CN116445947A - Alkaline water electrolysis hydrogen production thermoelectric coupling system and working method - Google Patents
Alkaline water electrolysis hydrogen production thermoelectric coupling system and working method Download PDFInfo
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- 230000008878 coupling Effects 0.000 title claims abstract description 73
- 238000010168 coupling process Methods 0.000 title claims abstract description 73
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 67
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 107
- 239000007788 liquid Substances 0.000 claims abstract description 76
- 230000001502 supplementing effect Effects 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
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- 238000010248 power generation Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 230000005619 thermoelectricity Effects 0.000 claims description 4
- 238000012935 Averaging Methods 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
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- 238000002955 isolation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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Abstract
An alkaline electrolysis water hydrogen production thermoelectric coupling system and a working method thereof, wherein an alkaline liquor outlet end of an alkaline liquor preparation module is respectively communicated with a heat exchanger and a liquid inlet of a gas-liquid separation device; the liquid outlet of the heat exchanger is communicated with the inlet of the alkali supplementing pump, and the liquid outlet of the alkali supplementing pump is communicated with the liquid inlet of the thermoelectric coupling device; the liquid outlet of the thermoelectric coupling device is communicated with the liquid inlet of the electrolytic tank, and the electrolytic tank electrolyzes the alkali liquid heated by the thermoelectric coupling device; the liquid outlet of the electrolytic tank is communicated with the liquid inlet of the gas-liquid separation device, and the gas discharged by the gas-liquid separation device is treated by the purification and drying system through the gas outlet; the water supplementing pump is communicated with a water supplementing port of the gas-liquid separation device; the thermal field control module collects alkali liquor temperature values from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time. The thermoelectric coupling device is arranged at the front end of the electrolytic tank, so that high-energy conductive ions can quickly enter the electrolytic tank to carry out electrolytic reaction, and the electrolytic reaction time is shortened.
Description
Technical Field
The invention relates to the field of hydrogen production by water electrolysis, in particular to a thermoelectric coupling system for hydrogen production by alkaline water electrolysis and a working method.
Background
In order to improve the efficiency of hydrogen production by water electrolysis, alkali liquor needs to be heated in the hydrogen production process by water electrolysis.
In the existing electrolytic water hydrogen production system, the resistance wire in the heating device is additionally arranged in the heat exchanger module, so that the structural design of the heat exchanger module is hindered, and meanwhile, the temperature regulation and control function of the heat exchanger module serving as a cooling device of an alkali liquor circulation system is also influenced. The alkaline water electrolysis hydrogen production system cannot be well adapted to renewable energy sources with high fluctuation, so that the time for establishing an electric field and a thermal field of the hydrogen production system is long, and the fluctuation speed of responding to the renewable energy sources is low.
Meanwhile, the heating mode of the existing heating device for the electrolytic water hydrogen production patent is that the resistance wire is directly stretched into the alkali liquor to be contacted with the alkali liquor for heating the alkali liquor. The fact that the resistance wire is directly located in the alkali liquor has the following defects that in the heating of the alkali liquor, the resistance wire is immersed in the alkali liquor, and movement of conductive ions is affected.
Therefore, in order to solve the above problems, there is a need for an alkaline electrolyzed water hydrogen production thermoelectric coupling system capable of rapidly responding to hydrogen production.
Disclosure of Invention
The invention aims to accelerate the establishment speed of an electric field in alkali liquor, increase the heat conduction path among water molecules and improve the heat conduction efficiency of an electrolytic solution. Therefore, the alkaline electrolytic tank can adapt to renewable energy sources with strong volatility and high intermittence, and the applicability of the renewable energy sources for hydrogen production is improved.
Therefore, the invention provides a thermoelectricity coupling system for producing hydrogen by alkaline water electrolysis and a working method thereof.
