CN119177458A - Water electrolysis hydrogen production system based on proton exchange membrane electrolysis bath - Google Patents
Water electrolysis hydrogen production system based on proton exchange membrane electrolysis bath Download PDFInfo
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Abstract
The application is mainly used in the technical field of electrolytic hydrogen production. The application discloses an electrolytic water hydrogen production system based on a proton exchange membrane electrolytic tank, which comprises an electrolytic unit, a water circulation unit and a gas-liquid separation unit, wherein the electrolytic unit is used for carrying out electrolytic treatment on liquid water to obtain hydrogen, oxygen and gas-liquid mixed state water, the gas-liquid separation unit comprises a primary separation module and a secondary separation module, the primary separation module is used for carrying out separation treatment on the gas-liquid mixed state water to obtain separated liquid water, the secondary separation module is used for carrying out gas release treatment on the separated liquid water to obtain gas released liquid water, and the water circulation unit is used for transmitting the gas released liquid water to the electrolytic unit. The technical scheme of the application can accelerate the release speed of the gas dissolved in the liquid water and reduce the content of the gas in the liquid water, thereby reducing the safety risk of the electrolytic water hydrogen production system in the hydrogen production process.
Description
Technical Field
The invention relates to the technical field of electrolytic hydrogen production, in particular to a water electrolysis hydrogen production system based on a proton exchange membrane electrolyzer.
Background
Currently, the new energy industry represented by hydrogen energy is highly valued and strongly supported by governments from country to local. The hydrogen energy has the characteristics of wide sources, energy conservation, environmental protection, high efficiency, cleanness, high heat efficiency and the like, has a strong substitution effect on traditional fossil energy, and is considered as an important scheme for realizing energy conversion to green low carbon. When the existing water electrolysis hydrogen production system works, electrochemical reaction is carried out through a proton exchange membrane electrolytic tank, so that water is electrolyzed into hydrogen and oxygen. However, part of oxyhydrogen gas is dissolved in the non-electrolyzed liquid discharged from the proton exchange membrane electrolyzer, and the existing electrolyzed water hydrogen production system cannot separate the gas from the liquid to the greatest extent, and meanwhile, the liquid at the two sides of the proton exchange membrane electrolyzer needs to be recycled, so that the gas dissolved in the liquid escapes in the same gas phase space to easily form an explosive environment, and therefore, the existing electrolyzed water hydrogen production system has a huge potential safety hazard.
Disclosure of Invention
The invention provides a water electrolysis hydrogen production system based on a proton exchange membrane electrolytic tank, which can accelerate the release speed of gas dissolved in liquid water and reduce the content of the gas in the liquid water, thereby reducing the safety risk of the water electrolysis hydrogen production system in the hydrogen production process.
The invention provides an electrolytic water hydrogen production system based on a proton exchange membrane electrolytic tank, which comprises an electrolytic unit, a water circulation unit and a gas-liquid separation unit, wherein the electrolytic unit is connected with the water circulation unit;
the electrolysis unit is used for carrying out electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed state water;
the gas-liquid separation unit comprises a primary separation module and a secondary separation module;
The primary separation module is used for separating the gas-liquid mixed state water to obtain liquid water after separation treatment;
The secondary separation module is used for carrying out gas release treatment on the liquid water after separation treatment so as to obtain liquid water after gas release;
the water circulation unit is used for transmitting the liquid water released by the gas to the electrolysis unit after the conductivity of the liquid water is reduced.
Optionally, the gas-liquid separation unit comprises a first gas-liquid separation subunit and a second gas-liquid separation subunit;
The electrolysis unit is also used for outputting hydrogen and liquid water after electrolysis treatment through the first end of the electrolysis unit, and outputting oxygen and liquid water after electrolysis treatment through the second end of the electrolysis unit;
the first gas-liquid separation unit comprises a first primary separation module and a first secondary separation module;
The first primary separation module is used for separating the hydrogen so as to obtain liquid water in the hydrogen;
The first secondary separation module is used for carrying out gas release treatment on the liquid water in the hydrogen and the liquid water after the electrolytic treatment so as to obtain the liquid water after the gas release;
The second gas-liquid separation unit comprises a second primary separation module and a second secondary separation module;
the second stage separation module is used for separating the oxygen to obtain liquid water in the oxygen;
the second-stage separation module is used for carrying out gas release treatment on the liquid water in the oxygen and the liquid water after the electrolytic treatment so as to obtain the liquid water after the gas release;
The water circulation unit is also used for collecting the liquid water which is released by the gas output by the first secondary separation module and the second secondary separation module and transmitting the liquid water to the electrolysis unit.
Optionally, the first gas-liquid separation subunit includes a first regulating valve module, and the second gas-liquid separation subunit includes a second regulating valve module;
the first regulating valve module is used for regulating the air pressure in the first air-liquid separation subunit;
The second regulating valve module is used for controlling the air pressure in the second air-liquid separation subunit according to a preset air pressure value.
