CN107326387B - The equipment and its application method of hydrogen can be directly produced using salt error - Google Patents
The equipment and its application method of hydrogen can be directly produced using salt error Download PDFInfo
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- CN107326387B CN107326387B CN201710483766.3A CN201710483766A CN107326387B CN 107326387 B CN107326387 B CN 107326387B CN 201710483766 A CN201710483766 A CN 201710483766A CN 107326387 B CN107326387 B CN 107326387B
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- 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
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- 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
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- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
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- 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
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- 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
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- 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
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention provides a kind of equipment and its application method that hydrogen can be directly produced using salt error.Specifically, the equipment that can directly produce hydrogen using salt error includes electrodialysis reversal device, anolyte hold-up tank, catholyte hold-up tank, concentrated solution hold-up tank and dilute solution hold-up tank.According to the technique and scheme of the present invention, in not additional power source, utilize the potential energy difference of various concentration salting liquid, alkaline electrolyte and acidic electrolyte bath is respectively adopted in the anode chamber of electrodialysis reversal device two sides and cathode chamber, hydrolysis half-reaction occurs directly on the electrode of electrodialysis reversal device and generates hydrogen and oxygen, and gas is separated by Separate System of Water-jet online.The equipment and its application method can not only reduce hydrolytic hydrogen production energy consumption, improve electrode stability, and simple process, without external energy, pollution-free, hydrogen generation efficiency height.
Description
Technical field
The invention belongs to hydrogen as energy source technical fields, and in particular to it is a kind of using salt error can be direct driving force, by anti-
The equipment and its application method of hydrogen are directly produced to electrodialysis.
Background technique
With the development of world economy, the traditional fossil energies such as petroleum, natural gas, coal, which are faced with, is stranded exhausted
Border, and because global warming caused by the combusts fossil energy and air pollution problems inherent are also got worse, it studies and develops novel
Renewable energy is to solve an important means of energy and environment crisis.Research has shown that wind energy, solar energy, tide energy, salt error
Conventional fossil fuel can be substituted with renewable energy such as Hydrogen Energies, wherein Hydrogen Energy is due to its easily storage, energy density height, source
Extensively and combustion product is water, no pollution to the environment, it is considered to be one of most potential energy.However, institute in current chemical industry
The hydrogen used is the gasification cracking for originating from the fossil fuels such as natural gas, petroleum and coal, such as the reformation of methane mostly, this
A little methods still result in the discharge and air pollution of carbon dioxide.And High Purity Hydrogen can be produced using the method for electrolysis water, but low
Energy efficiency and ever-increasing power price hinder the development of this technique.Simultaneously as the electric energy in electrolytic process is very
Big a part derives from the burning of fossil fuel, this also restricts its application advantage to a certain extent.Renewable energy is generated
Electric energy be applied to electrolytic hydrogen production process, can be to avoid above drawback.Additionally, due to most renewable energy by weather
Environment, season and the influence in geographical location, can not be directly incorporated into power grid application, it usually needs other form of energy are converted into,
Or storage is converted electrical energy into using flow battery, this increases cost of investment to a certain extent, reduces the feasible of process
Property.
For example, most of salt errors can be used to produce electricity, electrodialysis reversal (RED) is (to generate salt error by concentration difference
Chemical energy) carry out energy conversion one of main method, transformation efficiency is about 10%, however, since there are regional disparities
Property and season unstability, the electricity for generating it be connected to the grid it is more difficult, therefore, the electric energy that electrodialysis reversal is generated
The problem of being converted into other energy, just can solve storage transport.Pass through electrolysis aquatic products again to electric energy can be converted by salt error as a result,
There is the interest and demand for increasing and updating in the Hydrogen Energy of raw high-efficiency environment friendly.
It is produced electricl energy according to conventional electrodialysis reversal device, the electrolytic cell conventional as the driving of energy source prepares hydrogen
Gas has following problems: (1) two covering devices are both needed to that there are a pair of electrodes in two sides, and electrochemical reaction occurs, energy consumption
Greatly；(2) water electrolyser only has a diaphragm, the hydrogen generated in two lateral electrode of diaphragm and oxygen meeting between a cathode and an anode
It is mixed across diaphragm；(3) in conventional hydropower solution slot, standard electrode potential E0=1.229V, hydrolysis energy consumption is high, and is electrolysed
Matter is all the same in cathode chamber and anode chamber, very harsh for the selection of metal electrode.In consideration of it, developing a kind of utilization salt error energy
For direct driving force, the new method that hydrogen is prepared using electrodialysis reversal is had great importance.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of can directly produce hydrogen and divide online using salt error
From system and its technique.
