CN113215592A - Comprehensive heat management system of large alkaline electrolyzed water hydrogen production device - Google Patents
Comprehensive heat management system of large alkaline electrolyzed water hydrogen production device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/18—Arrangement or mounting of grates or heating means
- F24H9/1809—Arrangement or mounting of grates or heating means for water heaters
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The application relates to the field of a water electrolysis hydrogen production system, and particularly discloses a comprehensive heat management system of a large alkaline water electrolysis hydrogen production device, wherein an auxiliary heater is adopted to heat circulating alkali liquor, and a heat exchange medium stored in a heat storage barrel is not used, so that adverse influence factors of the working stability of the comprehensive heat management system are reduced; the comprehensive heat exchanger has two functions of integrating the heat recovered from the hydrogen and the heat recovered from the oxygen and heating and redistributing the hot fluid used by the heat exchanger, is beneficial to storing energy at the initial working stage of the heat storage medium of the heat storage bin in the comprehensive heat exchanger, releases the energy when the heat transfer temperature difference value of the comprehensive heater is reduced, relieves the influence of the heat transfer efficiency reduction caused by the temperature difference value on the heating effect of the circulating alkaline solution, improves the working stability of the comprehensive heat management system, and reduces the possibility of parameter false alarm in the production process.
Description
Technical Field
The application relates to a water electrolysis hydrogen production system, in particular to a comprehensive heat management system of a large alkaline water electrolysis hydrogen production device.
Background
The hydrogen production by water electrolysis is that direct current is introduced into an electrolytic cell filled with electrolyte, and water molecules are subjected to electrochemical reaction on an electrode and are decomposed into hydrogen and oxygen. In order to improve the ionic conductivity of water and reduce the interference of other ions in the hydrogen production process by water electrolysis in the current production process, the electrolyte of the current production process generally adopts alkali liquor (NaOH solution), and the process and the production system are called as alkaline water electrolysis hydrogen production process and system.
Meanwhile, in the process of producing hydrogen by large-scale alkaline electrolyzed water at present, due to large production quantity and heating of the alkaline liquor in the electrolysis process, the specific volume flow of hydrogen gas phase and byproduct oxygen gas phase respectively extracted by the two electrodes is large, and the hydrogen gas phase and byproduct oxygen gas phase are carried with alkaline liquor liquid mist and high temperature. On one hand, the alkali liquor is separated from the obtained hydrogen and oxygen for purification, and on the other hand, the heat in the hydrogen gas phase and the oxygen gas phase is recovered, so that the large-scale alkaline water electrolysis hydrogen production is configured with a heat management system.
For example, before gas-liquid separation of the hydrogen gas phase and the oxygen gas phase, heat exchange is carried out to recover heat by using the heat exchanger, water vapor in the hydrogen gas phase and the oxygen gas phase is condensed, so that purification of the hydrogen and the oxygen is facilitated, and on the other hand, the recovered heat heats the circulating alkali liquor recovered by gas-liquid separation. And the system also collects the redundant recovered heat in the hydrogen production process of the high-power electrolyzed water, namely the redundant heat outside the heat required by the circulating alkali liquor heating in the gas phase recovered heat, and stores the redundant heat exchange medium with higher temperature in the heat storage tank.
The inventor researches and finds that the defects still exist, because the heat recovered from the hydrogen and the heat recovered from the oxygen are combined and are transferred for many times to heat the circulating alkali liquor, the heating effect of the circulating alkali liquor is also fluctuated by the recovered heat due to the small-range fluctuation of the flow and the water content of the hydrogen and the oxygen in the electrolytic process; on the other hand, the heat storage tank stores the heat exchange medium with higher temperature in the high-power electrolysis process, the quantity of the heat exchange medium in the heat exchange pipeline for indirectly exchanging heat and recovering heat for hydrogen gas phase and oxygen gas phase in the storage process is continuously reduced, the heat exchange medium needs to be supplemented, the temperature of the supplemented heat exchange medium is inconsistent with the temperature of the outflow heat exchange medium, a heat exchange system is fluctuated, the fluctuation of the system can also influence the temperature of the heat exchange medium extracted into the heat storage tank, a feedback cycle is formed, the temperature fluctuation time of the heat exchange system is prolonged, the heating stability is reduced, and the dynamic balance of working conditions is difficult.