Optionally, the first primary separation module comprises a first primary separator, a first heat exchanger, and a first demister;
The first end of the first-stage separator is used for inputting hydrogen and electrolyzed liquid water, the second end of the first-stage separator is connected with the input end of the first heat exchanger, the third end of the first-stage separator is connected with the third end of the first demister, and the fourth end of the first-stage separator is used for outputting the liquid water in the hydrogen and the electrolyzed liquid water;
the output end of the first heat exchanger is connected with the first end of the first demister, and the first heat exchanger is used for acquiring hydrogen through the input end of the first heat exchanger, condensing the acquired hydrogen and outputting the condensed hydrogen through the output end of the first heat exchanger;
The first demister is used for separating the condensed hydrogen to obtain liquid water in the hydrogen and the separated hydrogen, and outputting the separated hydrogen through the second end of the first demister and the liquid water in the hydrogen through the third end of the first demister.
Optionally, the second stage separation module comprises a second stage separator, a second heat exchanger, and a second demister;
The first end of the second primary separator is used for inputting oxygen and electrolyzed liquid water, the second end of the second primary separator is connected with the input end of the second heat exchanger, the third end of the second primary separator is connected with the third end of the second demister, the fourth end of the second primary separator is used for transmitting the liquid water in the oxygen and the electrolyzed liquid water to the electrolysis unit and the second secondary separation module, and the fifth end of the second primary separator is used for obtaining the liquid water which is output by the water circulation unit and is released by gas;
the output end of the second heat exchanger is connected with the second end of the second demister, and the second heat exchanger is used for acquiring oxygen through the input end of the second heat exchanger, condensing the acquired oxygen and outputting the condensed oxygen through the output end of the second heat exchanger;
the second demister is used for separating the condensed oxygen to obtain liquid water in the oxygen and the separated oxygen, and outputting the separated oxygen through the second end of the second demister and the liquid water in the oxygen through the third end of the second demister.
Optionally, the water circulation unit comprises a circulating water tank, a resin tank, a first water pump and a second water pump;
the circulating water tank is used for storing the liquid water released by the gas and transmitting the liquid water stored in the circulating water tank to the resin tank through the first water pump;
the resin tank is used for carrying out deionized treatment on the liquid water and outputting the deionized liquid water through the second water pump.
Optionally, the first secondary separation module comprises a first secondary separator, the second secondary separation module comprises a second secondary separator, and the first secondary separator and the second secondary separator are both liquid containers;
The input end of the first secondary separator and the input end of the second secondary separator are respectively provided with a pressure reducing valve, and the output end of the first secondary separator and the output end of the second secondary separator are respectively connected with the circulating water tank through overflow pipes.
Optionally, the first secondary separator includes a first input terminal, a first output terminal, a second input terminal, and a second output terminal;
The first input end of the first secondary separator is used for inputting liquid water in the hydrogen and the electrolyzed liquid water;
The first output end of the first secondary separator is used for outputting liquid water after gas release;
the second input end of the first secondary separator is used for inputting inert gas;
and the second output end of the first secondary separator is used for outputting the gas in the first secondary separator.
Optionally, the system comprises a control unit comprising a plurality of sensors;
Each sensor is used for detecting the electrolysis unit, the water circulation unit or the gas-liquid separation unit to obtain a process parameter value;
And the control unit is used for judging whether the process parameter value is in a first preset value range, if not, controlling the electrolysis unit, the water circulation unit and the gas-liquid separation unit to stop working, and if so, controlling the electrolysis unit, the water circulation unit or the gas-liquid separation unit to regulate until the process parameter value is in a second preset value range when the process parameter value is not in the second preset value range.
Optionally, the electrolysis unit comprises:
the proton exchange membrane electrolysis module is used for carrying out electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed state water;
the voltage control module is used for detecting the cell voltage and the cell current voltage of the proton exchange membrane electrolysis module, and controlling the proton exchange membrane electrolysis module to stop working when any detected cell voltage is higher than a preset voltage value or the detected cell current voltage is higher than a preset current voltage value.
The invention has at least the following beneficial effects:
In the technical scheme of the application, after the electrolysis unit carries out electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed water, gas-liquid separation is carried out in the primary separation module, mainly the liquid water in the gas is separated, and the liquid water in the primary separation module passes through the secondary separation module to release the gas dissolved in the water. The scheme adopts a secondary separation technology, can accelerate the release speed of the gas dissolved in the liquid water, and releases the gas dissolved in the water as much as possible. And finally, the liquid water released by the gas is transmitted to the electrolysis unit through the water circulation unit for repeated use for electrolytic treatment, so that the water resource is saved, meanwhile, the gas content in the liquid water is reduced because the gas in the recycled water is escaped, and the situation that the hydrogen and oxygen escaped in the recycled liquid water are converged in the electrolysis unit to form an explosive gas environment is avoided, thereby reducing the safety risk of the electrolytic water hydrogen production system in the hydrogen production process.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate and do not limit the invention.
