CN109811358B - Low-grade heat energy driven electrode liquid self-circulation type hydrogen production method - Google Patents
Low-grade heat energy driven electrode liquid self-circulation type hydrogen production method Download PDFInfo
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- CN109811358B CN109811358B CN201910103003.0A CN201910103003A CN109811358B CN 109811358 B CN109811358 B CN 109811358B CN 201910103003 A CN201910103003 A CN 201910103003A CN 109811358 B CN109811358 B CN 109811358B
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Images
Classifications
-
- 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
- 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
- Y02E60/50—Fuel cells
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- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A low-grade heat energy driven electrode liquid self-circulation hydrogen production method belongs to the technical field of new energy, and continuous hydrogen production is realized by taking low-grade heat energy as a driving force and by means of concentration change of a working solution. The method comprises the following steps: firstly, converting low-grade heat energy into chemical potential energy of a working solution by using a low-temperature multi-effect distillation method; then the chemical potential energy is converted into the potential difference between two electrodes of the cell stack based on the reverse electrodialysis principle; then the hydrogen and oxygen are respectively produced on the hydrogen producing electrode and the oxygen producing electrode in the same electrode liquid by reduction reaction or oxidation reaction, thus realizing the production of hydrogen and oxygen. The waste liquid losing part of chemical potential energy is recovered after flowing out of the cell stack, and then the regeneration is realized under the drive of low-grade heat energy. The electrode liquid is self-circulated between the hydrogen-producing electrode liquid cavity and the oxygen-producing electrode liquid cavity at two ends of the cell stack. The low-grade heat energy can be continuously, efficiently and stably converted and utilized; the hydrogen production system does not need to operate at high temperature and high pressure, the number of mechanical moving parts is small, and the capacity configuration is flexible; the single type of electrode liquid is adopted and is in closed circulation with electrolyte, and the operation can be carried out for a long time only by supplying deionized water.
Description
Technical Field
The invention belongs to the technical field of new energy, and relates to a method for continuously producing hydrogen by using low-grade heat energy as a driving force and by means of concentration change of a working solution.
Background
The hydrogen energy is considered as a new energy source with great development potential due to the advantages of high energy density, environment-friendly combustion products, rich source (water) reserves, wide applicable range and the like. At present, the common hydrogen production methods mainly comprise hydrogen production by water electrolysis, hydrogen production by coal gasification, hydrogen production by catalytic conversion of heavy oil, hydrogen production by steam of natural gas and the like, but the energy consumed by the methods is more than the energy generated by the methods, and some methods can increase carbon emission and aggravate air pollution. The widespread use of hydrogen energy is certainly hampered if the process for producing hydrogen is not effectively improved.
The nature and industrial production have abundant low-grade heat energy (such as solar energy, geothermal energy, industrial waste heat and the like) with huge supply quantity, and if the low-grade heat energy can be efficiently converted and utilized, the low-grade heat energy has important significance on sustainable development of energy sources. The current low-grade heat energy conversion and utilization technologies mainly comprise two types: one is based on a temperature-level lifting reverse circulation system (such as a heat pump), and the temperature-level lifting reverse circulation system is converted into heat or cold at a high temperature level and then is output to a user; and secondly, converting low-grade heat energy into high-grade electric energy to be output to users based on a power conversion positive circulation system (such as an organic Rankine circulation system). The former technology is mature at present, but the application is restricted by time (seasonal demand) and space (difficult to transmit over long distance). The latter is one of the research hotspots which have been paid keen attention in recent years in the field of energy, but there are still problems to be deeply explored in the technology, such as heat-work conversion efficiency, initial investment and maintenance cost, home-made capability of key components, and the like.
From the hydrogen production perspective, even if the above-mentioned heat-electricity conversion technology based on the power conversion positive circulation system is developed in the future, the hydrogen production by electrolyzing water by directly using the high-grade electric energy generated by the technology still has some defects, such as high electrode potential, large energy consumption, and much energy conversion loss, and the driving heat source temperature is usually required to be above 150 ℃. If low-grade heat energy (which can be as low as 85 ℃) is used as driving energy, and the low-grade heat energy power generation process is spanned, continuous hydrogen production is realized directly by means of the electrochemical process of the working solution, so that the development competitiveness of the hydrogen energy can be greatly improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for realizing continuous hydrogen production by using low-grade heat energy as a driving force and by means of the concentration change of a working solution. The basic technical principle is that low-grade heat energy is converted into chemical potential energy of a working solution by using a low-temperature multi-effect distillation method, the chemical potential energy is converted into potential difference at two ends of a cell stack based on a reverse electrodialysis principle, and then hydrogen and oxygen are respectively prepared through reduction reaction or oxidation reaction on hydrogen production electrodes and oxygen production electrodes. The waste liquid losing part of chemical potential energy is recovered after flowing out of the cell stack, and then the regeneration is realized under the drive of low-grade heat energy. And the electrode liquid is self-circulated between the hydrogen generating electrode liquid cavity and the oxygen generating electrode liquid cavity at the two ends of the cell stack.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low-grade heat energy driven electrode liquid self-circulation hydrogen production method takes low-grade heat energy as a driving force and realizes continuous hydrogen production by means of concentration change of a working solution, and the whole hydrogen production system consists of three subsystems: comprises a thermal subsystem, a reverse electrodialysis subsystem and a hydrogen production subsystem. The hydrogen production method comprises the following steps:
firstly, low-grade heat energy input from the outside is converted into concentration energy of working solution through a thermal subsystem
The thermal subsystem mainly comprises a generator 1, a condenser 2, a concentrated solution storage tank 3, a dilute solution storage tank 4, a waste liquid storage tank 5, a solution switching valve 6, a concentrated solution pump 7, a dilute solution pump 8, a waste liquid pump 9 and a solution flow pipeline. The inlet of the waste liquid storage tank 5 is connected with a solution outlet of the reverse electrodialysis subsystem; the outlet of the waste reservoir 5 is connected to the solution inlet of the generator 1 and the driving force for the flow of solution is provided by a waste pump 9 located therebetween. After the waste liquid flowing into the generator 1 is heated by low-grade hot streams (at the temperature of 80-200 ℃) in the generator 1, part of solvent can be evaporated, and a very small amount of solute can escape from a top steam outlet of the generator 1 along with the vaporized solvent and then enters the condenser 2. The inlet of the condenser 2 is connected with the top steam outlet of the generator 1, and the outlet is connected with the dilute solution storage tank 4. The condenser 2 is an air-cooled heat exchanger, and is used for condensing gaseous working solution into liquid, and then the working solution flowing out of the condenser 2 enters the dilute solution storage tank 4. In the generator 1, the waste liquid originally introduced from the waste liquid storage tank 5 is regenerated into a concentrated solution due to the evaporation of part of the solvent, the concentrated solution flows out from a solution outlet at the bottom of the generator 1, is radiated along the way in a pipeline, and then flows into the concentrated solution storage tank 3. The concentrated solution in the concentrated solution storage tank 3 and the dilute solution in the dilute solution storage tank 4 are respectively pumped into the reverse electrodialysis subsystem by a concentrated solution pump 7 and a dilute solution pump 8. And a solution switching valve 6 is arranged between the dilute solution storage tank 4 and the concentrated solution storage tank 3.