The present invention utilizes electrodialysis reversal device, is passed through properly in the cathode chamber of electrodialysis reversal device two sides and anode chamber
Acidic electrolyte bath and alkaline electrolyte, directly on the electrode of electrodialysis reversal device occur hydrolysis half-reaction, generate hydrogen
And oxygen, compared with conventional hydropower solution slot standard electrode potential E0=1.229V, standard electrode potential E0It is reduced to 0.4V.Together
When, by different electrode environment, separated two is allowed to hydrolyze catalyst/electrolyte pairing independent optimization of half-reaction,
Eliminate the drawback that oxygen-separating catalyst is unstable in acid environment and liberation of hydrogen catalyst is unstable in alkali environment.It is noticeable
Be, between two lateral electrode of electrodialysis reversal between be separated with the anion-exchange membrane and cation-exchange membrane of repeated arrangement, avoid
Electrolyte interpenetrates, while hindering the mixing between gaseous product, improves the purity of hydrogen product.Therefore, of the invention
Described in using electrodialysis reversal be means, in conjunction with gas on-line checking and separation system, can directly be prepared using salt error
The method of novel hydrogen energy source can reduce the hydrolysis voltage in electrolytic process, reduce energy consumption, improve electrode stability, and technique letter
It is single, without external energy, pollution-free, hydrogen generation efficiency height.
According to an aspect of the invention, there is provided a kind of equipment that can directly produce hydrogen using salt error, the equipment include:
Electrodialysis reversal device, the electrodialysis reversal device include anode plate, cathode plate and are arranged in the anode
The more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes between plate and cathode plate, wherein
The quantity of the cation-exchange membrane is equal with the quantity of the anion-exchange membrane；The anode plate is folded with described successively replace
Space structure between the more than two cation-exchange membranes set and the cation-exchange membrane of more than two anion-exchange membranes one end
At anode chamber；The cathode plate and the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion are handed over
It changes the space between the anion-exchange membrane of the film other end and constitutes cathode chamber；There is the anode chamber positioned at lower end to enter for the anode chamber
Mouth and the anode compartment outlet positioned at upper end, and the cathode chamber has the yin positioned at the cathode chamber inlet of lower end and positioned at upper end
Pole room outlet；It is each pair of in the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes
Space between adjacent cation-exchange membrane and anion-exchange membrane constitutes n concentrated solution room being successively arranged alternately and n+1
A dilute solution room, wherein n is greater than or equal to 1；The anode chamber and the n concentrated solution room being successively arranged alternately and n+1 are a
The dilute solution room of dilute solution room one end is adjacent, and the cathode chamber and n concentrated solution room being successively arranged alternately and n+1 are light
The dilute solution room of the solution room other end is adjacent；There is the concentrated solution room positioned at lower end to enter for each of n concentrated solution room
Mouthful and positioned at upper end concentrated solution room export, and each of n+1 dilute solution room have be located at lower end it is light molten
Chamber inlet and positioned at upper end dilute solution room export；
Anolyte hold-up tank, the anolyte hold-up tank have oxygen outlet and with the Anode chamber inlets and the sun
Pole room communication；
Catholyte hold-up tank, the catholyte hold-up tank have hydrogen outlet and with the cathode chamber inlet and the yin
Pole room communication；
Concentrated solution hold-up tank, the concentrated solution hold-up tank and the concentrated solution room of each of n concentrated solution room enter
Mouth is in fluid communication；With
The dilute solution room of each of dilute solution hold-up tank, the dilute solution hold-up tank and n+1 dilute solution room
Entrance is in fluid communication.
According to another aspect of the present invention, setting for hydrogen can directly be produced using salt error as described above by providing a kind of utilize
The method of standby production hydrogen, the method includes the following steps:
1) make the lye in the anolyte hold-up tank via the Anode chamber inlets and the anode compartment outlet and
It is recycled between the anolyte hold-up tank and the anode chamber；
2) make the acid solution in the catholyte hold-up tank via the cathode chamber inlet and the cathode chamber outlet and
It is recycled between the catholyte hold-up tank and the cathode chamber；
3) dilute solution in the concentrated solution and the dilute solution hold-up tank in the concentrated solution hold-up tank is introduced between
The concentrated solution room and the dilute solution room, wherein the concentrated solution and the dilute solution are the aqueous solution of strong electrolyte, institute
The strong electrolyte concentration for stating concentrated solution be 0.5 rub/liter or more, the strong electrolyte concentration of the dilute solution be 0.01 rub/liter or more,
And the strong electrolyte concentration of the concentrated solution is greater than the strong electrolyte concentration of the dilute solution；With
4) it will be electrically connected between the anode plate and the cathode plate.
Compared with prior art, the equipment provided by the invention that can directly produce hydrogen using salt error, in conjunction with gas on-line checking
It, can be come the method that directly prepares novel hydrogen energy source, in not additional power source, using different dense using salt error with separation system
The potential energy difference for spending salting liquid, is respectively adopted alkaline electrolyte and acid in the anode chamber of electrodialysis reversal device two sides and cathode chamber
Property electrolyte, hydrolysis half-reaction occurs directly on the electrode of electrodialysis reversal device generates hydrogen and oxygen, the system and its
Technique can not only reduce hydrolytic hydrogen production energy consumption, improve electrode stability, and simple process, without external energy, pollution-free, production hydrogen
It is high-efficient.
Detailed description of the invention
Fig. 1 is the structural schematic diagram according to the equipment that can directly produce hydrogen using salt error of one embodiment of the invention；
Fig. 2 is the working principle diagram of the equipment provided by the invention that hydrogen can be directly produced using salt error；
Fig. 3 is the curent change figure that can be directly produced during hydrogen using salt error according to embodiment 1,2,3 and 4；With
Fig. 4 is the hydrogen output variation diagram that can be directly produced during hydrogen using salt error according to embodiment 1,2,3 and 4.