The specific technical scheme of the alkaline water electrolysis hydrogen production thermoelectric coupling system is as follows:
a thermoelectricity coupling system for producing hydrogen by alkaline electrolysis of water is characterized in that: comprises an alkali liquor configuration module, a thermoelectric coupling device, an electrolytic tank, a gas-liquid separation system and a thermal field control module;
the alkali liquor outlet end of the alkali liquor preparation module is respectively communicated with the liquid inlet of the heat exchanger and the liquid inlet of the gas-liquid separation device;
the liquid outlet of the heat exchanger is communicated with the inlet of the alkali supplementing pump, and the liquid outlet of the alkali supplementing pump is communicated with the liquid inlet of the thermoelectric coupling device;
the liquid outlet of the thermoelectric coupling device is communicated with the liquid inlet of the electrolytic tank, and the electrolytic tank electrolyzes the alkali liquid heated by the thermoelectric coupling device;
the liquid outlet of the electrolytic tank is communicated with the liquid inlet of the gas-liquid separation device, and the gas discharged by the gas-liquid separation device is treated by the purification and drying system through the gas outlet;
the water supplementing pump is communicated with a water supplementing port of the gas-liquid separation device;
the thermal field control module collects alkali liquor temperature values from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time;
the thermal field control module is used for controlling the rotating speeds of the alkali supplementing pump and the water supplementing pump, the opening amount of the heat exchanger and the heating power of the thermoelectric coupling device.
To better implement the invention, it is further possible to: the thermoelectric coupling device comprises a shell, wherein the shell is provided with a heating chamber, a heating pipe is arranged in the shell, an alkali liquor pipeline is spirally wound on the periphery of the heating pipe, two ends of the alkali liquor pipeline respectively extend out of the shell, and the heating pipe heats the spiral pipeline.
By adopting the mode, the alkali liquor pipeline is spiral, and has a longer distance compared with a linear pipeline, so that the heating time of the alkali liquor in the pipeline is prolonged. The resistance wire and the alkali liquor are wound in a non-contact heating mode, so that the resistance wire cannot influence the components of the alkali liquor and particles to participate in the electrolytic reaction, and meanwhile, the corrosion of the alkali liquor to the resistance wire is avoided. In addition, the resistance wire is wrapped by the heating cavity, so that heat conduction to the outside of the heating cavity is reduced.
Further: an isolation layer is arranged on the inner wall of the heating chamber. By providing the insulating layer, the heat loss in the heating cavity is small.
The working method of the alkaline water electrolysis hydrogen production thermoelectric coupling system comprises the following specific technical scheme:
a working method of a thermoelectric coupling system for producing hydrogen by alkaline water electrolysis is characterized by comprising the following steps:
s1, pure water and KOH solid enter an alkali liquor preparation module and then are stirred to generate alkali liquor;
s2, alkali liquor flows into the gas-liquid separation device through the pipe, is pumped by the alkali supplementing pump, enters the thermoelectric coupling device after heat exchange by the heat exchanger, and enters the electrolytic tank for electrolysis after heating by the thermoelectric coupling device;
s3, enabling the alkali liquor entering the electrolytic tank to participate in the electrolytic reaction to generate hydrogen, and enabling the hydrogen and hot alkali liquor steam to enter a gas-liquid separation device together;
s4, the separated hydrogen enters a purification and drying system, and alkali liquor in the gas-liquid separation device is circularly enters an electrolytic tank after being heated by a thermoelectric coupling device through an alkali supplementing pump;
s5, the thermal field control center module collects alkali liquor temperature data from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time;
s6, the thermal field control module receives the renewable energy generating capacity data in real time, and the thermal field control module adjusts the electrolytic water hydrogen production system to adapt to the renewable energy;
when the power generation amount of the renewable energy sources is lower than the rated power, a heat preservation mode is started, and a thermal field control center controls a thermoelectric coupling device, an alkali supplementing pump, a water supplementing pump and a heat exchanger module to maintain the temperature of the thermoelectric coupling electrolytic water hydrogen production system at the minimum power;
when the renewable energy generating capacity meets rated power, the thermal field control module enables the water electrolysis hydrogen production system to quickly respond to hydrogen production.