The heat-conducting medium of the low-grade heat stream can be water, saline inorganic matters such as NaCl aqueous solution and the like, low-boiling-point alcohols such as ethanol and the like, common heat-conducting silicone oil such as dimethyl silicon oil and the like, or halogenated hydrocarbon refrigerant; the temperature range of the low-grade heat stream is 80-200 ℃, the temperature range of a heat source is 85-205 ℃, and the heat source can be solar energy, geothermal energy, industrial waste heat or electric energy.
The concentration range of the dilute solution is 0.001-2 mol/L, and the concentration range of the concentrated solution is 0.5-10 mol/L.
Secondly, the concentration energy of the solution is converted into the potential difference between the cathode and the anode of the cell stack by a reverse electrodialysis subsystem
The reverse electrodialysis subsystem mainly comprises a reverse electrodialysis cell stack, an electrode liquid pump, a load and various electrical connection assemblies thereof. The reverse electrodialysis cell stack is a core component and comprises a cation exchange membrane 10, an anion exchange membrane 11, a hydrogen production electrode 12, an oxygen production electrode 13, end plates 14 at two ends and a spacer layer 15, wherein a working solution inlet of the reverse electrodialysis cell stack is connected with outlets of a concentrated solution storage tank 3 and a dilute solution storage tank 4 in a thermal subsystem, and a working solution outlet of the reverse electrodialysis cell stack is connected with an inlet of a waste liquid storage tank 5 in the thermal subsystem. The cation exchange membranes 10 and the anion exchange membranes 11 respectively allow only cations and anions in the working solution to pass through, the number of the cation exchange membranes 10 is at least 5 pairs, and the number of the cation exchange membranes is at most 500 pairs, and the number of the cation exchange membranes 10 is one more than that of the anion exchange membranes 11. The cation exchange membranes 10 and the anion exchange membranes 11 are alternately arranged in the reverse electrodialysis cell stack, so that a flow channel can be formed between any two ion exchange membranes. The flow path is divided into a concentrated solution flow path S1 and a dilute solution flow path S2, which are alternately arranged. The concentrated solution in the concentrated solution tank 3 is pumped into the concentrated solution flow path S1, and the dilute solution in the dilute solution tank 4 is pumped into the dilute solution flow path S2. Thus, a concentration gradient exists between any two adjacent flow channels. The cations in the concentrated solution flow passage S1 will migrate through the cation exchange membrane 10 to the adjacent dilute solution flow passage S2; at the same time, the anions migrate through the anion exchange membrane toward the adjacent dilute solution flow path S2 in the opposite direction. By adding up, ion flow is formed in the reverse electrodialysis cell stack, and a potential difference is formed between the two ends. Then, the concentrated solution losing part of ions and the dilute solution obtaining part of ions respectively flow out from the bottom outlet of the reverse electrodialysis cell stack and enter a waste liquid storage tank 5.
The negative and positive ion exchange membranes are alternately arranged in the reverse electrodialysis cell stack, and the positive ion exchange membranes are more than the negative ion exchange membranes, so that the two outermost sides are positive ion exchange membranes, and a hydrogen-producing electrode liquid cavity S3 is formed between the positive ion exchange membrane 10 on the outermost layer of one side, the hydrogen-producing electrode 12 and the end plate 14; correspondingly, an oxygen generating electrode liquid cavity S4 is formed between the other outermost cation exchange membrane and the oxygen generating electrode 13 and the end plate 14. Driven by the electrode liquid circulating pump 17, the electrode liquid circularly flows between the hydrogen producing electrode liquid cavity S3 and the oxygen producing electrode liquid cavity S4. Adjacent to the hydrogen production electrode liquid cavity S3 is a concentrated solution flow passage S1, and adjacent to the oxygen electrode liquid cavity S4 is a dilute solution flow passage S2.
The electrode liquid added into the reverse electrodialysis cell stack can be acid electrode liquid or alkaline electrode liquid, and the condition that the electrode liquid is neutral can occur in a certain dynamic process when the system operates is also included. The electrode solution mainly comprises hydrochloric acid (HCl), hypochlorous acid (HOCl) and sulfuric acid (H)2SO4) Nitric acid (HNO)3) Nitrous acid (HNO)2) Formic acid (HCOOH), acetic acid (CH)3COOH), oxalic acid (H)2C2O4) Carbonic acid (H)2CO3) Hydrofluoric acid (HF), sodium bisulfate (NaHSO)4) Aqueous solution, sodium hydrogen sulfate (NaSO)4) Aqueous solution, potassium hydroxide (KOH) aqueous solution, sodium hydroxide (NaOH) aqueous solution, lithium hydroxide (LiOH) aqueous solution, rubidium hydroxide (RbOH) aqueous solution, cesium hydroxide (CsOH) aqueous solution, sodium carbonate (Na)2CO3) Aqueous solution, sodium bicarbonate (NaHCO)3) Aqueous solution, calcium hydroxide (Ca (OH)2) Aqueous solutions, and the like. The concentration of the electrode solution ranges from 0.005mol/L to the saturated solution.