FIG. 1 is a first schematic diagram of a proton exchange membrane electrolyzer-based electrolyzed water hydrogen production system;
FIG. 2 is a second schematic diagram of a proton exchange membrane electrolyzer-based electrolyzed water hydrogen production system;
FIG. 3 is a third schematic diagram of a proton exchange membrane electrolyzer based electrolyzed water hydrogen production system;
Wherein, 1, a proton exchange membrane electrolyzer; 2, a hydrogen primary separator, a hydrogen gas circuit heat exchanger, a hydrogen demister, a 5, a hydrogen regulating valve, a 6, a hydrogen intermediate oxygen analyzer, an 8, an oxygen primary separator, a 9, an oxygen gas circuit heat exchanger, a 10, an oxygen demister, an 11, an oxygen regulating valve, a 12, an oxygen intermediate hydrogen analyzer, a 14, a circulating pump, a 15, an oxygen side waterway heat exchanger, a 16, an oxygen side reducing valve, a 17, a hydrogen side reducing valve, a 18, a hydrogen secondary separator, a 19, an oxygen secondary separator, a 20, a circulating water tank, a 21, a water supplementing pump, a 22, a water supplementing heat exchanger, a 23, a resin tank, a 24, a high-pressure pump.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The electrolyte hydrogen production technology mainly comprises three technologies, namely Alkali Lye (ALK), proton Exchange Membrane (PEM) and Solid Oxide (SOEC) water electrolysis technology, wherein the proton exchange membrane has the advantages of stable chemical property, high proton conductivity, no pore, gas isolation and the like compared with other membranes, can be integrated with an electrode, reduces extra resistance and electric energy loss caused by the distance between two electrodes, can improve the purity of hydrogen production, obtains high current density and quick response, and is suitable for a renewable energy power generation system with larger volatility.
However, when the existing proton exchange membrane electrolytic water system works, a series of problems exist:
the conductivity of deionized water is increased in the electrolysis process, and water with higher conductivity is directly discharged, so that the utilization efficiency of the deionized water is low and resource waste is caused;
the liquid level of the liquid storage tank is controlled by an instrument detection valve, the instrument valve has high cost, and meanwhile, if the instrument valve fails, the system control cannot be realized and dangerous conditions are easy to occur;
the proton exchange membrane electrolyzer is easily affected by voltage, and the too high voltage can break down the proton exchange membrane to cause the cathode and anode to be short-circuited, and the too low voltage can not meet the requirement of gas production;
The pressure difference requirement of the electrolytic tank is very high, and the liquid level fluctuation of the separator is very easy to influence the pressure difference of two sides, so that the risk of forming explosive gas by hydrogen and oxygen channeling exists;
When the electrolytic water hydrogen production system is started and stopped or abnormal working conditions occur, manual operation intervention is needed, and potential safety hazards exist;
The cooling water with the temperature of about 40 ℃ is used for exchanging heat for the hydrogen, so that the gas-water separation in the gas is not thorough, and the concentration of the separated hydrogen can not meet the requirement.
It should be noted that, part of the gas is dissolved in the gas-liquid two-phase flow generated by the proton exchange membrane electrolyzer, and the gas cannot be separated from the liquid to the greatest extent, so that the equipment of the water electrolysis hydrogen production system is easy to explode when working in the environment of the gas-liquid mixing state, and therefore, the existing water electrolysis hydrogen production system has great potential safety hazard.
In order to solve the problems, the technical scheme of the application can accelerate the release speed of the gas dissolved in the liquid water and reduce the content of the gas in the liquid water, thereby reducing the safety risk of the electrolytic water hydrogen production system in the hydrogen production process. The following is an example of the technical scheme of the present application.
Referring to fig. 1, fig. 1 is a schematic diagram of a first structure of a water electrolysis hydrogen production system based on a proton exchange membrane electrolyzer.
The embodiment provides an electrolytic water hydrogen production system based on a proton exchange membrane electrolytic tank, which comprises an electrolytic unit, a water circulation unit and a gas-liquid separation unit.
And the electrolysis unit is used for carrying out electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed state water.
The gas-liquid separation unit comprises a primary separation module and a secondary separation module.
The first-stage separation module is used for separating the gas-liquid mixed state water to obtain liquid water after separation treatment.
The secondary separation module is used for carrying out gas release treatment on the liquid water after separation treatment so as to obtain the liquid water after gas release.
And the water circulation unit is used for conveying the liquid water released by the gas to the electrolysis unit.
It can be understood that the technical scheme of the application is to convey the liquid water among the electrolysis unit, the water circulation unit and the gas-liquid separation unit through the pipeline, the oxygen and the hydrogen obtained by electrolysis in the liquid water are led into the preset gas storage device through the pipeline, the liquid water is continuously recycled among the electrolysis unit, the water circulation unit and the gas-liquid separation unit until the liquid water volume is less than the preset water volume, and new liquid water is added into the electrolytic water hydrogen production system based on the proton exchange membrane electrolysis tank.
In some embodiments, the electrolysis cell is an electrolysis cell, optionally a proton exchange membrane electrolysis cell.
It can be understood that in the technical scheme of the application, after the electrolysis unit performs electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed water, gas-liquid separation is performed in the primary separation module, mainly separating the liquid water in the gas, and the liquid water in the primary separation module passes through the secondary separation module to release the gas dissolved in the water. The scheme adopts a secondary separation technology, can accelerate the release speed of the gas dissolved in the liquid water, and releases the gas dissolved in the water as much as possible. And finally, the liquid water released by the gas is transmitted to the electrolysis unit through the water circulation unit for repeated use for electrolytic treatment, so that the water resource is saved, meanwhile, the gas content in the liquid water is reduced because the gas in the recycled water is escaped, and the situation that the hydrogen and oxygen escaped in the recycled liquid water are converged in the electrolysis unit to form an explosive gas environment is avoided, thereby reducing the safety risk of the electrolytic water hydrogen production system in the hydrogen production process.