To better implement the invention, it is further possible to:
s1, pure water and KOH solid enter an alkali liquor preparation module and then are stirred to generate alkali liquor with the concentration of 30 weight percent.
Can further: s6 specifically comprises the following steps:
establishing a renewable energy source generation power prediction model;
determining thermal parameters of the electrolytic cell through experiments, and establishing a thermodynamic model of the electrolytic cell to obtain an electrolytic cell temperature change curve under the input power of the electrolytic cell and the ambient temperature;
when the renewable energy source output can not maintain the operation of the electrolytic hydrogen production system and the system needs to be shut down, the thermal control field module immediately turns off the alkali liquor cooling equipment and the alkali liquor circulating system after the direct current power supply input is disconnected, so that the electrolytic water hydrogen production thermoelectric coupling system is in a static state, and the electrolytic water hydrogen production thermoelectric coupling system enters a heat preservation state;
when the electrolytic water hydrogen production thermoelectric coupling system stops working, the thermal control field module calculates power required for heating the temperature of the electrolyte to 75 ℃ and corresponding time at each moment according to the current parameters of each temperature sensor and the thermodynamic model of the electrolytic tank;
the thermal control field module predicts a renewable energy input power curve in a period of time according to the renewable energy generation power prediction model;
the thermal control field module starts prediction according to the renewable energy input power curve, so that the system is just started when the renewable energy input power reaches the minimum power required by the electrolysis system;
if the temperature of the electrolyte is higher than 75 ℃, the thermoelectric coupling heating device is not started;
when the electrolytic water hydrogen production thermoelectric coupling system operates normally, the heat production is large when the electrolytic tank works, so that the temperature of the electrolytic tank is increased, and the opening of the valve of the heat exchanger is gradually increased after the temperature exceeds 80 ℃, so that cooling water and electrolyte can exchange heat through the heat exchanger to reduce the temperature of the electrolyte, and the opening of the valve of the heat exchanger is regulated and controlled by PID, so that the temperature of the electrolyte is maintained at 80 ℃.
Further: the thermal control field module starts prediction according to the renewable energy input power curve, so that the specific method for starting the system just when the renewable energy input power reaches the minimum power required by the electrolysis system is as follows:
first from measurements made by sensors firstWhen the current electrolyte temperature T (T) is set as deltat, the renewable energy source input power sequence P of a future period is obtained through power prediction by setting the time interval of renewable energy source predicted power pred ，
P pred ＝[P 1 P 2 ...P N ]
N is the prediction time domain, P 1 To P N Averaging the renewable energy power over the next N time intervals for the predicted;
the heating power of the electrolytic tank arranged in any time interval is constant to be P heat The power of the circulating pump is P c The heating power is adjusted after each time interval. According to the obtained thermodynamic model of the electrolytic cell, establishing a functional relation between the temperature change and the heating power of the electrolytic cell
T(t+Δt)＝f(T(t),P heat )
First, a power sequence P is input to renewable energy sources pred Searching, namely determining the time interval number n between the moment when the input power of renewable energy sources is larger than the minimum power of the operation of the electrolytic tank and the moment when the input power of renewable energy sources is separated from the moment, if the moment when the input power of renewable energy sources is larger than the minimum power of the operation of the electrolytic tank can not be searched in a predictable range, the heating device and the circulating pump are not operated, and re-searching is carried out at the next moment, and repeating the steps;
after determining the number n of time intervals in which the input power of renewable energy sources is greater than the minimum power of the operation of the electrolytic tank, calculating a constrained optimization problem, inputting the constrained energy sources into the heating power of the next n times, wherein the constrained energy sources are the heating power of the next n times, the electrolyte temperature is required to be higher than 75 ℃, and the power used for heating and circulating is required to be smaller than the renewable energy source power predicted in the period, and the aim is to minimize the energy consumed by heating and circulating in the period;
the electrolyte temperature after n time intervals has the following calculation formula:
T(t+nΔt)＝f(T(t),P heat1 ,P heat2 ,...,P heatn )
the mathematical expression of the optimization problem is:
st.P heat (i)≤max(P pred (i)-P c ,0)
T(t+nΔt)≥75
after the power control sequence of the heater is calculated according to the method, the first item of the power sequence is applied to the heater at the current moment, data of the temperature sensor of the electrolytic cell is collected at the next moment, optimization calculation is carried out again, the first item of the obtained power sequence is applied to the heater again, and the process is circulated until the temperature of the electrolyte meets the requirement, and starting is completed.