And the concentrated solution channel S1 and the dilute solution channel S2 are also provided with a spacer layer 15 which plays a role in supporting the channels, sealing the solution and guiding the solution. The spacer layer 15 mainly comprises a spacer and a spacer net, wherein the spacer is made of rubber and similar materials, and the thickness of the spacer is 50-1000 um; the separation net is woven by polymer materials such as polytetrafluoroethylene and the like or metal wires or alloy wires such as copper, silver, aluminum, stainless steel and the like, and the mesh number is 5-300.
The variable load 24 is connected between the hydrogen producing electrode 12 and the oxygen producing electrode 13, and the variable load 24 can be an electric appliance, a sliding rheostat or an electrolytic cell and the like. The material matrixes of the hydrogen production electrode 12 and the oxygen production electrode 13 are titanium, and ruthenium-iridium alloy, platinum-rhodium alloy, cerium-nickel-cobalt alloy and the like are plated on the outer surfaces of the hydrogen production electrode and the oxygen production electrode.
And thirdly, the hydrogen generation subsystem generates hydrogen and oxygen by utilizing the potential difference between two ends of the cell stack of the reverse electrodialysis subsystem through the hydrogen generation subsystem, and mainly comprises an electrode liquid recovery tank 16, an electrode liquid circulating pump 17, a hydrogen separator 18, a hydrogen storage tank 19, an electrode liquid supplement tank 20, an electrode supplement pump 21, an oxygen separator 22, an oxygen storage tank 23, a variable load 24, an electrode liquid switching valve 25 and a pipeline.
The electrode liquid inlet of the hydrogen-producing electrode liquid cavity S3 is connected with the outlet of the oxygen-producing electrode liquid cavity S4; the electrode liquid outlet of the hydrogen generating electrode liquid cavity S3 is connected with the inlet of the oxygen generating electrode liquid cavity S4. Then, the electrode solution circulates in the hydrogen-producing electrode solution chamber S3 and the oxygen-producing electrode solution chamber S4 by the driving of the electrode solution circulation pump 17. The hydrogen-producing electrode liquid chamber S3 is not communicated with the electrode liquid recovery tank 16, and the oxygen-producing electrode liquid chamber S4 is indirectly communicated with the electrode liquid replenishing tank 20 (with the electrode liquid switching valve 25 in between). The electrode liquid switching valve 25 is opened and the electrode liquid or deionized water is supplied to the system by the electrode liquid replenishment pump 21, if necessary.
If acidic electrode liquid is added into the reverse electrodialysis cell stack, the acidic electrode liquid passes through the 2e hydrogen-producing electrode liquid cavity S3-+2H+→H2The reaction at ≈ er; and in the oxygen generating electrode liquid cavity S4, H passes2O→2e-+1/2O2 -↑+2H+The reaction produces oxygen. H loss in hydrogen-producing electrode liquid cavity S3+The electrode solution can recover H in the oxygen generating electrode solution cavity+. If alkaline electrode liquid is added into the reverse electrodialysis cell stack, 2e is passed through the hydrogen-producing electrode liquid cavity S3-+2H2O→2OH-+H2The reaction at ≈ er; and 2OH is passed through the oxygen generating electrode liquid cavity S4-→H2O+1/2O2↑+2e-The reaction produces oxygen. In the hydrogen-producing electrode liquid cavityThe water consumed in S3 is recovered in the oxygen producing electrode chamber.
The hydrogen generated in the hydrogen-producing electrode liquid cavity S3 escapes from the top gas outlet of the hydrogen-producing electrode liquid cavity S3 and enters the hydrogen separator 18. The hydrogen separator 18 is a gas-liquid separator and is used for separating and purifying the hydrogen generated by the system and the carried electrode solution and performing basic safety protection. The inlet of the hydrogen separator 18 is connected with the hydrogen escape port, and two outlets of the hydrogen separator 18 are provided, one of the outlets is a gas outlet, is positioned at the top and is connected with the hydrogen storage tank 19; the second is a liquid outlet which is positioned at the bottom and is connected with the electrode liquid recovery tank 16. After passing through the hydrogen separator 18, the gaseous hydrogen enters the hydrogen storage tank 19, and the liquid electrode solution flows back into the electrode solution recovery tank 16.
Oxygen generated in the oxygen generating electrode liquid cavity S4 can escape from the top air outlet of the oxygen generating electrode liquid cavity S4 and enter the oxygen separator 22. The oxygen separator 22 is a gas-liquid separator, and is used for separating and purifying oxygen generated by the system and electrode liquid carried by the oxygen separator, and for basic safety protection. The inlet of the oxygen separator 22 is connected with the outlet at the top of the oxygen generating electrode liquid cavity S4, and two outlets of the oxygen separator 22 are provided, one of the outlets is a gas outlet, is positioned at the top and is connected with the oxygen storage tank 23; the second is a liquid outlet which is positioned at the bottom and is connected with an electrode liquid replenishing tank 20. After passing through the oxygen separator 22, the gaseous oxygen enters the oxygen storage tank 23, and the liquid electrode solution flows back into the electrode solution replenishing tank 20.
So far, the electrode liquid self-circulation type hydrogen and oxygen combined technology based on the reverse electrodialysis principle and the low-temperature multi-effect distillation principle is realized.
The working solution is formed by dissolving a solute in a solvent. The working solution is in closed circulation flow between the thermal subsystem and the reverse electrodialysis subsystem. The solute consists of cations (including lithium Li)+Sodium Na+Potassium K+Rubidium Rb+Cesium Cs+Magnesium Mg2+Calcium, Ca2+Strontium Sr+Silver Ag+Hydrogen H+And ammonium NH4 +) And anions (including fluorine F)-Chlorine Cl-Bromine Br-Iodine I-And carbonate radical CO3 2-Hydrogen carbonate radical HCO3 -Sulfuric acid radical SO3 2-Hydrogen sulfate radical HSO3 -CoO, cobaltate CoO2 -Nitrate radical NO3 -ClO of chlorate radical3 -Formate HCOO-And acetate COOH-) And (4) forming. The standard boiling point temperature of the solvent is between 50 and 200 ℃, and the solvent comprises ethanol (C)2H6O), methanol (CH)3OH), water (H)2O), acetonitrile (CH)3CN), diethyl ether (C)4H10O), acetone (CH)3COCH3) Isopropyl alcohol (C)3H8O), hexafluoroisopropanol (C)3H2F6O), trifluoroethanol (C)2H3F3O), trifluoroacetic acid (CF)3COOH), tetrahydrofuran (C)4H8O), Dimethylformamide (DMF), Dimethylacetamide (DMAC) and binary mixtures thereof. In order to adjust the thermodynamic and electrochemical properties of a solution composed of the above solute and solvent, it is sometimes necessary to add an additive thereto. The additive may be octanol (C)8H18O), decanol (C)10H22O) or the like, and block copolymers such as Polyoxyethylene (PEO) -polyoxypropylene (PPO) -Polyoxyethylene (PEO) may be used. The volume content of the additive does not exceed 5 percent of the total mass of the solution.