Optionally, the primary separation module is set to operate in a high pressure state, and the secondary separation module is set to operate in a normal pressure state.
It will be appreciated that the solubility of the gases at different pressures is different, and that part of the gases can be separated in the high pressure gas-liquid separator, and that part of the gases must still be dissolved in the water, and when the external conditions change (such as temperature, pressure, etc.), the gases dissolved in the water escape, and the escaped oxyhydrogen merges in the electrolytic cell to form an explosive gas environment, with a certain risk. In the embodiment, a secondary separation technology, namely high-pressure gas-liquid separation and low-pressure gas-liquid separation, is adopted to release the gas dissolved in the water as far as possible, so that gas explosion is avoided.
Referring to fig. 2, fig. 2 is a schematic diagram of a second structure of a water electrolysis hydrogen production system based on a proton exchange membrane electrolyzer.
In some embodiments, the gas-liquid separation unit includes a first gas-liquid separation subunit and a second gas-liquid separation subunit.
The electrolysis unit is also used for outputting hydrogen and liquid water after electrolysis treatment through the first end of the electrolysis unit and outputting oxygen and liquid water after electrolysis treatment through the second end of the electrolysis unit.
The first gas-liquid separation unit comprises a first primary separation module and a first secondary separation module.
The first-stage separation module is used for separating the hydrogen so as to obtain liquid water in the hydrogen.
The first secondary separation module is used for carrying out gas release treatment on the liquid water in the hydrogen and the liquid water after the electrolytic treatment so as to obtain the liquid water after the gas release.
The second gas-liquid separation unit comprises a second primary separation module and a second secondary separation module.
And the second-stage separation module is used for separating and treating the oxygen to obtain liquid water in the oxygen.
The second-stage separation module is used for carrying out gas release treatment on the liquid water in the oxygen and the liquid water after the electrolytic treatment so as to obtain the liquid water after the gas release.
The water circulation unit is also used for collecting the liquid water which is released by the gas output by the first secondary separation module and the second secondary separation module and transmitting the liquid water to the electrolysis unit.
In some embodiments, the electrolysis unit further comprises an electrolysis cell, a circulation pump, and a third heat exchanger.
The circulating pump is used for conveying the liquid water after the gas release to the third heat exchanger.
The third heat exchanger is used for adjusting the temperature of the liquid water after the gas is released to a preset temperature.
The electrolyzer is used for electrolyzing the liquid water released by the gas at the preset temperature to obtain hydrogen, oxygen and gas-liquid mixed water.
It can be understood that the liquid water after the gas release is conveyed to the third heat exchanger by the circulating pump for cooling, so that the temperature of the liquid water after the gas release is reduced to the optimal operation temperature of the electrolytic tank. The electrolytic cell is subjected to electrolytic reaction under the action of direct current, a small amount of liquid water carried by hydrogen obtained by electrolysis is discharged from the cathode side of the electrolytic cell and is further sent to the first-stage separation module for gas-liquid separation, and unreacted liquid water carried by oxygen is discharged from the anode side of the electrolytic cell and is further sent to the second-stage separation module for gas-liquid separation.
In some embodiments, the electrolyzer is a proton exchange membrane electrolyzer, and the electrolyzer unit further comprises an electrolyzer temperature control module for monitoring the temperature of the electrolyzer, and when it is detected that the temperature of the electrolyzer is not within a preset range of values, regulating the temperature or flow rate at the input of the electrolyzer until the temperature of the electrolyzer is within the preset range of values.
It will be appreciated that overheating of the pem electrolyzer temperature will affect the pem performance and lifetime, so that part of the water in the pem electrolyzer is used as the electrolysis feed and part is used to carry away the heat generated by the pem electrolyzer electrolysis. In order to ensure that the temperature of the proton exchange membrane electrolytic cell is within a set range, a temperature detector is arranged at the outlet of the proton exchange membrane electrolytic cell, and when the temperature abnormality is detected, the temperature detector can be automatically adjusted according to a control program, such as adjusting the cooling water flow of the electrolytic cell.
In some embodiments, the first gas-liquid separation sub-unit comprises a first regulator valve module and the second gas-liquid separation sub-unit comprises a second regulator valve module.
The first regulating valve module is used for regulating the air pressure in the first air-liquid separation subunit.
The second regulating valve module is used for controlling the air pressure in the second air-liquid separation subunit according to a preset air pressure value.
In some embodiments, the first regulator valve module comprises a first regulator valve and the second regulator valve module comprises a second regulator valve and a vent valve.
It can be understood that the second regulating valve and the emptying valve are arranged in the pipeline, the second regulating valve ensures the discharge pressure of oxygen in the second gas-liquid separation subunit, so that the proton exchange membrane electrolyzer can produce hydrogen at the optimal pressure, and meanwhile, when the device has abnormal working conditions, the emptying valve can be opened in time to ensure the safety of the device.