And insert the heat transfer medium of higher temperature into original heat transfer pipeline to circulation alkali lye heating during low-power electrolysis and carry out the auxiliary heating, but the heat transfer medium volume after the increase must not conform to original pipeline reserves, unnecessary heat transfer medium must have some storage device, the live time of auxiliary heating receives heat storage tank size restriction, the heat storage tank can't carry out the auxiliary heating after original higher temperature's heat transfer medium finishes using, continue to cause the hindrance to production, and too big heat storage tank makes equipment cost, heat transfer medium quantity cost and heat preservation cost are for improving greatly.
Disclosure of Invention
In order to improve the stability of the heating effect of the recovered heat of the comprehensive heat management system of the alkaline water electrolysis device, the application provides the comprehensive heat management system of the large-scale alkaline water electrolysis hydrogen production device.
The application provides a comprehensive heat management system of a large alkaline electrolyzed water hydrogen production device, which adopts the following technical scheme:
a comprehensive heat management system of a large alkaline electrolytic water hydrogen production device comprises an alkaline electrolytic water hydrogen production unit, a heat recovery unit, a heat redistribution unit, a gas phase processing unit and a liquid phase circulation unit,
the alkaline electrolyzed water hydrogen production unit comprises an electrolytic bath, and the electrolytic bath is provided with a liquid alkali circulation inlet;
the gas phase treatment unit comprises a hydrogen gas-liquid separator and an oxygen gas-liquid separator;
a hydrogen gas production pipe section is connected between the electrolytic cell and the hydrogen gas-liquid separator, and an oxygen gas production pipe section is connected between the electrolytic cell and the oxygen gas-liquid separator;
the heat recovery unit comprises a comprehensive heat exchanger, a hydrogen heat recovery heat exchanger arranged on the hydrogen extraction pipe section and an oxygen heat recovery heat exchanger arranged on the oxygen extraction pipe section;
a heat storage bin which is in contact with a heat exchange medium is arranged in the comprehensive heat exchanger, the heat storage bin is sealed and stores the heat storage medium, the heat storage medium comprises one or both of a dissolution enthalpy variant and a phase change material, and the dissolution enthalpy variant is a mixture of a dissolution enthalpy change material and a saturated solution of the dissolution enthalpy change material;
the hydrogen heat recovery heat exchanger is connected with the oxygen heat recovery heat exchanger in parallel;
the cold fluid outlet of the hydrogen heat recovery heat exchanger and the cold fluid outlet of the oxygen heat recovery heat exchanger are connected to the hot fluid inlet of the comprehensive heat exchanger;
the liquid phase circulating unit comprises an alkali liquor circulating pipe section, an alkali liquor circulating pump is installed on the alkali liquor circulating pipe section, and the alkali liquor circulating pipe section is connected with alkali liquor and an electrolytic bath which are extracted from the liquid phase of the gas phase processing unit;
the heat redistribution unit comprises a redistribution heat exchanger and an auxiliary heater which are arranged on the alkali liquor circulating pipe section, the redistribution heat exchanger is positioned at the downstream of the alkali liquor circulating pump, a cold fluid inlet and a cold fluid outlet of the redistribution heat exchanger are connected with the alkali liquor circulating pipe section, and a hot fluid inlet and a hot fluid outlet of the redistribution heat exchanger are respectively connected with a cold fluid inlet and a cold fluid outlet of the comprehensive heat exchanger;
the supplemental heater is located downstream of the redistribution heat exchanger.
Through adopting above-mentioned technical scheme, at first adopt auxiliary heater to circulate alkali lye heating in this application, do not use the heat storage bucket to store and outer heat transfer medium, avoid heat transfer medium to adopt the heat transfer pipeline, incorporate into the temperature fluctuation that original heat transfer pipeline arouses to and avoid supplementing new heat transfer medium after heat transfer medium draws, heat transfer medium incorporates into the problem that original heat transfer medium discharged the storage after, reduce the adverse effect factor of thermal management system job stabilization nature of synthesizing.