The invention has the beneficial effects that: (1) the low-grade heat energy can be continuously, efficiently and stably converted and utilized; (2) the cost of hydrogen production can be effectively reduced, and the high-grade energy loss is effectively reduced; (3) the single type of electrode liquid is adopted and is in closed circulation with electrolyte, the consumption of the electrode liquid is very little, and the electrode liquid can be used for a long time only by supplying deionized water. (4) The hydrogen production system does not need to operate at high temperature and high pressure, mechanical moving parts are few, the operation is quiet, and the large-scale manufacturing difficulty is small; (5) the available working solution has rich types, dynamically adjustable concentration and simple and easy recovery; (6) the hydrogen production and oxygen production system is easy to realize modularization, and the hydrogen production capacity can be flexibly set according to the user demand.
Drawings
FIG. 1 is a working flow chart of a low-grade heat energy driven electrode liquid self-circulation type (no external hanging) hydrogen production method based on the reverse electrodialysis principle
FIG. 2 is a working flow chart of a low-grade heat energy driven electrode liquid self-circulation type (with external hanging) hydrogen production method based on the reverse electrodialysis principle
In the figure: the device comprises a generator 1, a condenser 2, a concentrated solution storage tank 3, a dilute solution storage tank 4, a waste liquid storage tank 5, a solution switching valve 6, a concentrated solution pump 7, a dilute solution pump 8, a waste liquid pump 9, a cation exchange membrane 10, an anion exchange membrane 11, a hydrogen production electrode 12, an oxygen production electrode 13, an end plate 14, a spacer layer 15, an electrode liquid recovery tank 16, an electrode liquid circulating pump 17, a hydrogen separator 18, a hydrogen storage tank 19, an electrode liquid supplement tank 20, an electrode liquid supplement pump 21, an oxygen separator 22, an oxygen storage tank 23, a variable load 24 and an electrode liquid switching valve 25; an S1 concentrated solution flow passage, an S2 dilute solution flow passage, an S3 hydrogen producing electrode liquid cavity and an S4 oxygen producing electrode liquid cavity; s5 hanging the anode half cell of the electrolytic cell; s6 hanging the electrolytic bath cathode half bath outside; qinThe low-grade heat flow enters a generator; qoutThe low-grade heat stream leaves the generator after releasing heat; h2Hydrogen, O2Oxygen gas.
Detailed Description
The following describes the specific implementation process of the present invention in detail with reference to the technical scheme and the attached drawings.
Example 1: FIG. 1 shows the working flow of a low-grade heat energy driven electrode liquid self-circulation (no external hanging) hydrogen production method based on the reverse electrodialysis principle. With acid NaHSO4The aqueous solution is electrode circulating liquid. The method comprises the following steps:
firstly, a low-grade heat energy stream (for example, low-temperature heat conducting oil with the temperature of 120-130 ℃) enters the generator 1 from a driving heat source inlet at the lower left of the generator 1, a working solution (for example, a sodium chloride aqueous solution) is heated in the generator 1, the heat is released and cooled to about 60 ℃, and then the low-grade heat energy stream leaves the generator 1 from a driving heat source outlet at the upper left of the generator 1. After the waste liquid in the generator 1 is heated by the low grade heat energy stream, part of the solvent and a very small amount of solute are evaporated and escape from the top of the generator in gaseous form to enter the condenser 2. After being condensed, phase-changed and cooled to about 50 ℃ in the condenser 2, the solution is converted into dilute working solution, is discharged from the lower outlet of the condenser 2 and flows into a dilute solution storage tank 4. The condenser 2 is an air-cooled heat exchanger (such as a finned tube condenser) and is used for condensing the gaseous working solution into a liquid state and further cooling the working solution. While the waste liquid in the generator 1 is regenerated into a high-concentration working solution (for example, concentrated to 5mol/kg) as a result of partial solvent evaporation, the concentrated solution is then discharged from a solution outlet at the bottom of the generator 1 and gradually releases heat to the environment to about 50 ℃ in a pipeline, and then flows into a concentrated solution storage tank 3.
As previously mentioned, in the generator 1, the solvent is evaporated by heating and escapes from the working solution, carrying a very small amount of solute. The higher the temperature of the low grade heat energy stream, the higher the generator generation temperature and thus the greater the amount of solute carried out. Therefore, the supercooled liquid discharged from the condenser 2 is not a pure solvent, but a dilute solution having a very low concentration. If the dilute solution concentration in the dilute solution tank 4 does not reach a preset value (e.g., 0.03mol/kg), the solution switching valve 6 between the dilute solution tank 4 and the concentrated solution tank 3 is opened, and a small amount of concentrated solution is pumped into the dilute solution tank 4 by the concentrated solution pump 7 to perform physical mixing.
And secondly, pumping the concentrated solution in the concentrated solution storage tank 3 and the dilute solution in the dilute solution storage tank 4 into a concentrated solution flow channel S1 and a dilute solution flow channel S2 which are separated by a cation exchange membrane 10 and an anion exchange membrane 11 which are alternately arranged in the reverse electrodialysis galvanic pile respectively by using a concentrated solution pump 7 and a dilute solution pump 8. In this embodiment, the main material of the cation exchange membrane is sulfonated polyether ether ketone, the number of the cation exchange membrane is 11, the main material of the anion exchange membrane is polyepichlorohydrin, the number of the anion exchange membrane is 10, the length of the anion exchange membrane and the length of the cation exchange membrane are both 20cm, and the width of the anion exchange membrane and the width of the cation exchange membrane are both 10 cm. The flow rates of the dilute solution and the concentrated solution entering the concentrated solution flow channel S1 (10 in number) and the dilute solution flow channel S2 (10 in number) are controlled to be about 0.1cm/S, and the inflow mode is concurrent flow. The concentrated solution pump 7 and the dilute solution pump 8 are preferably constant flow pumps (peristaltic pumps may also be used if limited by cost control). In the concentrated solution flow path S1 and the dilute solution flow path S2, spacer layers 15 (21 in number) are disposed to perform the functions of flow guiding, supporting and sealing, and have a thickness of 200 um.