It can be understood that the pressure difference range of the hydrogen and oxygen sides of the existing alkaline tank hydrogen production system is within 3Kpa to 5Kpa, the pressure difference is regulated by the control valve of the oxygen outlet, very accurate pressure difference control is needed, otherwise hydrogen and oxygen channeling is easy to occur, meanwhile, the allowable pressure difference range is too small, the liquid level of the hydrogen and oxygen liquid separator greatly influences the pressure difference, the liquid level is monitored by adding a liquid level meter at present, the pressure difference change caused by the overlarge fluctuation of the liquid level is prevented, and the cost is increased by adding the liquid level meter. In the embodiment, the pressure difference of the oxyhydrogen side can reach 5 bar, and the pressure of the oxyhydrogen side can be regulated by using the regulating valve to meet the pressure difference requirement of the proton exchange membrane electrolytic cell, so that the use of the liquid level meter is reduced, the cost is reduced, the frequent action of the valve caused by liquid level fluctuation is avoided, and the service life of the valve is prolonged.
In some embodiments, the first primary separation module includes a first primary separator, a first heat exchanger, and a first mist eliminator.
The first end of the first primary separator is used for inputting hydrogen and liquid water after electrolytic treatment, the second end of the first primary separator is connected with the input end of the first heat exchanger, the third end of the first primary separator is connected with the third end of the first demister, and the fourth end of the first primary separator is used for outputting the liquid water in the hydrogen and the liquid water after electrolytic treatment.
The output end of the first heat exchanger is connected with the first end of the first demister, and the first heat exchanger is used for acquiring hydrogen through the input end of the first heat exchanger and outputting the acquired hydrogen through the output end of the first heat exchanger after condensing the acquired hydrogen.
The first demister is used for carrying out separation treatment on the hydrogen after condensation treatment so as to obtain liquid water in the hydrogen and the hydrogen after separation treatment, and outputting the hydrogen after separation treatment through the second end of the first demister and the liquid water in the hydrogen through the third end of the first demister.
In some embodiments, the second stage separation module includes a second stage separator, a second heat exchanger, and a second mist eliminator.
The first end of the second primary separator is used for inputting oxygen and liquid water after electrolytic treatment, the second end of the second primary separator is connected with the input end of the second heat exchanger, the third end of the second primary separator is connected with the third end of the second demister, the fourth end of the second primary separator is used for transmitting the liquid water in the oxygen and the liquid water after electrolytic treatment to the electrolytic unit and the second secondary separation module, and the fifth end of the second primary separator is used for obtaining the liquid water after gas release output by the water circulation unit.
The output end of the second heat exchanger is connected with the second end of the second demister, and the second heat exchanger is used for acquiring oxygen through the input end of the second heat exchanger and outputting the acquired oxygen through the output end of the second heat exchanger after condensing treatment.
The second demister is used for carrying out separation treatment on the oxygen after condensation treatment so as to obtain liquid water in the oxygen and the oxygen after separation treatment, and outputting the oxygen after separation treatment through a second end of the second demister and the liquid water in the oxygen through a third end of the second demister.
In some embodiments, the water circulation unit includes a circulation water tank, a resin tank, and first and second water pumps.
And the circulating water tank is used for storing the liquid water released by the gas and transmitting the liquid water stored in the circulating water tank to the resin tank through the first water pump.
And the resin tank is used for carrying out deionized treatment on the liquid water and outputting the deionized liquid water through a second water pump.
It can be understood that in the electrolytic water hydrogen production system based on the proton exchange membrane electrolytic tank of the embodiment, the long-time operation inevitably leads to the increase of the conductivity of deionized water, namely the increase of conductive ions, while the proton exchange membrane is very sensitive to ions, and the long-time operation in water with higher conductivity shortens the service life of the proton exchange membrane electrolytic tank. To avoid this, the prior art directly discharges water with unqualified conductivity and re-injects water with qualified conductivity, which results in waste of water resources, which is acceptable in areas with abundant water resources and unacceptable in areas with insufficient water resources. In the embodiment, through the resin tank, the conductivity of deionized water refined by the resin tank can be lower than 0.5 mu S/cm, so that the requirements of the proton exchange membrane electrolytic tank are completely met, the conductivity is reduced, and the recycling of liquid water is facilitated.
In some embodiments, the first secondary separation module comprises a first secondary separator and the second secondary separation module comprises a second secondary separator, the first secondary separator and the second secondary separator each being a liquid vessel.
The input end of the first secondary separator and the input end of the second secondary separator are both provided with pressure reducing valves, and the output end of the first secondary separator and the output end of the second secondary separator are both connected with the circulating water tank through overflow pipes.
It will be appreciated that current alkaline cell water electrolysis systems control the liquid level in the vessel by means of meter monitoring, valve action coordination, and the use of meters and valves results in increased costs. The embodiment keeps the liquid level constant through the overflow pipe, reduces the use of the valve and the instrument, reduces the cost, and simultaneously avoids the safety risk caused by the failure of the instrument or the valve.
In some embodiments, the first secondary separator includes a first input, a first output, and a second input, a second output.
The first input end of the first secondary separator is used for inputting liquid water in the hydrogen and liquid water after electrolytic treatment.
The first output end of the first secondary separator is used for outputting liquid water after gas release.
A second input of the first secondary separator for inputting inert gas.
