalytic electrode reactor, wherein the particle electrode is saturated by the printing and dyeing wastewater and loaded with gamma MnO2The particle size of the active carbon particles is 2-4mm, and the current density provided by the photovoltaic panel is 100mA/cm2The Hydraulic Retention Time (HRT) was 10m in, the treatment time was 3 hours, and the cathode compartment was NaOH in an alkali solution at a concentration of 0.2 g/L.
2(a), 2(b) and 2(c), the device and the method for producing hydrogen by coupling solar-driven wastewater treatment in the invention fill and load gamma MnO in the cathode and anode chambers2The activated carbon particle electrode improves the chroma of the wastewater and the removal efficiency of COD, and simultaneously, the yield of hydrogen is also greatly improved.

Claims (6)

1. A device for producing hydrogen by coupling solar-driven wastewater treatment comprises a three-dimensional catalytic electrode reactor for treating wastewater and generating hydrogen, a photoelectric system for supplying power, a pipeline system, a water storage system for storing wastewater and a hydrogen collecting system for collecting hydrogen;
wherein, the three-dimensional catalytic electrode reactor is respectively connected with the water storage system and the hydrogen collection system through the pipeline system, and the photoelectric system supplies power to the three-dimensional catalytic electrode reactor, and the device is characterized in that the structure of the device is as follows:
the three-dimensional catalytic electrode reactor comprises a monovalent cation exchange membrane (1), an anode chamber (2) and a cathode chamber (3);
the photovoltaic system comprises a solar photovoltaic panel (7), a voltage-stabilizing emergency power supply (8) and a single-pole double-throw switch (9);
the pipeline system comprises a wastewater inlet pipe (10), a wastewater inlet pipe (11 a), a wastewater inlet pump (12 a), a wastewater return pipe (13 a), a wastewater outlet valve (14 a) and a wastewater outlet pipe (15 a); a dilute alkali liquid lead-in pipe (11 b), a dilute alkali liquid lead-in pump (12 b), a concentrated alkali liquid return pipe (13 b), a concentrated alkali liquid outlet valve (14 b) and a concentrated alkali liquid outlet pipe (15 b);
the water storage system comprises a waste water storage tank (16) and an alkali liquor storage tank (17);
the hydrogen collecting system comprises a gas guide pipe (18) and a hydrogen tank (19);
wherein an anode electrode plate (4) and a cathode electrode plate (5) are respectively arranged in the anode chamber (2) and the cathode chamber (3); the anode chamber (2) and the cathode chamber (3) are respectively filled with a loaded type activated carbon particle electrode (6), and the surface of the activated carbon particle electrode (6) is loaded with gamma MnO2Particles forming a stereo catalytic electrode anode population and a cathode population; the waste water storage tank (16) and the alkali liquor storage tank (17) are respectively arranged at two ends of the anode chamber (2) and the cathode chamber (3), the waste water storage tank (16) is connected with the bottom of the anode chamber (2) through a waste water introducing pump (12 a) and a waste water introducing pipe (11 a), the anode chamber (2) is connected with the top of the waste water storage tank (16) through a waste water return pipe (13 a), the waste water inlet pipe (10) and a waste water outlet valve (14 a) are arranged on the waste water storage tank (16), and the waste water outlet pipe (15 a) is connected with the waste water storage tank (16) through the waste water outlet valve (14 a);
the alkali liquor storage tank (17) is connected with the bottom of the cathode chamber (3) through a dilute alkali liquor lead-in pump (12 b) and a dilute alkali liquor lead-in pipe (11 b), the cathode chamber (3) is connected with the top of the alkali liquor storage tank (17) through a concentrated alkali liquor return pipe (13 b), a concentrated alkali liquor outlet pipe (15 b) is arranged at the bottom of the alkali liquor storage tank (17), a concentrated alkali liquor outlet valve (14 b) is arranged on the concentrated alkali liquor outlet pipe (15 b), and the hydrogen tank (19) is connected with the alkali liquor storage tank (17) through the air duct (18);
one end of the solar photovoltaic panel (7) is respectively connected with the anode plate (4) and one end of the single-pole double-throw switch (9), the other end of the solar photovoltaic panel (7) is respectively connected with the voltage-stabilizing emergency power supply (8) and one end of the single-pole double-throw switch (9), and the other end of the voltage-stabilizing emergency power supply (8) is respectively connected with the cathode plate (5) and the single-pole double-throw switch (9);