There is a chemical potential difference that drives the migration of ions between the concentrated solution (aqueous NaCl solution, concentration 5mol/kg) in the concentrated solution flow path S1 and the dilute solution (aqueous NaCl solution, concentration 0.03mol/kg) in the adjacent dilute solution flow path S2. Then, the cation (Na in this embodiment) in the concentrated solution flow path S1+) Will migrate through the cation exchange membrane 10 to the adjacent dilute solution flow path S2; and an anion (Cl in this embodiment)-) Will migrate through the anion exchange membrane 11 to the adjacent dilute solution flow path S2 in the opposite direction. By adding up, ion flow is formed inside the reverse electrodialysis cell stack, and a potential difference is formed between the two ends. In this embodiment, the potential difference can reach 1.5V. Then, the concentrated solution losing part of ions and the dilute solution obtaining part of ions respectively flow out from the flow channel outlet of the reverse electrodialysis cell stack and enter a waste liquid storage tank 5. And the working solution in the waste liquid storage tank 5 is pumped into the generator 1 by the waste liquid pump 9 for solution regeneration. Therefore, the closed circulation of the working solution is completed once, and the working principle is that the heat energy in the low-grade heat source is converted into the potential difference at two ends of the electrodialysis cell stack by means of the concentration difference change of the working solution.
In a third step, the potential difference across the reverse electrodialysis cell stack will be used to produce hydrogen and oxygen.
The number of the cation exchange membranes (11 sheets) is one more than that of the anion exchange membranes (10 sheets), which means that the outermost layers of the cation exchange membranes and the anion exchange membranes which are arranged in a staggered mode are cation exchange membranes. A hydrogen-producing electrode liquid cavity S3 (1 in number) is formed among the outermost cation exchange membrane 10, the hydrogen-producing electrode 12 and the end plate 14 in the cation moving direction; correspondingly, oxygen generating electrode liquid chambers S4 (number 1) are formed between the outermost cation exchange membrane 10 in the anion moving direction and the oxygen generating electrode 13 and the end plate 14. An electrode liquid inlet of the hydrogen-producing electrode liquid cavity S3 is connected with an outlet of the oxygen-producing electrode liquid cavity S4, and an electrode liquid outlet of the hydrogen-producing electrode liquid cavity S3 is connected with an inlet of the oxygen-producing electrode liquid cavity S4. Driven by the electrode liquid circulating pump 17, the electrode liquid circularly flows between the hydrogen producing electrode liquid cavity S3 and the oxygen producing electrode liquid cavity S4.
A variable load 24 is connected between the hydrogen producing electrode 12 and the oxygen producing electrode 13. In this embodiment, the hydrogen generating electrode 12 and the oxygen generating electrode 13 are made of titanium ruthenium iridium plated alloy, and the variable load 24 is a sliding rheostat.
In the hydrogen-producing electrode liquid cavity S3, the flowing electrode liquid is mainly NaHSO4The aqueous solution (acidic) also has Na migrated from the adjacent concentrated solution channel S1+. Hydrogen may be produced by the following reaction: 2NaHSO4+2Na+→2Na2SO4+2H+；2e-+2H+→H2×) @. The generated hydrogen can escape from the top gas outlet of the hydrogen-generating electrode liquid cavity S3 and enter the hydrogen separator 18. The inlet of the hydrogen separator 18 is connected with the hydrogen escape port, and two outlets of the hydrogen separator 18 are provided, one of the outlets is a gas outlet, is positioned at the top and is connected with the hydrogen storage tank 19; the second is a liquid outlet which is positioned at the bottom and is connected with the electrode liquid recovery tank 16. After passing through the hydrogen separator 18, the gaseous hydrogen enters the hydrogen storage tank 19, and the entrained small amount of liquid electrode solution flows back to the electrode solution recovery tank 16. After reaction in the hydrogen-producing electrode liquid cavity S3, the original NaHSO4The aqueous solution is converted to Na by replacement of the hydrogen ions with sodium ions2SO4The water solution flows out of the hydrogen producing electrode liquid cavity S3 and is pumped into the oxygen producing electrode liquid cavity S4 by the electrode liquid circulating pump 17.
In the oxygen generating electrode liquid cavity S4, the flowing electrode liquid is mainly Na2SO4The aqueous solution is neutral and has part of Na+To migrate out of the oxygen generating electrode chamber S4 and into the adjacent dilute solution channel S2. Oxygen can be generated and thus the regeneration of the electrode liquid can be achieved by the following reaction: h2O→O2-+2H+；O2-→2e-+1/2O2↑，2Na2SO4+2H+→2NaHSO4+2Na+. The generated oxygen can escape from the top air outlet of the oxygen generating electrode liquid cavity S4 and enter the oxygen separator 22. The inlet of the oxygen separator 22 is connected with the oxygen escape port, andtwo outlets are arranged on the oxygen separator 22, one of the outlets is a gas outlet, is positioned at the top and is connected with an oxygen storage tank 23; the second is a liquid outlet which is positioned at the bottom and is connected with an electrode liquid replenishing tank 20. After passing through the oxygen separator 22, the gaseous oxygen enters the oxygen storage tank 23, and the entrained small amount of liquid electrode solution flows back to the electrode solution replenishing tank 20. The electrode solution replenishing tank 20 is originally stored with only deionized water or dilute electrode solution, and is replenished by turning on the electrode solution replenishing pump 21 and the electrode solution switching valve 25 when necessary. After reaction in the oxygen generating electrode liquid cavity S4, the original Na2SO4The aqueous solution is converted into NaHSO due to partial replacement of sodium ions by hydrogen ions4The aqueous solution flows out of the oxygen producing electrode liquid cavity S4 and is pumped into the hydrogen producing electrode liquid cavity S3. The steps are circularly carried out.