And a second output end of the first secondary separator is used for outputting the gas in the first secondary separator.
It will be appreciated that to avoid the build-up of hydrogen in the gas phase space of the first secondary separator to form an explosive gas mixture, increasing the safety hazard, a stream of nitrogen is introduced from the side of the first secondary separator, diluting the hydrogen concentration below the lower explosion limit, while a blow-down pipe is installed to vent the gas inside the first secondary separator to a safe area, and liquid water is vented from the bottom of the first secondary separator. By diluting and discharging the hydrogen, the creation of an explosive gaseous environment is avoided.
In some embodiments, the system includes a control unit including a plurality of sensors.
Each sensor is used for detecting an electrolysis unit, a water circulation unit or a gas-liquid separation unit to obtain a process parameter value.
And the control unit is used for judging whether the process parameter value is in a first preset value range, if not, controlling the electrolysis unit, the water circulation unit and the gas-liquid separation unit to stop working, and if so, controlling the electrolysis unit, the water circulation unit or the gas-liquid separation unit to adjust when the process parameter value is not in a second preset value range until the process parameter value is in the second preset value range.
It will be appreciated that after the operator presses the start key, the system automatically detects whether hydrogen production conditions are achieved according to the logic control program. For example, before hydrogen production, the oxygen content of the gas in the equipment is detected, if the content is too high, nitrogen is required to be supplemented, if the content is below a set value, the nitrogen supplementation is stopped, other indexes are detected besides the oxygen content, and the equipment can continue to operate after all indexes reach the standard. The equipment is provided with meters such as a liquid level meter, a thermometer, a pressure meter, a flowmeter and the like all around to detect technological parameters, a second preset value range in normal production is set, when the technological parameter value is not in the second preset value range, the electrolysis unit, the water circulation unit or the gas-liquid separation unit is controlled to be adjusted until the technological parameter value is in the second preset value range, and when the technological parameter value exceeds the first preset value range, the system jumps a power failure, and the electrolysis unit, the water circulation unit and the gas-liquid separation unit are controlled to stop working.
In some embodiments, the electrolysis unit comprises:
The proton exchange membrane electrolysis module is used for carrying out electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed state water.
The voltage control module is used for detecting the cell voltage and the cell current voltage of the proton exchange membrane electrolysis module, and controlling the proton exchange membrane electrolysis module to stop working when any detected cell voltage is higher than a preset voltage value or the detected cell current voltage is higher than a preset current voltage value.
It can be understood that the too high voltage applied to the two sides of the proton exchange membrane electrolyzer possibly breaks down the proton exchange membrane to cause cathode and anode short circuit, so that the safety risk is caused by hydrogen-oxygen channeling, and the electrolyzer is also greatly destroyed, if the voltage is too low, the requirement of gas production cannot be met, therefore, the embodiment can protect the proton exchange membrane electrolyzer by monitoring the voltage of the electrolysis cell and monitoring the voltage and the current of the electrolyzer, and when abnormality occurs, the system can stop the power supply and trip.
Referring to fig. 3, fig. 3 is a schematic diagram of a third structure of a water electrolysis hydrogen production system based on a proton exchange membrane electrolyzer.
In the embodiment, the gas-liquid separation unit comprises a first gas-liquid separation subunit and a second gas-liquid separation subunit, wherein the first gas-liquid separation unit comprises a first primary separation module and a first secondary separation module, and the second gas-liquid separation unit comprises a second primary separation module and a second secondary separation module.
The electrolysis unit comprises a proton exchange membrane electrolysis cell 1, a circulating pump 14 and an oxygen side waterway heat exchanger 15.
The first-stage separation module comprises a hydrogen first-stage separator 2, a hydrogen gas path heat exchanger 3 and a hydrogen demister 4, and the first regulating valve module comprises a hydrogen regulating valve 5 and a hydrogen medium oxygen analyzer 6.
The first secondary separation module comprises a hydrogen-side pressure reducing valve 17, a hydrogen secondary separator 18.
The second-stage separation module comprises an oxygen first-stage separator 8, an oxygen gas circuit heat exchanger 9 and an oxygen demister 10, and the second regulating valve module comprises an oxygen regulating valve 11 and an in-oxygen hydrogen analyzer 12.
The second stage separation module comprises an oxygen pressure reducing valve 16, an oxygen second stage separator 19.
The water circulation unit includes a circulation water tank 20, a water replenishment pump 21, a water replenishment heat exchanger 22, a resin tank 23, and a high pressure pump 24.
Deionized water in the oxygen primary separator 8 is transported to the proton exchange membrane electrolytic tank 1 through the circulating pump 14 to be used as a raw material for electrolysis, the proton exchange membrane electrolytic tank 1 is subjected to electrolytic reaction under the action of direct current, a small amount of liquid water carried by hydrogen is discharged from a cathode side through a pipeline at a and is further sent to the hydrogen primary separator 2 for gas-liquid separation, unreacted liquid water carried by oxygen is discharged from an anode side through a pipeline at i and is further sent to the oxygen primary separator 8 for gas-liquid separation.