Description of symbols:
1: the equipment that can directly produce hydrogen using salt error；2: electrodialysis reversal device；3. anode plate；4: cathode plate；5: sun from
Proton exchange；6: anion-exchange membrane；7: anode chamber；8: cathode chamber；9: Anode chamber inlets；10: anode compartment outlet；11: cathode
Chamber inlet；12: cathode chamber outlet；13: concentrated solution room；14: dilute solution room；15: concentrated solution chamber inlet；16: the outlet of concentrated solution room；
17: dilute solution chamber inlet；18: the outlet of dilute solution room；19: anolyte hold-up tank；20: oxygen outlet；21: catholyte hold-up tank；
22: hydrogen outlet；23: concentrated solution hold-up tank；24: dilute solution hold-up tank；25: gas on-line checking and separator；26: anode
Liquid transfer tube；27: catholyte transfer tube；28: concentrated solution transfer tube；29: dilute solution transfer tube；30: air bag.
Specific embodiment
Below with reference to specific embodiment, present invention is further described in detail.It will be appreciated that, it is contemplated that other realities
Mode is applied, and does not depart from the scope or spirit of the invention, it is possible to implement these other embodiments.Therefore, below to retouch in detail
It states and is non-limiting.
Unless otherwise specified, expression characteristic size, quantity and materialization used in specification and claims are special
All numbers of property be construed as to be modified by term " about " in all cases.Therefore, unless there are opposite
Illustrate, the numerical parameter otherwise listed in description above and the appended claims is approximation, those skilled in the art
Member can seek the required characteristic obtained using teachings disclosed herein, suitably change these approximations.With endpoint table
The use for the numberical range shown includes all numbers within the scope of this and any range within the scope of this, for example, 1 to 5 includes
1,1.1,1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
The present invention provides a kind of equipment that can directly produce hydrogen using salt error, and the equipment includes:
Electrodialysis reversal device, the electrodialysis reversal device include anode plate, cathode plate and are arranged in the anode
The more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes between plate and cathode plate, wherein
The quantity of the cation-exchange membrane is equal with the quantity of the anion-exchange membrane；The anode plate is folded with described successively replace
Space structure between the more than two cation-exchange membranes set and the cation-exchange membrane of more than two anion-exchange membranes one end
At anode chamber；The cathode plate and the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion are handed over
It changes the space between the anion-exchange membrane of the film other end and constitutes cathode chamber；There is the anode chamber positioned at lower end to enter for the anode chamber
Mouth and the anode compartment outlet positioned at upper end, and the cathode chamber has the yin positioned at the cathode chamber inlet of lower end and positioned at upper end
Pole room outlet；It is each pair of in the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes
Space between adjacent cation-exchange membrane and anion-exchange membrane constitutes n concentrated solution room being successively arranged alternately and n+1
A dilute solution room, wherein n is greater than or equal to 1；The anode chamber and the n concentrated solution room being successively arranged alternately and n+1 are a
The dilute solution room of dilute solution room one end is adjacent, and the cathode chamber and n concentrated solution room being successively arranged alternately and n+1 are light
The dilute solution room of the solution room other end is adjacent；There is the concentrated solution room positioned at lower end to enter for each of n concentrated solution room
Mouthful and positioned at upper end concentrated solution room export, and each of n+1 dilute solution room have be located at lower end it is light molten
Chamber inlet and positioned at upper end dilute solution room export；
Anolyte hold-up tank, the anolyte hold-up tank have oxygen outlet and with the Anode chamber inlets and the sun
Pole room communication；
Catholyte hold-up tank, the catholyte hold-up tank have hydrogen outlet and with the cathode chamber inlet and the yin
Pole room communication；
Concentrated solution hold-up tank, the concentrated solution hold-up tank and the concentrated solution room of each of n concentrated solution room enter
Mouth is in fluid communication；With
The dilute solution room of each of dilute solution hold-up tank, the dilute solution hold-up tank and n+1 dilute solution room
Entrance is in fluid communication.
Preferred embodiment according to the present invention, the anode chamber are sealed by gasket seal, and in the anode plate and
The cation exchange of the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes one end
Runner grid is provided between film.
Preferred embodiment according to the present invention, the cathode chamber are sealed by gasket seal, and the cathode plate with
The anion of the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membrane other ends is handed over
It changes between film and is provided with runner grid.
Preferred embodiment according to the present invention, each of n concentrated solution room and n+1 dilute solution room
It is sealed by gasket seal, and is handed in the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion
It changes between each pair of adjacent cation-exchange membrane and anion-exchange membrane in film and is provided with runner grid.
The concrete type of used runner grid is not particularly limited, it can be using usually used in this field each
Kind runner grid, and the specific size of the runner grid can be adjusted according to specific needs.In addition, to used sealing
The material of gasket is not particularly limited, and can use various gasket seals usually used in this field, and can be according to tool
Body needs to adjust the specific size of the gasket seal.