the surface of the active carbon particle electrode (6) is loaded with gamma MnO2The specific process of the particles comprises the following steps: step 1: firstly, filling activated carbon particles between an anode electrode plate and a cathode electrode plate, and simultaneously adding MnSO into an electrolytic cell4Solution and H2SO4The mixed solution of the solution is electrolyte;
step 2: performing electrodeposition reaction, namely switching on a circuit at a certain voltage or current density, introducing oxygen with a certain concentration, and uniformly dispersing the oxygen to the gaps among the active carbon particles through a gas uniform distribution plate;
and step 3: the electrolytic bath is in a water bath heating state, and electrodeposition is carried out for a period of time;
and 4, step 4: after the electrodeposition is finished, taking out the activated carbon particles, washing the activated carbon particles with water, and removing unreacted MnSO on the surfaces of the activated carbon particles4Solution and H2SO4Drying the solution at a suitable temperature for a period of time to obtain the gamma-loaded MnO2The activated carbon particle electrode of (1).
2. The device for producing hydrogen by coupling solar-driven wastewater treatment according to claim 1, wherein the anode electrode plate (4) is made of: Ti/RuO2One of an electrode plate and a Pt electrode plate; the cathode electrode plate (5) is made of the following materials: one of a stainless steel fiber felt electrode plate, a glass carbon electrode plate, a Cu electrode plate and a graphite electrode plate, wherein the distance between the anode electrode plate (4) and the cathode electrode plate (5) is 3-10 cm.
3. The device of claim 1, wherein the activated carbon particles are one or a combination of coconut shell and fruit shell, and the activated carbon particles are blocky particles with the particle size of 2-4 mm; or columnar granules with the grain diameter of 2mm, 4mm and 6 mm.
4. A method for producing hydrogen by coupling the treatment of wastewater by using the device as claimed in any one of claims 1 to 3, which comprises the following steps:
the method comprises the following steps: the anode chamber (2) and the cathode chamber (3) are respectively filled with a certain amount of surface-loaded gamma MnO2The activated carbon particles of (1);
step two: injecting wastewater to be treated into a wastewater storage tank (16) through a wastewater inlet pipe (10), and then entering the anode chamber (2) through a wastewater inlet pipe (11 a) through a wastewater inlet pump (12 a); dilute alkali liquor enters the cathode chamber (3) through a dilute alkali liquor lead-in pump (12 b) and a dilute alkali liquor lead-in pipe (11 b), a power supply is switched on, and organic pollutants in the anolyte are degraded and decolored in the anode chamber (2); h in the cathode chamber (3)+Obtaining electrons at the cathode to form hydrogen, OH-Accumulating to increase the alkalinity of catholyte, wherein the dilute alkali solution is prepared from concentrated alkali obtained from the cathode chamber and wastewater obtained from the anode chamber;
step three: meanwhile, the anolyte flows back to a waste water storage tank (16); the catholyte flows back to the alkali liquor storage tank (17), H2Then enters a hydrogen tank (19) through a gas guide pipe (18);
step four: after a period of circulating electrolysis, the concentrated alkali is discharged from a concentrated alkali liquor outlet pipe (15 b), the purified wastewater is discharged from a wastewater outlet pipe (15 a), and a part of concentrated alkali liquor and purified water are prepared into dilute alkali liquor for treating the refractory wastewater of the next batch.
5. The method of claim 4, wherein: the wastewater to be treated is wastewater which is difficult to biodegrade and has a B/C ratio of less than 0.3; the dilute alkali solution added into the cathode chamber is one or the combination of dilute NaOH solution and dilute KOH solution, and the concentration is lower than 0.4 g/L.
6. The method of claim 4, wherein: the wastewater enters a three-dimensional catalytic electrode reactor, the hydraulic retention time is 3-20min, and the current density is 100-2The treatment time is 1-3 h.
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