Therefore, the working process of the low-grade heat energy driven acid electrode liquid self-circulation type (no external hanging) hydrogen production method based on the reverse electrodialysis principle is realized.
Example 2: also is a low-grade heat energy driven electrode liquid circulating (no external hanging) hydrogen production method based on the reverse electrodialysis principle, and the working principle is still shown in figure 1. In contrast to embodiment 1, the reverse electrodialysis cell stack of embodiment 2 is fed with an alkaline electrode solution, such as NaOH aqueous solution, which circulates between the hydrogen-producing electrode solution chamber S3 and the oxygen-producing electrode solution chamber S4. The first step and the second step in the working process of embodiment 2 are completely the same as those in embodiment 1, and are not described herein, but the difference lies in the third step.
Third, first, embodiment 2 is also the same as embodiment 1 in terms of hardware conditions, and redundant description is not necessary. The difference is the chemical reaction process characteristics of all solutions in the hydrogen producing electrode liquid chamber S3 and in the oxygen producing electrode liquid chamber S4. In the oxygen generating electrode liquid cavity S4, the flowing electrode liquid is alkaline NaOH aqueous solution, and part of Na is also contained+To migrate out of the oxygen generating electrode chamber S4 and into the adjacent dilute solution channel S2. Oxygen may be generated by the following reaction: 2NaOH → 2OH-+2Na+；2OH-→H2O+1/2O2↑+2e-. The generated oxygen can flow from the oxygen-generating electrode liquid cavity S4 escapes out of the top gas outlet and enters the oxygen separator 22. The inlet of the oxygen separator 22 is connected with the oxygen escape port, and two outlets of the oxygen separator 22 are provided, one of the outlets is a gas outlet, is positioned at the top and is connected with the oxygen storage tank 23; the second is a liquid outlet which is positioned at the bottom and is connected with an electrode liquid replenishing tank 20. After passing through the oxygen separator 22, the gaseous oxygen enters the oxygen storage tank 23, and the entrained small amount of liquid electrode solution flows back to the electrode solution replenishing tank 20. The electrode solution replenishing tank 20 is originally stored with only deionized water or dilute electrode solution, and is replenished by turning on the electrode solution replenishing pump 21 and the electrode solution switching valve 25 when necessary. After reaction in the oxygen producing electrode liquid cavity S4, the electrode liquid flows out of the oxygen producing electrode liquid cavity S4 and is pumped into the hydrogen producing electrode liquid cavity S3.
In the hydrogen-producing electrode liquid cavity S3, the flowing electrode liquid is also NaOH aqueous solution, and Na migrated from the adjacent concentrated solution flow passage S1 is also provided+. Hydrogen can be generated and NaOH regeneration can be achieved by the following reaction: 2e-+2H2O→2OH-+H2↑；2OH-+2Na+→ 2 NaOH. The generated hydrogen can escape from the top gas outlet of the hydrogen-generating electrode liquid cavity S3 and enter the hydrogen separator 18. The inlet of the hydrogen separator 18 is connected with the hydrogen escape port, and two outlets of the hydrogen separator 18 are provided, one of the outlets is a gas outlet, is positioned at the top and is connected with the hydrogen storage tank 19; the second is a liquid outlet which is positioned at the bottom and is connected with the electrode liquid recovery tank 16. After passing through the hydrogen separator 18, the gaseous hydrogen enters the hydrogen storage tank 19, and the entrained small amount of liquid electrode solution flows back to the electrode solution recovery tank 16. After reaction in the hydrogen-producing electrode liquid cavity S3, the electrode liquid flows out and is pumped into the oxygen-producing electrode liquid cavity S4. The steps are circularly carried out.
Therefore, the working process of the low-grade heat energy driven alkaline electrode liquid self-circulation (without external hanging) hydrogen production method based on the reverse electrodialysis principle is realized.
Example 3: FIG. 2 shows the working flow of a low-grade heat energy driven electrode liquid self-circulation (with external hanging) hydrogen production method based on the reverse electrodialysis principle.
On the basis of the specific embodiment 1 or the specific embodiment 2, if the number of the anion-cation exchange membranes and the cation-exchange membranes (which can obviously improve the output voltage of the reverse electrodialysis cell stack) is increased to more than 30 pairs, and the variable load 24 is selected as the external electrolytic tank, then the hydrogen production and the oxygen production are simultaneously carried out by the hydrogen production and the water electrolysis method of the reverse electrodialysis method, more hydrogen and oxygen can be produced on the original basis, as shown in the attached drawing 2.
The principle is basically similar to that of embodiment 1 and embodiment 2, and the description of the same parts is omitted. The key difference, in addition to increasing the ion exchange membrane pair number, is that the embodiment 3 uses an external electrolysis cell 24 to increase the hydrogen production capacity. The externally hung electrolytic tank 24 is a common direct current electrolytic water hydrogen production electrolytic tank, and the cathode and the anode of the externally hung electrolytic tank are respectively connected with the anode and the cathode of the reverse electrodialysis galvanic pile through leads. The electrolytic cell is filled with strong electrolyte aqueous solution (such as NaOH aqueous solution, only exists in the electrolytic cell), is separated into an external electrolytic cell anode half-cell S5 and an external electrolytic cell cathode half-cell S6 by a diaphragm (quantity 1), and is respectively inserted with a cathode electrode and an anode electrode. The cathode electrode and the anode electrode are common electrodes of a common direct current electrolytic water hydrogen production electrolytic tank, and have no special characteristics. The membrane allows OH-By, Na is not allowed+The diaphragm is also a common diaphragm of the common direct current water electrolysis hydrogen production electrolytic cell, and has no special requirement. The strong electrolyte aqueous solution contained in the electrolytic cell is not communicated with the electrode liquid of the reverse electrodialysis cell stack.