The beneficial effects of the invention are as follows: first, the thermocouple reduces the dielectric adhesion of particles in the electrolyte solution and slows down the effect of the activation overvoltage on the electrolytic reaction. Meanwhile, the electric field establishment speed is increased, the heat conduction paths among water molecules are increased, and the heat conduction efficiency of the electrolytic solution is improved.
Secondly, the thermal coupling device adopts non-contact heating, and the thermal coupling device and alkali liquor are mutually independent and are not influenced. And the thermoelectric coupling device is arranged at the front end of the electrolytic tank, so that high-energy conductive ions can quickly enter the electrolytic tank to carry out electrolytic reaction, and the electrolytic reaction time is shortened. Meanwhile, a thermoelectric coupling system is constructed, and the system can be maintained at a temperature suitable for electrolytic reaction with minimum power by controlling part of modules in the electrolytic system.
Third, the invention can be adapted to renewable energy sources. When the renewable energy power generation amount is small, the thermal field control center can control the thermoelectric coupling device, the alkali supplementing pump, the water supplementing pump and the heat exchanger module, the whole hydrogen production system is maintained at a proper temperature with minimum power, and when the renewable energy power generation is increased, the water electrolysis hydrogen production system can quickly respond, the starting time is reduced, and the hydrogen production is efficient.
Drawings
FIG. 1 is an overall block diagram of the present invention;
FIG. 2 is a block diagram of a thermocouple device;
FIG. 3 is a schematic diagram of a method of operation of an alkaline electrolyzed water hydrogen production thermoelectric coupling system;
the drawing illustrates an alkali liquor configuration module 1, a heat exchanger 2, a thermoelectric coupling device 3, an alkali supplementing pump 4, an electrolytic tank 5, a gas-liquid separation device 6, a thermal field control module 7, a shell 8, a heating chamber 9, a heating pipe 10, a pipeline 11, a flange plate 12, a purification drying system 13 and a water supplementing pump 14.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1:
a thermoelectricity coupling system for producing hydrogen by alkaline electrolysis of water is characterized in that: comprises an alkali liquor configuration module 1, a thermoelectric coupling device 3, an electrolytic tank 5, a gas-liquid separation system and a thermal field control module 7;
the alkali liquor outlet end of the alkali liquor preparation module 1 is respectively communicated with the inlet of the heat exchanger 2 and the inlet of the gas-liquid separation device 6;
the liquid outlet of the heat exchanger 2 is communicated with the inlet of the alkali supplementing pump 4, and the liquid outlet of the alkali supplementing pump 4 is communicated with the liquid inlet of the thermoelectric coupling device 3;
the liquid outlet of the thermoelectric coupling device 3 is communicated with the liquid inlet of the electrolytic tank 5, and the electrolytic tank 5 electrolyzes the alkali liquid heated by the thermoelectric coupling device 3;
the liquid outlet of the electrolytic tank 5 is communicated with the liquid inlet of the gas-liquid separation device 6, and the gas discharged by the gas-liquid separation device 6 is processed by the purification and drying system 13 through a gas outlet;
the water supplementing pump 14 is communicated with a water supplementing port of the gas-liquid separation device 6;
the thermal field control module 7 collects the alkali liquor temperature values from the heat exchanger 2 module, the gas-liquid separation module and the electrolysis tank 5 module in real time.
Pure water and KOH solid enter an alkali liquor preparation module 1 and are stirred to generate alkali liquor required by reaction, the alkali liquor flows into a gas-liquid separation module through a pipeline 11, and then is pumped by an alkali supplementing pump 4 to enter a thermoelectric coupling device and an electrolytic tank 5 through a heat exchanger 2. The alkaline solution entering the electrolytic tank 5 participates in the electrolytic reaction to generate hydrogen.