The overheating of the temperature of the proton exchange membrane electrolytic tank 1 affects the performance and the service life of the proton exchange membrane, so that part of water in the proton exchange membrane electrolytic tank 1 is used as an electrolytic raw material, and the other part of water is used for taking away heat generated by the electrolysis of the proton exchange membrane electrolytic tank 1. In order to ensure that the temperature of the proton exchange membrane electrolytic cell 1 is within a set range, a temperature detector is arranged at the outlet of the proton exchange membrane electrolytic cell 1, and when the temperature abnormality is detected, the temperature is automatically adjusted according to a control program, such as the cooling water flow rate l in an oxygen system is regulated. The proton exchange membrane electrolyzer is provided with cell voltage detection and electrolyzer current voltage abnormality detection, once abnormality is detected, the system is automatically adjusted, and if the abnormality exceeds a certain limit of a set value, the system is automatically powered off and stopped.
The main function of the oxygen separation system is to collect the unreacted deionized water at the anode side and recycle it back to the proton exchange membrane electrolyzer system under pressure. The oxygen entering the oxygen primary separator 8 is subjected to primary separation under high pressure, is sent to an oxygen gas circuit heat exchanger 9 to condense gaseous water, is filtered by an oxygen demister 10 to remove liquid water and is then discharged, and the filtered liquid water returns to the oxygen primary separator 8 from the g position pipeline again. In order to check the quality of the product, an in-oxygen hydrogen analyzer 12 is arranged in the oxygen outlet pipeline n to detect the hydrogen content in oxygen, and if the monitoring is failed, an alarm signal is generated and the power is cut off. The deionized water of the oxygen primary separator 8 is pressurized from a pipeline w to an oxygen side waterway heat exchanger 15 through a circulating pump 14 to cool the deionized water, at the moment, the temperature of the deionized water is the optimal operation temperature of the proton exchange membrane electrolytic tank 1, the deionized water is split, one part of high-pressure deionized water flows from a pipeline m to the proton exchange membrane electrolytic tank 1, the other part of high-pressure deionized water flows from a pipeline o to the oxygen secondary separator 19 for secondary separation through the pressure reduction valve on the oxygen side, a small amount of oxygen dissolved in water under the condition of low pressure is released, and the deionized water flows into the circulating water tank 20 from a pipeline p for conductivity reduction treatment.
The temperature detection instrument is arranged before and after the oxygen side waterway heat exchanger 15 in the oxygen separation system, once the temperature is higher or lower than the optimal operation temperature of the proton exchange membrane electrolytic tank 1, the flow l of the cold end of the oxygen side waterway heat exchanger 15 is regulated, so that the temperature of deionized water conveyed to the proton exchange membrane electrolytic tank 1 is recovered to a normal range, the proton exchange membrane electrolytic tank has the highest working efficiency, the liquid level meter is arranged on the oxygen primary separator 8 to ensure that the liquid level is at a reasonable position, if the liquid level is higher, the valve for supplementing water to the oxygen primary separator 1 is closed, the flow u of the water supplementing pipeline is reduced, when the electrolysis consumption is to be carried out, and the oxygen side pressure reducing valve 16 is opened, a part of water is discharged to the oxygen secondary separator 19 to reduce the liquid level, excessive water is conveyed to the deionized water system, if the liquid level is lower, the water supplementing valve is opened to increase the flow through the pipeline at the position u to supplement water to the oxygen primary separator 1, and the drain valve of the oxygen secondary separator 19 is closed until the liquid level of the oxygen primary separator 8 is recovered to a set point. The branch for supplementing water to the proton exchange membrane electrolyzer is provided with a flow detection instrument, if the flow is too low, the rotating speed of the circulating pump 14 is increased, the flow of the proton exchange membrane electrolyzer is ensured to be certain, so that heat generated by the reaction of the proton exchange membrane electrolyzer can be taken away, the temperature of the proton exchange membrane electrolyzer is reduced, the oxygen discharge pipeline is provided with a regulating valve 11 and a vent valve, the regulating valve 11 ensures the discharge pressure of an oxygen end, the proton exchange membrane electrolyzer can produce hydrogen at the optimal pressure, and meanwhile, when the device has abnormal working conditions, the vent valve can be opened in time, so that the safety of the device is ensured.
The primary function of the hydrogen primary separator 2 is to separate the hydrogen and the liquid deionized water at high pressure from the cathode outlet of the proton exchange membrane electrolyzer through a pipeline at a, and mainly separate the liquid water in the gas, so that the liquid water is settled in the hydrogen primary separator 2. The separated hydrogen and gaseous water are led out from the top of the hydrogen primary separator 2 through a pipeline at the position C, condensed by the hydrogen gas circuit heat exchanger 3, and the cold end of the hydrogen gas circuit heat exchanger 3 adopts chilled water with the temperature of 8 ℃ to be conveyed through a pipeline at the position b, so that the gaseous water is maximally condensed into liquid water, and the liquid water is convenient for subsequent separation. The cooled hydrogen passes through a silk screen of a hydrogen demister 4, liquid water is filtered, and the hydrogen is stabilized in pressure through a regulating valve 5 and then is sent to the downstream. Condensed deionized water is led out from the lower position of the hydrogen demister 4 and flows back to the hydrogen primary separator 2. The hydrogen primary separator 2 is provided with a liquid level meter, when the liquid level is higher than a set value, the deionized water enters the hydrogen secondary separator 18 close to normal pressure after the program control is performed on the big hydrogen side pressure reducing valve 17 so that the hydrogen primary separator 2 returns to the normal liquid level, and meanwhile, the deionized water entering the hydrogen secondary separator 18 further releases dissolved hydrogen. To avoid the formation of explosive gas mixtures by accumulation of hydrogen in the gas phase space of the hydrogen secondary separator 18, a stream of nitrogen is introduced from the side of the hydrogen secondary separator 18 to dilute the hydrogen concentration below the lower explosion limit, and a blow-down pipe is installed to discharge the gas to a safe area. The remaining deionized water is discharged from the bottom of the hydrogen secondary separator 18 to the circulating water tank 20.