When an electric current is passed through both ends of the electrolytic bath 24, the reaction 4e is carried out in the vicinity of the electrodes of the cathode half-bath S6-+H2O→2H2↑+4OH-Generating hydrogen gas; and 4OH passes through the vicinity of the electrode of the anode half-cell S5-＝2H2O+O2↑+4e-Oxygen is generated. The generated hydrogen and oxygen respectively pass through the hydrogen separator 18 and the oxygen separator 22 and finally enter the hydrogen storage tank 19 and the oxygen storage tank 23 to be stored as described in the embodiment 1. The rest of the process is the same as that in embodiment 1 or embodiment 2, and need not be described in detail.
Therefore, the low-grade heat energy hydrogen production by the independent electrode liquid (externally hung electrolytic bath) reverse electrodialysis method is realized.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (7)
1. A low-grade heat energy driven electrode liquid self-circulation hydrogen production method is characterized in that the hydrogen production method is realized based on a hydrogen production system, continuous hydrogen production is realized by taking low-grade heat energy as a driving force and by means of concentration change of a working solution, wherein the hydrogen production system comprises a thermal subsystem, a reverse electrodialysis subsystem and a hydrogen production subsystem; the hydrogen production method comprises the following steps:
firstly, low-grade heat energy input from the outside is converted into concentration energy of working solution through a thermal subsystem
The heating subsystem comprises a generator (1), a condenser (2), a concentrated solution storage tank (3), a dilute solution storage tank (4), a waste liquid storage tank (5), a solution switching valve (6), a concentrated solution pump (7), a dilute solution pump (8), a waste liquid pump (9) and a solution flow pipeline; the inlet of the waste liquid storage tank (5) is connected with a solution discharge port of the reverse electrodialysis subsystem, the outlet of the waste liquid storage tank is connected with a solution inlet of the generator (1), and the driving force for the solution flow is provided by a waste liquid pump (9) positioned between the waste liquid storage tank and the generator; the inlet of the condenser (2) is connected with the top steam outlet of the generator (1), and the outlet is connected with the dilute solution storage tank (4); after the waste liquid flowing into the generator (1) is heated by the low-grade heat flow in the generator (1), part of solvent can be evaporated, and a very small amount of solute escapes from a vapor outlet at the top of the generator (1) along with the vaporized solvent and enters the condenser (2); in the generator (1), the waste liquid led in from the waste liquid storage tank (5) is regenerated into a concentrated solution due to the evaporation of part of the solvent, the concentrated solution flows out from a solution outlet at the bottom of the generator (1), radiates heat along the way in a pipeline, and then flows into the concentrated solution storage tank (3); the concentrated solution in the concentrated solution storage tank (3) and the dilute solution in the dilute solution storage tank (4) are respectively pumped into the reverse electrodialysis subsystem by a concentrated solution pump (7) and a dilute solution pump (8); a solution switching valve (6) is arranged between the dilute solution storage tank (4) and the concentrated solution storage tank (3);
secondly, the concentration energy of the solution is converted into the potential difference between the cathode and the anode of the cell stack by a reverse electrodialysis subsystem
The reverse electrodialysis subsystem mainly comprises a reverse electrodialysis cell stack, an electrode liquid pump, a load and various electrical connection components thereof; the reverse electrodialysis cell stack is a core component and comprises a cation exchange membrane (10), an anion exchange membrane (11), a hydrogen production electrode (12), an oxygen production electrode (13) and end plates (14) at two ends, wherein a working solution inlet of the reverse electrodialysis cell stack is connected with outlets of a concentrated solution storage tank (3) and a dilute solution storage tank (4) in a thermal subsystem, and a working solution outlet of the reverse electrodialysis cell stack is connected with an inlet of a waste liquid storage tank (5) in the thermal subsystem; the cation exchange membranes (10) and the anion exchange membranes (11) are alternately arranged in the reverse electrodialysis cell stack, only cations and anions in the working solution are allowed to pass through respectively, and the number of the cation exchange membranes (10) is one more than that of the anion exchange membranes (11); a concentrated solution channel S1 and a dilute solution channel S2 which are alternately arranged are formed between the anion-cation exchange membrane and the cation-anion exchange membrane, the concentrated solution in the concentrated solution storage tank (3) is pumped into the concentrated solution channel S1, the dilute solution in the dilute solution storage tank (4) is pumped into the dilute solution channel S2, and a concentration gradient exists between any two adjacent channels; cations in the concentrated solution flow passage S1 migrate to the adjacent dilute solution flow passage S2 through the cation exchange membrane (10), and meanwhile, anions migrate to the adjacent dilute solution flow passage S2 in the opposite direction through the anion exchange membrane; so as to accumulate, finally, ion current is formed in the reverse electrodialysis cell stack, and a potential difference is formed between the two ends; then, the concentrated solution losing part of ions and the dilute solution obtaining part of ions respectively flow out from the bottom outlet of the reverse electrodialysis cell stack and enter a waste liquid storage tank (5);
the outermost sides of the reverse electrodialysis cell stack are respectively provided with a cation exchange membrane, and a hydrogen-producing electrode liquid cavity S3 is formed among the outermost cation exchange membrane (10) on one side, the hydrogen-producing electrode (12) and the end plate (14); correspondingly, an oxygen generating electrode liquid cavity S4 is formed between the other outermost cation exchange membrane and the oxygen generating electrode (13) and the end plate (14); under the drive of the electrode liquid circulating pump (17), the electrode liquid circularly flows between the hydrogen-producing electrode liquid cavity S3 and the oxygen-producing electrode liquid cavity S4; a concentrated solution flow passage S1 is adjacent to the hydrogen production electrode liquid cavity S3, and a dilute solution flow passage S2 is adjacent to the oxygen electrode liquid cavity S4;
the electrode liquid added into the reverse electrodialysis cell stack can be acid electrode liquid or alkaline electrode liquid, and the condition of possible electric neutrality can occur in a certain dynamic process during the operation of the system; the electrode solution mainly comprises hydrochloric acid, hypochlorous acid, sulfuric acid, nitric acid, nitrous acid, formic acid, acetic acid, oxalic acid, carbonic acid, hydrofluoric acid, a sodium hydrogen sulfate aqueous solution, a potassium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a lithium hydroxide aqueous solution, a rubidium hydroxide aqueous solution, a cesium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution and a calcium hydroxide aqueous solution; the concentration of the electrode solution ranges from 0.005mol/L to the saturated solution;