The hydrogen and the hot alkali liquor steam enter a gas-liquid separation device 6 together, the separated hydrogen enters a purification and drying system 13, and the alkali liquor enters the electrolytic tank 5 again through an alkali supplementing pump 4.
The thermal field control center module receives alkali liquor temperature information from the heat exchanger 2 module, the gas-liquid separation module and the electrolysis tank 5 module, and controls the rotating speeds of the alkali supplementing pump 4 and the water supplementing pump 14, the opening amount of the heat exchanger 2 and the heating power of the thermoelectric coupling device 3 according to the temperature information of each part.
In this embodiment, the thermocouple device 3 comprises a housing 8, the housing 8 having a heating chamber 9 with an insulating layer disposed on the inner wall of the heating chamber. A heating pipe 10 is arranged in the shell 8, an alkali liquor pipeline 11 is spirally wound on the periphery of the heating pipe 10, two ends of the alkali liquor pipe respectively extend out of the shell 8, and the heating pipe 10 heats the spiral pipeline 11.
The alkali liquor pipeline 11 is spiral, and compared with the linear pipeline 11, the alkali liquor pipeline 11 has a longer distance, so that the heating time of the alkali liquor of the pipeline 11 is prolonged. The resistance wire and the alkali liquor are wound in a non-contact heating mode, so that the resistance wire cannot influence the components of the alkali liquor and particles to participate in the electrolytic reaction, and meanwhile, the corrosion of the alkali liquor to the resistance wire is avoided. In addition, the resistance wire is wrapped by the heating cavity, so that heat conduction to the outside of the heating cavity is reduced.
A working method of a thermoelectric coupling system for producing hydrogen by alkaline water electrolysis comprises the following steps:
s1, pure water and KOH solid enter an alkali liquor preparation module and then are stirred to generate alkali liquor with the concentration of 30 weight percent.
S2, alkali liquor flows into the gas-liquid separation device through the pipe, is pumped by the alkali supplementing pump, enters the thermoelectric coupling device after heat exchange by the heat exchanger, and enters the electrolytic tank for electrolysis after heating by the thermoelectric coupling device;
s3, enabling the alkali liquor entering the electrolytic tank to participate in the electrolytic reaction to generate hydrogen, and enabling the hydrogen and hot alkali liquor steam to enter a gas-liquid separation device together;
s4, the separated hydrogen enters a purification and drying system, and alkali liquor in the gas-liquid separation device is circularly enters an electrolytic tank after being heated by a thermoelectric coupling device through an alkali supplementing pump;
s5, the thermal field control center module collects alkali liquor temperature data from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time;
s6, the thermal field control module receives the renewable energy generating capacity data in real time, and the thermal field control module adjusts the electrolytic water hydrogen production system to adapt to the renewable energy;
when the power generation amount of the renewable energy sources is lower than the rated power, a heat preservation mode is started, and a thermal field control center controls a thermoelectric coupling device, an alkali supplementing pump, a water supplementing pump and a heat exchanger module to maintain the temperature of the thermoelectric coupling electrolytic water hydrogen production system at the minimum power;
when the renewable energy generating capacity meets rated power, the thermal field control module enables the water electrolysis hydrogen production system to quickly respond to hydrogen production.
Wherein, the implementation of S6 is as follows,
by acquiring meteorological data and historical power generation data of renewable energy sources, a renewable energy source ultra-short-term power generation power prediction model is established, and then renewable energy source input power for 1-6 hours can be obtained.
The thermal parameters of the electrolytic cell are determined through experiments, a thermodynamic model of the electrolytic cell is established, and the temperature change curve of the electrolytic cell under various input power of the electrolytic cell and environmental temperature can be obtained.