Preferred embodiment according to the present invention, the hydrogen outlet and/or the anode of the catholyte hold-up tank
The oxygen outlet of liquid hold-up tank is connect with gas on-line checking with separator.The gas on-line checking and separator
Including gas-liquid separator and gas sensor, wherein the hydrogen outlet of the gas-liquid separator and the catholyte hold-up tank
And/or the oxygen outlet connection of the anolyte hold-up tank.
Preferably, the anode plate and cathode plate are by metal and metal compound material structure with special microstructure
At.The anode plate and the cathode plate are selected from nickel sheet, titanium sheet, stainless steel substrates, the foam nickel sheet, bubble that surface is coated with catalyst
One of foam titanium sheet, nickel screen, titanium net and stainless (steel) wire are a variety of, the catalyst for promote oxidation and reduction reaction and
Selected from platinum, ruthenium, iridium, cobalt, molybdenum and one of their oxide or sulfide or a variety of.Preferably, the anode plate and
The cathode plate is the titanium plate that surface is coated with ruthenium.
Preferably, the cation-exchange membrane is selected from one of monovalence or polyvalent cation exchange membrane, charged perforated membrane
Or it is a variety of, and the anion-exchange membrane is selected from one of monovalence or multivalent anions exchange membrane, charged perforated membrane or more
Kind.The specific example of cation-exchange membrane and anion-exchange membrane includes raw by Hefei Ke Jia high molecular material Science and Technology Ltd.
The CJMC-1 and CJMA-1 of production.
Preferred embodiment according to the present invention, the anolyte hold-up tank is via anolyte transfer tube and the anode chamber
Entrance and anode compartment outlet are in fluid communication.
Preferred embodiment according to the present invention, the catholyte hold-up tank is via catholyte transfer tube and the cathode chamber
Entrance and the cathode chamber outlet are in fluid communication.
Preferred embodiment according to the present invention, the concentrated solution hold-up tank are dense via concentrated solution transfer tube and the n
The concentrated solution chamber inlet of each of solution room is in fluid communication.
Preferred embodiment according to the present invention, the dilute solution hold-up tank is via dilute solution transfer tube and the n+1
The dilute solution chamber inlet of each of dilute solution room is in fluid communication.
The present invention also provides it is a kind of using as described above using salt error can directly produce hydrogen equipment production hydrogen method,
The method includes the following steps:
1) make the lye in the anolyte hold-up tank via the Anode chamber inlets and the anode compartment outlet and
It is recycled between the anolyte hold-up tank and the anode chamber；
2) make the acid solution in the catholyte hold-up tank via the cathode chamber inlet and the cathode chamber outlet and
It is recycled between the catholyte hold-up tank and the cathode chamber；
3) dilute solution in the concentrated solution and the dilute solution hold-up tank in the concentrated solution hold-up tank is introduced between
The concentrated solution room and the dilute solution room, wherein the concentrated solution and the dilute solution are the aqueous solution of strong electrolyte, institute
The strong electrolyte concentration for stating concentrated solution be 0.5 rub/liter or more, the strong electrolyte concentration of the dilute solution be 0.01 rub/liter or more,
And the strong electrolyte concentration of the concentrated solution is greater than the strong electrolyte concentration of the dilute solution；With
4) it will be electrically connected between the anode plate and the cathode plate.
Preferred embodiment according to the present invention, the strong electrolyte concentration of the concentrated solution rubs 0.5/liter up to described
In the range of the saturated concentration of strong electrolyte in water.The strong electrolyte concentration of the dilute solution rubs 0.01/liter up to institute
In the range of stating the saturated concentration of strong electrolyte in water.
Preferred embodiment according to the present invention, the lye be concentration be greater than or equal to 0.05 rub/liter strong basicity without
The aqueous solution of machine salt；The acid solution be concentration be greater than or equal to 0.05 rub/liter highly acid inorganic acid or organic acid aqueous solution.
Preferably, the concentration of the strong basicity inorganic salts of the lye is rubbed/rises to the saturation of the strong basicity inorganic salts in water 0.05
In the range of concentration.
Preferred embodiment according to the present invention, the strong basicity inorganic salts are selected from sodium hydroxide, potassium hydroxide, hydroxide
One of lithium, barium hydroxide are a variety of；The highly acid inorganic acid or organic acid are selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, Asia
One of sulfuric acid is a variety of；And the strong electrolyte be selected from sodium chloride, potassium chloride, calcium chloride, ammonium carbonate, ammonium hydrogen carbonate,
One of sodium sulphate, potassium sulfate, calcium sulfate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate are a variety of.
Below in conjunction with attached drawing to the structure and working principle of the equipment according to the present invention that can directly produce hydrogen using salt error
It is described in detail, it should be noted however that the attached drawing is used only for exemplary effect, technical solution of the present invention is never
It is defined in this.