thirdly, hydrogen and oxygen are produced by the hydrogen production subsystem by utilizing the potential difference between two ends of the cell stack of the reverse electrodialysis subsystem
The hydrogen production subsystem comprises an electrode liquid recovery tank (16), an electrode liquid circulating pump (17), a hydrogen separator (18), a hydrogen storage tank (19), an electrode liquid supplement tank (20), an oxygen separator (22), an oxygen storage tank (23) and a pipeline; an electrode liquid inlet of the hydrogen-producing electrode liquid cavity S3 is connected with an outlet of the oxygen-producing electrode liquid cavity S4, and an electrode liquid outlet of the hydrogen-producing electrode liquid cavity S3 is connected with an inlet of the oxygen-producing electrode liquid cavity S4; driven by an electrode liquid circulating pump (17), the electrode liquid circularly flows in the hydrogen-producing electrode liquid cavity S3 and the oxygen-producing electrode liquid cavity S4; the hydrogen-producing electrode liquid cavity S3 is not communicated with the electrode liquid recovery tank (16), and the oxygen-producing electrode liquid cavity S4 is communicated with the electrode liquid supplement tank (20);
hydrogen generated in the hydrogen-producing electrode liquid cavity S3 escapes from a top gas outlet of the hydrogen-producing electrode liquid cavity S3 and enters a hydrogen separator (18); after passing through the hydrogen separator (18), the gaseous hydrogen enters a hydrogen storage tank (19), and the liquid electrode liquid flows back to the electrode liquid recovery tank (16); oxygen generated in the oxygen generating electrode liquid cavity S4 escapes from a top air outlet of the oxygen generating electrode liquid cavity S4 and enters an oxygen separator (22); after passing through the oxygen separator (22), the gaseous oxygen enters the oxygen storage tank (23), and the liquid electrode liquid flows back into the electrode liquid supplement tank (20);
so far, the self-circulation hydrogen and oxygen combined preparation of the electrode liquid based on the reverse electrodialysis principle and the low-temperature multi-effect distillation principle is realized;
the working solution is formed by dissolving a solute in a solvent, and the working solution flows in a closed cycle between the thermal subsystem and the reverse electrodialysis subsystem; the solute is composed of cations and anions, and the cations include lithium Li+Sodium, Na+Potassium, K+Rb, Rb+Cesium Cs+Magnesium Mg2+Calcium, Ca2+Strontium, Sr+Ag, Ag+Hydrogen H+And ammonium NH4 +The anion comprises fluorine F-Chlorine (Cl)-Bromine Br-Iodine I-And carbonate CO3 2-Bicarbonate HCO3 -Sulfuric acid radical SO4 2-Hydrogen sulfate radical HSO4 -CoO, CoO2 -Nitrate radical NO3 -ClO, chlorate radical3 -Formate HCOO-And acetate CH3COO-(ii) a The standard boiling point temperature of the solvent is between 50 and 200 ℃, and the solvent comprises ethanol, methanol, water, acetonitrile, diethyl ether, acetone, isopropanol, hexafluoroisopropanol, trifluoroethanol, trifluoroacetic acid, tetrahydrofuran, dimethylformamide, dimethylacetamide and binary mixtures thereof.
2. The method for producing hydrogen by electrode liquid self-circulation driven by low-grade heat energy according to claim 1, wherein the heat conducting medium of the low-grade heat stream can be water, saline inorganic substances, low-boiling alcohols, common heat conducting silicone oil or halogenated hydrocarbon refrigerants; the temperature range of the low-grade heat stream is 80-200 ℃, and the temperature range of a heat source is 85-205 ℃.
3. The method for preparing hydrogen by self-circulation of electrode liquid driven by low-grade heat energy according to claim 1, characterized in that, in order to adjust the thermodynamic and electrochemical properties of the solution composed of the solute and the solvent of the working solution, the method is based onAn additive is required to be added into the solution, and the volume content of the additive does not exceed 5 percent of the total mass of the solution; the additive is octanol C8H18O, decanol C10H22O higher alcohols, or Polyoxyethylene (PEO) -polyoxypropylene (PPO) -Polyoxyethylene (PEO) block copolymers.
4. The low-grade heat energy driven electrode liquid self-circulation hydrogen production method according to claim 1, wherein the concentration range of the dilute solution is 0.001-2 mol/L, and the concentration range of the concentrated solution is 0.5-10 mol/L.
5. The low-grade heat energy-driven electrode liquid self-circulation hydrogen production method according to claim 1, wherein the number of the cation exchange membranes (10) and the anion exchange membranes (11) in the reverse electrodialysis subsystem is as follows: at least 5 pairs and at most 500 pairs.
6. The low-grade heat energy driven electrode liquid self-circulation hydrogen production method according to claim 1, characterized in that a variable load (24) can be connected between the hydrogen production electrode (12) and the oxygen production electrode (13), and the variable load (24) can be an electric appliance, a slide rheostat or an electrolytic cell.
7. The low-grade heat energy-driven electrode liquid self-circulation hydrogen production method according to claim 1, characterized in that an electrode liquid switching valve (25) is further arranged between the oxygen-producing electrode liquid cavity S4 and the electrode liquid replenishing tank (20) in the third step, and the electrode liquid switching valve (25) can be opened if necessary, and the electrode liquid or deionized water is replenished to the system through an electrode liquid replenishing pump (21).
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| 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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| CN111085219B (en) * | 2019-12-27 | 2021-04-30 | 大连理工大学 | Carbon-supported nickel oxide-modified platinum-rhodium nanorod electrocatalyst for alkaline hydrogen evolution reaction and preparation method and application thereof |
| CN112624234B (en) * | 2020-11-26 | 2021-12-14 | 大连理工大学 | System and method for treating organic wastewater by using low-grade heat energy |
| US11339483B1 (en) | 2021-04-05 | 2022-05-24 | Alchemr, Inc. | Water electrolyzers employing anion exchange membranes |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
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| CN105810985B (en) * | 2016-03-07 | 2018-07-06 | 大连理工大学 | Suitable for the ternary working medium pair of inverse electrodialysis formula thermo-electrically converting system |
| CN107326387B (en) * | 2017-06-22 | 2019-05-17 | 中国科学技术大学 | The equipment and its application method of hydrogen can be directly produced using salt error |
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| 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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