When the renewable energy source output is too low to maintain the operation of the electrolytic hydrogen production system, and the system needs to be shut down, immediately adjusting the opening of a cooling water valve to 0 after the direct current power supply input is disconnected, closing an alkali liquor cooling device, and simultaneously closing an alkali liquor circulation system to ensure that the system is in a static state, wherein alkali liquor in the system does not flow at the moment, the heat dissipation speed of the system is reduced, so that the system is maintained in a relatively high-temperature hot standby state, and meanwhile, the power consumption required by auxiliary equipment is maintained at a minimum value;
when the system is stopped, calculating power required for heating the electrolyte to 75 ℃ and corresponding time at each moment according to the current parameters of each temperature sensor and the thermodynamic model of the electrolytic tank, and predicting a renewable energy input power curve in a next period of time by a thermal control field module according to a renewable energy power generation power prediction model;
the thermal control field module starts prediction according to the renewable energy input power curve so that the system is just started when the renewable energy input power reaches the minimum power required by the electrolysis system.
If the electrolyte temperature is higher than 75 ℃, the heating device is not started.
When the system is in normal operation, the heat generated by the electrolytic tank is larger during operation, so that the temperature of the electrolytic tank is increased, and after the temperature exceeds 80 ℃, the opening of the valve of the heat exchanger is gradually increased, so that cooling water and electrolyte can exchange heat through the heat exchanger to reduce the temperature of the electrolyte, and the opening of the valve of the heat exchanger is controlled by PID (proportion integration differentiation) regulation, so that the temperature of the electrolyte is maintained at 80 ℃.
The thermal control field module starts prediction according to a renewable energy input power curve, so that the system is started just when the renewable energy input power reaches the minimum power required by the electrolysis system, and the specific method is as follows:
firstly, according to the current electrolyte temperature T (T) measured by a sensor, setting the time interval of renewable energy source predicted power as delta T, and obtaining a renewable energy source input power sequence P of a future period of time through power prediction pred ，
P pred ＝[P 1 P 2 ...P N ](0.1)
N is the prediction time domain, P 1 To P N Averaging the renewable energy power over the next N time intervals for the predicted;
the heating power of the electrolytic tank arranged in any time interval is constant to be P heat The power of the circulating pump is P c The heating power is adjusted after each time interval. According to the obtained thermodynamic model of the electrolytic cell, establishing a functional relation between the temperature change and the heating power of the electrolytic cell
T(t+Δt)＝f(T(t),P heat )(0.2)
First, a power sequence P is input to renewable energy sources pred Searching, namely determining the time interval number n between the moment when the input power of renewable energy sources is larger than the minimum power of the operation of the electrolytic tank and the moment when the input power of renewable energy sources is separated from the moment, if the moment when the input power of renewable energy sources is larger than the minimum power of the operation of the electrolytic tank can not be searched in a predictable range, the heating device and the circulating pump are not operated, and re-searching is carried out at the next moment, and repeating the steps;
after determining the number n of time intervals in which the input power of renewable energy sources is greater than the minimum power of the operation of the electrolytic tank, calculating a constrained optimization problem, inputting the constrained energy sources into the heating power of the next n times, wherein the constrained energy sources are the heating power of the next n times, the electrolyte temperature is required to be higher than 75 ℃, and the power used for heating and circulating is required to be smaller than the renewable energy source power predicted in the period, and the aim is to minimize the energy consumed by heating and circulating in the period;
the electrolyte temperature after n time intervals has the following calculation formula:
T(t+nΔt)＝f(T(t),P heat1 ,P heat2 ,...,P heatn )(0.3)
the mathematical expression of the optimization problem is:
st.P heat (i)≤max(P pred (i)-P c ,0)
T(t+nΔt)≥75(0.4)
after the power control sequence of the heater is calculated according to the method, the first item of the power sequence is applied to the heater at the current moment, data of the temperature sensor of the electrolytic cell is collected at the next moment, optimization calculation is carried out again, the first item of the obtained power sequence is applied to the heater again, and the process is circulated until the temperature of the electrolyte meets the requirement, and starting is completed.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A thermoelectricity coupling system for producing hydrogen by alkaline electrolysis of water is characterized in that: comprises an alkali liquor configuration module, a thermoelectric coupling device, an electrolytic tank, a gas-liquid separation system and a thermal field control module;
the alkali liquor outlet end of the alkali liquor preparation module is respectively communicated with the liquid inlet of the heat exchanger and the liquid inlet of the gas-liquid separation device;
the liquid outlet of the heat exchanger is communicated with the inlet of the alkali supplementing pump, and the liquid outlet of the alkali supplementing pump is communicated with the liquid inlet of the thermoelectric coupling device;
the liquid outlet of the thermoelectric coupling device is communicated with the liquid inlet of the electrolytic tank, and the electrolytic tank electrolyzes the alkali liquid heated by the thermoelectric coupling device;
the liquid outlet of the electrolytic tank is communicated with the liquid inlet of the gas-liquid separation device, and the gas discharged by the gas-liquid separation device is treated by the purification and drying system through the gas outlet;
the water supplementing pump is communicated with a water supplementing port of the gas-liquid separation device;
the thermal field control module collects alkali liquor temperature values from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time;
the thermal field control module is used for controlling the rotating speeds of the alkali supplementing pump and the water supplementing pump, the opening amount of the heat exchanger and the heating power of the thermoelectric coupling device.