As shown in Figure 1, the present invention provides a kind of equipment 1 that can directly produce hydrogen using salt error, the equipment includes:
Electrodialysis reversal device 2, the electrodialysis reversal device 2 include anode plate 3, cathode plate 4 and are arranged described
The more than two cation-exchange membranes 5 being successively alternately superimposed on and more than two anion-exchange membranes between anode plate and cathode plate
6, wherein the quantity of the cation-exchange membrane 5 is equal with the quantity of the anion-exchange membrane 6；The anode plate 3 with it is described
The cation-exchange membrane 5 of the more than two cation-exchange membranes 5 and more than two anion-exchange membranes one end that are successively alternately superimposed on
Between space constitute anode chamber 7；The cathode plate 4 and the more than two cation-exchange membranes 5 being successively alternately superimposed on and
Space between the anion-exchange membrane 6 of more than two 6 other ends of anion-exchange membrane constitutes cathode chamber 8；The anode chamber 7 has
There is the anode compartment outlet 10 positioned at the Anode chamber inlets 9 of lower end and positioned at upper end, and the cathode chamber 8 has positioned at lower end
Cathode chamber inlet 11 and cathode chamber outlet 12 positioned at upper end；The more than two cation-exchange membranes 5 being successively alternately superimposed on
Space structure between each pair of adjacent cation-exchange membrane 5 and anion-exchange membrane 6 in more than two anion-exchange membranes 6
At the n concentrated solution room 13 and n+1 dilute solution room 14 being successively arranged alternately, wherein n is greater than or equal to 1；The anode chamber 7 with
The dilute solution room 14 of 14 one end of the n concentrated solution room 13 being successively arranged alternately and n+1 dilute solution room is adjacent and described
Cathode chamber 8 is adjacent with the dilute solution room 14 of the n concentrated solution room 13 and n+1 14 other end of dilute solution room that are successively arranged alternately；
Each of n concentrated solution room 13 has the concentrated solution chamber inlet 15 for being located at lower end and goes out positioned at the concentrated solution room of upper end
Mouth 16, and each of n+1 dilute solution room 14 has positioned at the dilute solution chamber inlet 17 of lower end and positioned at upper end
Dilute solution room outlet 18；
Anolyte hold-up tank 19, the anolyte hold-up tank 19 have oxygen outlet 20 and with the Anode chamber inlets 9
It is in fluid communication with the anode compartment outlet 10；
Catholyte hold-up tank 21, the catholyte hold-up tank 21 have hydrogen outlet 22 and with the cathode chamber inlet 11
It is in fluid communication with the cathode chamber outlet 12；
The concentrated solution of each of concentrated solution hold-up tank 23, the concentrated solution hold-up tank 23 and n concentrated solution room
Chamber inlet 15 is in fluid communication；With
Dilute solution hold-up tank 24, the dilute solution hold-up tank 24 are light molten with each of n+1 dilute solution room
Chamber inlet 17 is in fluid communication.
According to the technique and scheme of the present invention, the anode chamber is sealed by gasket seal, and in the anode plate and described
More than two cation-exchange membranes for being successively alternately superimposed on and the cation-exchange membrane of more than two anion-exchange membranes one end it
Between be provided with runner grid.The cathode chamber is sealed by gasket seal, and is successively alternately superimposed in the cathode plate with described
More than two cation-exchange membranes and more than two anion-exchange membrane other end anion-exchange membrane between be provided with stream
Road grid.Each of n concentrated solution room and n+1 dilute solution room are sealed by gasket seal, and described
Each pair of adjacent cation in more than two cation-exchange membranes and more than two anion-exchange membranes being successively alternately superimposed on
Runner grid is provided between exchange membrane and anion-exchange membrane.Since the runner grid and gasket seal have this field skill
Structure known to art personnel and construction, without drawing runner grid and gasket seal in Fig. 1.
The oxygen of the hydrogen outlet 22 of the catholyte hold-up tank 21 and/or the anolyte hold-up tank 19 goes out
Mouth 20 is connect with gas on-line checking with separator 25.
According to the technique and scheme of the present invention, the gas on-line checking and separator 25 include gas-liquid separator and gas
Sensor, wherein the hydrogen outlet 22 and/or the anolyte of the gas-liquid separator and the catholyte hold-up tank 21
The oxygen outlet 20 of hold-up tank 19 connects.Since the gas-liquid separator and gas sensor have those skilled in the art
Known structure and construction do not have the specific structure of gas-liquid separator and gas sensor in Fig. 1.
As shown in Figure 1, the anolyte hold-up tank 19 is via anolyte transfer tube 26 and the Anode chamber inlets 9 and sun
Pole room outlet 10 is in fluid communication.The catholyte hold-up tank 21 is via catholyte transfer tube 27 and the cathode chamber inlet 11 and institute
State the fluid communication of cathode chamber outlet 12.The concentrated solution hold-up tank 23 is via concentrated solution transfer tube 28 and n concentrated solution room
Each of 13 concentrated solution chamber inlet 15 is in fluid communication.The dilute solution hold-up tank 24 is via dilute solution transfer tube 29 and institute
The dilute solution chamber inlet 17 for stating each of n+1 dilute solution room 14 is in fluid communication.
The hydrogen after tested, the hydrogen can be collected.The present invention is to the method for collecting recycling
There is no specifically limited.Well known to a person skilled in the art methods.The gas on-line checking goes out with separator 25
Mouth is connect with air bag 30.
Preferably, the anolyte transfer tube, catholyte transfer tube, concentrated solution transfer tube and dilute solution transfer tube are to wriggle
Pump.
Below in conjunction with Fig. 2, the technological principle provided by the invention that can directly produce hydrogen using salt error and separate online is carried out
It is described in detail.