As with the oxygen separation system, the hydrogen separation system is also provided with an online analysis system to avoid unqualified products, and when the oxygen analyzer 6 in the hydrogen detects that the oxygen content exceeds a set value, the system is stopped and the power is cut off to prompt a user to detect the system.
The deionized water from the oxygen secondary separator 19 and the hydrogen secondary separator 18 is gathered in the circulating water tank 20 of the deionized water system, the secondary separator adopts an overflow pipe to control the liquid level, and when the liquid level reaches a set value, the liquid level can be automatically discharged to the circulating water tank 20 without monitoring the liquid level through a meter, so that the safety risk caused by the failure of the meter is avoided, the use of a valve of the meter is reduced, and the cost is also reduced. A water supplementing pump 21 is arranged at the downstream of the circulating water tank 20, the water is sent to a resin tank 23 for refining after reaching a proper temperature through a water supplementing heat exchanger 22, the resin tank is filled with resin particles, the conductivity of deionized water discharged from the resin tank can be lower than 0.5 mu S/cm, and the conductivity is maintained within an acceptable range of a proton exchange membrane electrolytic cell, so that the waste of water resources caused by direct discharge of the deionized water is avoided. Refined deionized water is injected into the oxygen primary separator 8 at z-stage via high pressure pump 24. The circulating water tank 20 is mixed with deionized water of the oxygen secondary separator 19 and the hydrogen secondary separator 18, so that a trace amount of hydrogen or oxygen dissolved in water may be released therein to form an explosive gas mixture, and thus the circulating water tank 20 is also provided with a nitrogen line to dilute the gas in the circulating water tank while being evacuated.
In this embodiment, after the electrolysis unit performs electrolysis treatment on the liquid water to obtain hydrogen, oxygen and gas-liquid mixed water, gas-liquid separation is performed in the primary separation module, mainly separating the liquid water in the gas, and the liquid water in the primary separation module passes through the secondary separation module to release the gas dissolved in the water. The scheme adopts a secondary separation technology, can accelerate the release speed of the gas dissolved in the liquid water, and releases the gas dissolved in the water as much as possible. And finally, the liquid water released by the gas is transmitted to the electrolysis unit through the water circulation unit for repeated use for electrolytic treatment, so that the water resource is saved, meanwhile, the gas content in the liquid water is reduced because the gas in the recycled water is escaped, and the situation that the hydrogen and oxygen escaped in the recycled liquid water are converged in the electrolysis unit to form an explosive gas environment is avoided, thereby reducing the safety risk of the electrolytic water hydrogen production system in the hydrogen production process.
The terms "first," "second," "third," "fourth," and the like in the description of the application and in the above figures, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the application described herein may be implemented, for example, in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed or inherent to such process, method, article, or apparatus.
It should be understood that in the present application, "at least one (item)" means one or more, and "a plurality" means two or more. "and/or" is used to describe an association relationship of an associated object, and indicates that three relationships may exist, for example, "a and/or B" may indicate that only a exists, only B exists, and three cases of a and B exist simultaneously, where a and B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, at least one of a, b or c may represent a, b, c, "a and b", "a and c", "b and c", or "a and b and c", wherein a, b, c may be single or plural.
In the several embodiments provided in the present application, it should be understood that the disclosed system, apparatus and method may be implemented in other manners. For example, the apparatus embodiments described above are merely illustrative, e.g., the division of the units is merely a logical function division, and there may be additional divisions when actually implemented, e.g., multiple units or components may be combined or integrated into another system, or some features may be omitted or not performed. Alternatively, the coupling or direct coupling or communication connection shown or discussed with each other may be an indirect coupling or communication connection via some interfaces, devices, or units, which may be in electrical, mechanical, or other forms.
The units described as separate units may or may not be physically separate, and units shown as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.
In addition, each functional unit in the embodiments of the present application may be integrated in one processing unit, or each unit may exist alone physically, or two or more units may be integrated in one unit. The integrated units may be implemented in hardware or in software functional units.
While the present application has been described in considerable detail and with particularity with respect to several described embodiments, it is not intended to be limited to any such detail or embodiments or any particular embodiment, but is to be considered as providing a broad interpretation of such claims by reference to the appended claims in light of the prior art and thus effectively covering the intended scope of the application. Furthermore, the foregoing description of the application has been presented in its embodiments contemplated by the inventors for the purpose of providing a useful description, and for the purposes of providing a non-essential modification of the application that may not be presently contemplated, may represent an equivalent modification of the application.
Claims (10)
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