2. The alkaline water electrolysis hydrogen production thermoelectric coupling system according to claim 1, wherein: the thermoelectric coupling device comprises a shell, wherein the shell is provided with a heating chamber, a heating pipe is arranged in the shell, an alkali liquor pipeline is spirally wound on the periphery of the heating pipe, two ends of the alkali liquor pipeline respectively extend out of the shell, and the heating pipe heats the spiral pipeline.
3. The alkaline water electrolysis hydrogen production thermoelectric coupling system according to claim 1, wherein:
an isolation layer is arranged on the inner wall of the heating chamber.
4. A working method of a thermoelectric coupling system for producing hydrogen by alkaline water electrolysis is characterized by comprising the following steps:
s1, pure water and KOH solid enter an alkali liquor preparation module and then are stirred to generate alkali liquor;
s2, alkali liquor flows into the gas-liquid separation device through the pipe, is pumped by the alkali supplementing pump, enters the thermoelectric coupling device after heat exchange by the heat exchanger, and enters the electrolytic tank for electrolysis after heating by the thermoelectric coupling device;
s3, enabling the alkali liquor entering the electrolytic tank to participate in the electrolytic reaction to generate hydrogen, and enabling the hydrogen and hot alkali liquor steam to enter a gas-liquid separation device together;
s4, the separated hydrogen enters a purification and drying system, and alkali liquor in the gas-liquid separation device is circularly enters an electrolytic tank after being heated by a thermoelectric coupling device through an alkali supplementing pump;
s5, the thermal field control center module collects alkali liquor temperature data from the heat exchanger module, the gas-liquid separation module and the electrolytic tank module in real time;
s6, the thermal field control module receives the renewable energy generating capacity data in real time, and the thermal field control module adjusts the electrolytic water hydrogen production system to adapt to the renewable energy;
when the power generation amount of the renewable energy sources is lower than the rated power, a heat preservation mode is started, and a thermal field control center controls a thermoelectric coupling device, an alkali supplementing pump, a water supplementing pump and a heat exchanger module to maintain the temperature of the thermoelectric coupling electrolytic water hydrogen production system at the minimum power;
when the renewable energy generating capacity meets rated power, the thermal field control module enables the water electrolysis hydrogen production system to quickly respond to hydrogen production.
5. A method for operating an alkaline water electrolysis hydrogen production thermoelectric coupling system according to claim 3, wherein:
s1, pure water and KOH solid enter an alkali liquor preparation module and then are stirred to generate alkali liquor with the concentration of 30 weight percent.