When concentrated solution and dilute solution enter electrodialysis reversal device and when concentrated solution room and dilute solution room are flowed, in concentration
Under difference pushes, the anions and canons in concentrated solution room pass through anions and canons exchange membrane respectively and migrate into dilute solution room, thus shape
At the interior electric current of orientation Ion transfer；It, can be by Ion transfer by the electrochemical reaction of cathode and anode after connecting electronic load
Electric current is converted into the external current of electron transfer, forms complete circuit.And by being passed through acid, alkali electrolysis in yin, yang pole room
The decomposition half-reaction of water occurs on liquid, cathode and anode respectively, process is as follows: anode: 4OH-→2H2O+O2+4e-；Cathode: 4e-
+4H+→2H2.Hydrogen, the oxygen of reaction generation are separated through intermediate electrodialysis reversal device, are distinguished together with acid, alkaline electrolyte
It is discharged, is separated through gas-liquid separation device, hydrogen is collected after detection device detects from yin, yang pole room.
The present invention is improved on traditional electrodialysis reversal device basic, is passed through in the cathode chamber of two sides and anode chamber
Suitable acidic electrolyte bath and alkaline electrolyte, generate hydrogen, oxygen for water electrolysis directly on the electrode of electrodialysis reversal device
Gas, and it is separated online.The system can not only reduce hydrolysis voltage, reduce energy consumption, improve electrode stability, and technique
Simply, without external energy, pollution-free, and hydrogen generation efficiency is high.
For a further understanding of the present invention, hydrogen can be directly produced simultaneously using salt error to provided by the invention below with reference to embodiment
The system and its technique separated online is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Equipment of the present embodiment using can directly produce hydrogen using salt error shown in Fig. 1.Concentrated solution used is that concentration is
The sodium-chloride water solution of 4.0mol/L, dilute solution used are the sodium-chloride water solution that concentration is 0.017mol/L, alkali used
Liquid is the sodium hydrate aqueous solution that concentration is 0.5mol/L, and acid solution used is that the hydrochloric acid that concentration is 2.0mol/L is water-soluble
Liquid.
The equipment that can directly produce hydrogen using salt error according to shown in Fig. 1 is constructed, wherein altogether using 20 cation exchanges
Film and 20 anion-exchange membranes, are formed with the combination of 19 concentrated solution rooms and 20 dilute solution rooms in electrodialysis reversal device
Unit.Used anode plate and cathode plate are by the painting ruthenium titanium plate of the auspicious prosperous titanium industry production in Baoji, having a size of 9cm × 21cm.
The production of Hefei Ke Jia high molecular material Science and Technology Ltd. is respectively adopted in used anion-exchange membrane and cation-exchange membrane
CJMC-1 and CJMA-1, having a size of 9cm × 21cm after cutting.Wherein, single film, anode plate and cathode plate effective area
It is 189cm2。
The present embodiment carries out capable of directly producing hydrogen using salt error as follows and on-line checking and isolated operation:
1) make the lye sodium hydrate aqueous solution of 0.5mol/L (concentration for) in the anolyte hold-up tank via institute
It states Anode chamber inlets and the anode compartment outlet and is recycled between the anolyte hold-up tank and the anode chamber；
2) make the acid solution (aqueous hydrochloric acid solution that concentration is 2.0mol/L) in the catholyte hold-up tank via the yin
Pole room entrance and the cathode chamber outlet and recycled between the catholyte hold-up tank and the cathode chamber；
3) by the concentrated solution sodium-chloride water solution of 4.0mol/L (concentration be) in the concentrated solution hold-up tank and described light
Dilute solution (sodium-chloride water solution of 0.017mol/L) in solution hold-up tank is introduced between the concentrated solution room and described light
Solution room, flow velocity are 0.75L/min；
4) it will be electrically connected between the anode plate and the cathode plate, carry out electrodialysis reversal operation, and pass through anode
Programmable electronic load device (FT6300A, Shenzhen Tyke Fei Si Science and Technology Co., Ltd.) between plate and the cathode plate
Record current changes with time；
5) make anode chamber and cathode chamber generate gas and respectively enter anolyte hold-up tank and catholyte hold-up tank, Jin Erjin
Enter gas-liquid separation device, and passes through gas sensor on-line checking.
Pass through above-described programmable electronic load device (FT6300A, the limited public affairs of Shenzhen Tyke Fei Si science and technology share
Department) the measurement salt error can directly produce the electric current during hydrogen, and pass through digital gas mass flow meter device
(CS200A, Beijing Qixing Huachuang Electronics Co., Ltd) detects the variation of hydrogen-producing speed, Fig. 3 and Fig. 4 is as a result seen, wherein scheming
3 can directly produce the current graph during hydrogen for embodiment 1,2,3 and 4 salt errors；Fig. 4 is that salt error can directly produce the production hydrogen during hydrogen
Rate variation diagram.
In the present embodiment, it can continue to generate electric current using the device, and stable hydrogen-producing speed can be detected, be
2.27ml/min。
Embodiment 2
In a manner similar to example 1 by directly being produced shown in Fig. 1 using the equipment that salt error can directly produce hydrogen
Hydrogen, the difference is that the concentration of the hydrochloric acid in acid solution is changed to 1.0mol/L, and by the dense of the sodium hydroxide in lye
Degree is changed to 0.5mol/L.