Furthermore, be equipped with confined heat storage storehouse in synthesizing the heat exchanger in this application, heat storage storehouse and heat transfer medium contact for heat storage medium in the heat storage storehouse exchanges heat with the heat transfer medium who flows in synthesizing the heat exchanger, through phase transition or dissolve or appear the mode of solute, stores the heat.
Because the comprehensive heat exchanger has the two functions of integrating the heat recovered from the hydrogen and the heat recovered from the oxygen and heating the hot fluid used by the redistribution heat exchanger, the stability of the heating temperature of the hot fluid used by the redistribution heat exchanger by the comprehensive heat exchanger is influenced by the production capacity of the hydrogen/oxygen, the water content when the hydrogen/oxygen is extracted, and the like, and the production capacity of the hydrogen/oxygen and the water content when the hydrogen/oxygen is extracted are influenced by factors such as the voltage of an electrolytic bath, the purity of an alkali solution in the electrolytic bath, the temperature of the alkali solution and the temperature of the alkali solution are directly related by the temperature and the purity of a circulating alkali solution, so that the temperature of the heat recovered from the hydrogen/oxygen in the comprehensive heat exchanger fluctuates and has the characteristic of periodicity, the interference exists on the production capacities of the hydrogen and the oxygen, and the false alarm of parameters in the production process is easy to appear, affecting production monitoring.
Therefore, the heat storage medium stores energy at the initial working stage, when the heat transfer temperature difference value of the integrated heater is reduced, the energy is released, the influence of the heat transfer efficiency reduction caused by the temperature difference value on the heating effect of the circulating alkaline solution is alleviated, the working stability of the integrated heat management system is improved, and the possibility of parameter error and false alarm in the production process is reduced.
Preferably, the heat storage bin is located in a cold fluid flow chamber of the integrated heat exchanger.
Through adopting above-mentioned technical scheme, when the heat-retaining medium was not enough to be heated to cold fluid in the heat storage storehouse in this application, the heating of direct release heat, improved the heat transfer efficiency of heat-retaining medium to cold fluid promptly, utilize the heat transfer efficiency's that hot fluid exists the condition to cold fluid heat transfer in the comprehensive heat exchanger simultaneously, further weaken the temperature fluctuation of cold fluid.
Preferably, the heat storage bin is made of a mixed material of a dissolution enthalpy variant and a phase-change material.
By adopting the technical scheme, the phase-change material has large energy storage capacity, the dissolution enthalpy variant energy is released and distributed more uniformly on the temperature gradient, and the two are mixed for use, so that the buffer effect on temperature fluctuation is better.
Preferably, the heat recovery unit further comprises a hydrogen side direct preheater arranged between the hydrogen heat recovery heat exchanger and the electrolytic bath, and an oxygen side direct preheater arranged between the oxygen heat recovery heat exchanger and the electrolytic bath, the gas phase processing unit comprises a liquid phase conveying pipe for conveying a liquid phase separated from a gas phase, the downstream of the liquid phase conveying pipe is respectively connected with the oxygen side direct preheater and the hydrogen side direct preheater, the gas phase in the oxygen side direct preheater and the hydrogen side direct preheater is in direct contact heat exchange, and the oxygen side direct preheater and the hydrogen side direct preheater are also simultaneously connected to the alkali liquor circulation pipe section.
Through adopting above-mentioned technical scheme to circulation alkali lye and hydrogen extraction, oxygen extraction direct mixing heat transfer, to hydrogen, oxygen cooling, improve the temperature of circulation alkali lye simultaneously, improve hydrogen/oxygen heat recovery efficiency.
Preferably, the liquid-phase delivery pipe is divided into a hydrogen-side delivery pipe connected to the hydrogen-gas-liquid separator and an oxygen-side delivery pipe connected to the oxygen-gas-liquid separator.
By adopting the technical scheme, the circulating alkali liquor separated by the hydrogen gas-liquid separator is mixed with hydrogen for heat exchange, and the circulating alkali liquor separated by the oxygen gas-liquid separator is mixed with oxygen for heat exchange, so that the cross contamination of dissolved gas in the circulating alkali liquor to products is avoided.