6. The working method of the alkaline water electrolysis hydrogen production thermoelectric coupling system is characterized in that:
s6 specifically comprises the following steps:
establishing a renewable energy source generation power prediction model;
determining thermal parameters of the electrolytic cell through experiments, and establishing a thermodynamic model of the electrolytic cell to obtain an electrolytic cell temperature change curve under the input power of the electrolytic cell and the ambient temperature;
when the renewable energy source output can not maintain the operation of the electrolytic hydrogen production system and the system needs to be shut down, the thermal control field module immediately turns off the alkali liquor cooling equipment and the alkali liquor circulating system after the direct current power supply input is disconnected, so that the electrolytic water hydrogen production thermoelectric coupling system is in a static state, and the electrolytic water hydrogen production thermoelectric coupling system enters a heat preservation state;
when the electrolytic water hydrogen production thermoelectric coupling system stops working, the thermal control field module calculates power required for heating the temperature of the electrolyte to 75 ℃ and corresponding time at each moment according to the current parameters of each temperature sensor and the thermodynamic model of the electrolytic tank;
the thermal control field module predicts a renewable energy input power curve in a period of time according to the renewable energy generation power prediction model;
the thermal control field module starts prediction according to the renewable energy input power curve, so that the system is just started when the renewable energy input power reaches the minimum power required by the electrolysis system;
if the temperature of the electrolyte is higher than 75 ℃, the thermoelectric coupling heating device is not started;
when the electrolytic water hydrogen production thermoelectric coupling system operates normally, the heat production is large when the electrolytic tank works, so that the temperature of the electrolytic tank is increased, and the opening of the valve of the heat exchanger is gradually increased after the temperature exceeds 80 ℃, so that cooling water and electrolyte can exchange heat through the heat exchanger to reduce the temperature of the electrolyte, and the opening of the valve of the heat exchanger is regulated and controlled by PID, so that the temperature of the electrolyte is maintained at 80 ℃.
7. The working method of the alkaline water electrolysis hydrogen production thermoelectric coupling system is characterized in that:
the thermal control field module starts prediction according to the renewable energy input power curve, so that the specific method for starting the system just when the renewable energy input power reaches the minimum power required by the electrolysis system is as follows:
firstly, according to the current electrolyte temperature T (T) measured by a sensor, setting the time interval of renewable energy source predicted power as delta T, and obtaining a renewable energy source input power sequence P of a future period of time through power prediction pred ，
P pred ＝[P 1 P 2 ... P N ]
N is the prediction time domain, P 1 To P N Averaging the renewable energy power over the next N time intervals for the predicted;
the heating power of the electrolytic tank arranged in any time interval is constant to be P heat The power of the circulating pump is P c The heating power is adjusted after each time interval. According to the obtained thermodynamic model of the electrolytic cell, establishing a functional relation between the temperature change and the heating power of the electrolytic cell
T(t+Δt)＝f(T(t),P heat )
First, a power sequence P is input to renewable energy sources pred Searching to determine the time and phase when the input power of renewable energy sources is greater than the minimum power of the operation of the electrolytic cellIf the time interval number n is not longer than the minimum power of the operation of the electrolytic cell, the heating device and the circulating pump are not operated, and the searching is repeated at the next time;
after determining the number n of time intervals in which the input power of renewable energy sources is greater than the minimum power of the operation of the electrolytic tank, calculating a constrained optimization problem, inputting the constrained energy sources into the heating power of the next n times, wherein the constrained energy sources are the heating power of the next n times, the electrolyte temperature is required to be higher than 75 ℃, and the power used for heating and circulating is required to be smaller than the renewable energy source power predicted in the period, and the aim is to minimize the energy consumed by heating and circulating in the period;
the electrolyte temperature after n time intervals has the following calculation formula:
T(t+nΔt)＝f(T(t),P heat1 ,P heat2 ,...,P heatn )
the mathematical expression of the optimization problem is:
st.P heat (i)≤max(P pred (i)-P c ,0)
T(t+nΔt)≥75
after the power control sequence of the heater is calculated according to the method, the first item of the power sequence is applied to the heater at the current moment, data of the temperature sensor of the electrolytic cell is collected at the next moment, optimization calculation is carried out again, the first item of the obtained power sequence is applied to the heater again, and the process is circulated until the temperature of the electrolyte meets the requirement, and starting is completed.
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