The variation of electric current and hydrogen-producing speed during hydrogen can directly be produced by measuring the salt error, as a result see Fig. 3 and Fig. 4, wherein
Fig. 3 is that embodiment 1,2,3 and 4 salt errors can directly produce the current graph during hydrogen；Fig. 4 is that salt error can directly produce the production during hydrogen
Hydrogen rate variation diagram.
In the present embodiment, it can continue to generate electric current using the device, and stable hydrogen-producing speed can be detected, be
1.89ml/min。
Embodiment 3
In a manner similar to example 1 by directly being produced shown in Fig. 1 using the equipment that salt error can directly produce hydrogen
Hydrogen, difference is the difference is that be changed to 0.5mol/L for the concentration of the hydrochloric acid in acid solution, and by the hydrogen-oxygen in lye
The concentration for changing sodium is changed to 0.5mol/L.
The variation of electric current and hydrogen-producing speed during hydrogen can directly be produced by measuring the salt error, as a result see Fig. 3 and Fig. 4, wherein
Fig. 3 is that embodiment 1,2,3 and 4 salt errors can directly produce the current graph during hydrogen；Fig. 4 is that salt error can directly produce the production during hydrogen
Hydrogen rate variation diagram.
In the present embodiment, it can continue to generate electric current using the device, and stable hydrogen-producing speed can be detected, be
1.79ml/min。
Embodiment 4
In a manner similar to example 1 by directly being produced shown in Fig. 1 using the equipment that salt error can directly produce hydrogen
Hydrogen, difference is the difference is that be changed to 0.2mol/L for the concentration of the hydrochloric acid in acid solution, and by the hydrogen-oxygen in lye
The concentration for changing sodium is changed to 0.5mol/L.
The variation for measuring electric current and hydrogen-producing speed that the salt error can be produced directly during hydrogen, is as a result shown in Fig. 3 and Fig. 4,
Middle Fig. 3 is that embodiment 1,2,3 and 4 salt errors can directly produce the current graph during hydrogen；Fig. 4 can be produced directly for salt error during hydrogen
Hydrogen-producing speed variation diagram.
In the present embodiment, it can continue to generate electric current using the device, and stable hydrogen-producing speed can be detected, be
1.73ml/min。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (13)
1. a kind of method using the equipment production hydrogen that can directly produce hydrogen using salt error, described directly to produce hydrogen using salt error
Equipment includes:
Electrodialysis reversal device, the electrodialysis reversal device include anode plate, cathode plate and setting in the anode plate and
The more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes between cathode plate, wherein described
The quantity of cation-exchange membrane is equal with the quantity of the anion-exchange membrane；It the anode plate and described is successively alternately superimposed on
Space between more than two cation-exchange membranes and the cation-exchange membrane of more than two anion-exchange membranes one end constitutes sun
Pole room；The cathode plate and the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes
Space between the anion-exchange membrane of the other end constitutes cathode chamber；The anode chamber have positioned at lower end Anode chamber inlets and
Anode compartment outlet positioned at upper end, and the cathode chamber has the cathode chamber positioned at the cathode chamber inlet of lower end and positioned at upper end
Outlet；It is each pair of adjacent in the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes
Cation-exchange membrane and anion-exchange membrane between space constitute n concentrated solution room being successively arranged alternately and n+1 is a light
Solution room, wherein n is greater than or equal to 1；The anode chamber and the n concentrated solution room being successively arranged alternately and n+1 are light molten
The dilute solution room of liquid chamber one end is adjacent, and the cathode chamber and n concentrated solution room being successively arranged alternately and n+1 dilute solution
The dilute solution room of the room other end is adjacent；Each of n concentrated solution room have positioned at lower end concentrated solution chamber inlet and
Concentrated solution room positioned at upper end exports, and each of n+1 dilute solution room has positioned at the dilute solution room of lower end
Entrance and positioned at upper end dilute solution room export；
Anolyte hold-up tank, the anolyte hold-up tank have oxygen outlet and with the Anode chamber inlets and the anode chamber
Communication；
Catholyte hold-up tank, the catholyte hold-up tank have hydrogen outlet and with the cathode chamber inlet and the cathode chamber
Communication；
The concentrated solution chamber inlet stream of each of concentrated solution hold-up tank, the concentrated solution hold-up tank and n concentrated solution room
Body connection；With
The dilute solution chamber inlet of each of dilute solution hold-up tank, the dilute solution hold-up tank and n+1 dilute solution room
It is in fluid communication, and
The method includes the following steps:
1) make the lye in the anolyte hold-up tank via the Anode chamber inlets and the anode compartment outlet and described
It is recycled between anolyte hold-up tank and the anode chamber；
2) make the acid solution in the catholyte hold-up tank via the cathode chamber inlet and the cathode chamber outlet and described
It is recycled between catholyte hold-up tank and the cathode chamber；
3) dilute solution in the concentrated solution and the dilute solution hold-up tank in the concentrated solution hold-up tank is introduced between described
Concentrated solution room and the dilute solution room, wherein the concentrated solution and the dilute solution are the aqueous solution of strong electrolyte, it is described dense
The strong electrolyte concentration of solution be 0.5 rub/liter or more, the strong electrolyte concentration of the dilute solution be 0.01 rub/liter or more, and
The strong electrolyte concentration of the concentrated solution is greater than the strong electrolyte concentration of the dilute solution；With
4) it will be electrically connected between the anode plate and the cathode plate,
Wherein the lye be concentration be greater than or equal to 0.05 rub/liter strong basicity inorganic salts aqueous solution；The acid solution is dense
Degree be greater than or equal to 0.05 rub/liter highly acid inorganic acid or organic acid aqueous solution.
2. the method for production hydrogen according to claim 1, wherein the strong basicity inorganic salts are selected from sodium hydroxide, hydrogen-oxygen
Change one of potassium, lithium hydroxide, barium hydroxide or a variety of；The highly acid inorganic acid or organic acid are selected from hydrochloric acid, sulfuric acid, nitre
One of acid, acetic acid, sulfurous acid are a variety of；And the strong electrolyte be selected from sodium chloride, potassium chloride, calcium chloride, ammonium carbonate,
One of ammonium hydrogen carbonate, sodium sulphate, potassium sulfate, calcium sulfate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate are more
Kind.
3. the method for production hydrogen according to claim 1, wherein the anode chamber is sealed by gasket seal, and in institute
State anode plate and the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membranes one end
Runner grid is provided between cation-exchange membrane.
4. the method for production hydrogen according to claim 1, wherein the cathode chamber is sealed by gasket seal, and in institute
State cathode plate and the more than two cation-exchange membranes being successively alternately superimposed on and more than two anion-exchange membrane other ends
Anion-exchange membrane between be provided with runner grid.
5. the method for production hydrogen according to claim 1, wherein n concentrated solution room and the n+1 dilute solution
Each of room is sealed by gasket seal, and in the more than two cation-exchange membranes being successively alternately superimposed on and two
Runner grid is provided between each pair of adjacent cation-exchange membrane and anion-exchange membrane in the above anion-exchange membrane.
6. it is according to claim 1 production hydrogen method, wherein the hydrogen outlet of the catholyte hold-up tank and/
Or the oxygen outlet of the anolyte hold-up tank is connect with gas on-line checking with separator.
7. the method for production hydrogen according to claim 6, wherein the gas on-line checking and separator include gas
Liquid/gas separator and gas sensor, wherein the hydrogen outlet of the gas-liquid separator and the catholyte hold-up tank and/or
The oxygen outlet of the anolyte hold-up tank connects.
8. the method for production hydrogen according to claim 1, wherein the anode plate and the cathode plate are applied selected from surface
It is furnished with one of nickel sheet, titanium sheet, stainless steel substrates, foam nickel sheet, foam titanium sheet, nickel screen, titanium net and the stainless (steel) wire of catalyst
Or it is a variety of, the catalyst is selected from platinum, ruthenium, iridium, cobalt, molybdenum and one of their oxide or sulfide or a variety of.
9. the method for production hydrogen according to claim 1, wherein the cation-exchange membrane is selected from monovalence or multivalence sun
One of amberplex, charged perforated membrane are a variety of, and the anion-exchange membrane is selected from monovalence or multivalent anions
One of exchange membrane, charged perforated membrane are a variety of.
10. the method for production hydrogen according to claim 1, wherein the anolyte hold-up tank is via anolyte transfer tube
It is in fluid communication with the Anode chamber inlets and anode compartment outlet.
11. the method for production hydrogen according to claim 1, wherein the catholyte hold-up tank is via catholyte transfer tube
It is in fluid communication with the cathode chamber inlet and the cathode chamber outlet.
12. the method for production hydrogen according to claim 1, wherein the concentrated solution hold-up tank is via concentrated solution transfer tube
It is in fluid communication with the concentrated solution chamber inlet of each of n concentrated solution room.
13. the method for production hydrogen according to claim 1, wherein the dilute solution hold-up tank is via dilute solution transfer tube
It is in fluid communication with the dilute solution chamber inlet of each of n+1 dilute solution room.
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| CN108114599A (en) * | 2017-12-25 | 2018-06-05 | 中国科学技术大学 | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method |
| JPWO2019131341A1 (en) * | 2017-12-27 | 2020-12-10 | 昭和電工株式会社 | Redox flow battery |
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| CN109811359A (en) * | 2019-02-01 | 2019-05-28 | 大连理工大学 | A kind of each free-standing hydrogen production process of the electrode solution of low grade heat energy driving |
| CN110921796A (en) * | 2019-10-30 | 2020-03-27 | 同济大学 | System and method for synchronously producing hydrogen and oxygen by electrochemically recovering nitrogen and phosphorus in sewage |
| CN111155140A (en) * | 2020-01-15 | 2020-05-15 | 天津大学 | Hydrogen production system of reverse osmosis battery coupling photoelectricity hydrogen production device |
| GB2589649B (en) * | 2020-04-17 | 2022-02-23 | Atom Industries Int Ltd | Apparatus and method for production of hydrogen gas |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
| US12040517B2 (en) | 2022-11-15 | 2024-07-16 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell and methods of use thereof |
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