Preferably, the oxygen side direct preheater and the hydrogen side direct preheater are packed towers.
By adopting the technical scheme, liquid mist entrainment after hydrogen extraction and oxygen extraction heat exchange is reduced, and the heat exchange efficiency is improved.
Preferably, the liquid phase circulation unit further comprises a lye filter located upstream of the lye circulation pump.
By adopting the technical scheme, impurities brought into the electrolytic cell by the circulating alkali liquor are reduced.
Preferably, a piston pipe connected with the inside is arranged outside the heat storage bin, and a pressure-variable piston is connected in the piston pipe in a sealing sliding manner.
By adopting the technical scheme, the volume in the heat storage bin can adapt to the change according to the temperature change of the content, the pressure requirement of the container of the heat storage bin is reduced, the wall thickness of the heat storage bin is reduced, and the heat transfer is facilitated.
In summary, the present application has the following beneficial effects:
1. the circulating alkali liquor is heated by adopting the auxiliary heater, a heat exchange medium stored in the heat storage barrel is not used, the temperature fluctuation caused by the heat exchange medium being extracted from the heat exchange pipeline and merged into the original heat exchange pipeline is avoided, the problems that a new heat exchange medium is supplemented after the heat exchange medium is extracted, and the original heat exchange medium is discharged and stored after the heat exchange medium is merged into the original heat exchange pipeline are solved, and the adverse influence factors of the working stability of the comprehensive heat management system are reduced;
2. the heat storage medium in the heat storage bin in the comprehensive heat exchanger is beneficial to storing energy at the initial working stage, when the heat transfer temperature difference value of the comprehensive heater is reduced, the energy is released, the influence of the reduction of the heat transfer efficiency caused by the temperature difference value on the heating effect of the circulating alkali liquor is alleviated, the working stability of the comprehensive heat management system is improved, and the possibility of parameter error and false alarm in the production process is reduced;
3. the circulating alkali liquor and the hydrogen extraction and the oxygen extraction are directly mixed for heat exchange, so that the temperature of the hydrogen and the oxygen is reduced, the temperature of the circulating alkali liquor is increased, and the heat recovery efficiency of the hydrogen/the oxygen is improved.
4. The heat storage bin is connected with a piston with a sealing sliding function, the inner volume of the heat storage bin can adapt to change according to the temperature change of the content, the pressure requirement of the container of the heat storage bin is reduced, the thickness of the wall of the heat storage bin is reduced, and heat transfer is facilitated.
Description of the drawings:
FIG. 1 is a schematic view of an integrated thermal management system according to embodiment 1;
FIG. 2 is a schematic diagram of an integrated heat exchanger;
FIG. 3 is a schematic view of a piston tube;
FIG. 4 is a schematic view of the integrated thermal management system of example 2.
Reference numerals: 1. an alkaline water electrolysis hydrogen production unit; 11. an electrolytic cell; 12. a rectifier transformer; 2. a gas phase treatment unit; 21. a hydrogen gas-liquid separator; 22. an oxygen gas-liquid separator; 23. a hydrogen gas post-treatment device; 24. an oxygen post-treatment device; 25. a hydrogen production pipe section; 26. an oxygen production tubing section; 27. a hydrogen side delivery pipe; 28. an oxygen side delivery pipe; 3. a heat recovery unit; 31. a hydrogen heat recovery heat exchanger; 32. an oxygen heat recovery heat exchanger; 33. a comprehensive heat exchanger; 331. a housing; 332. a tube bundle; 3321. a heat exchange through pipe; 333. sealing the end; 334. a cold flow inlet; 335. a cold flow outlet; 336. a hot fluid outlet; 337. a heat flow inlet; 338. a tube sheet; 339. a heat storage bin; 3391. a piston tube; 3392. a pressure-variable piston; 34. a comprehensive heat exchange diverter; 35. a hydrogen side direct preheater; 36. an oxygen side direct preheater; 4. a liquid phase circulation unit; 41. a lye circulating pipe section; 42. an alkali liquor filter; 43. an alkali liquor circulating pump; 5. a heat redistribution unit; 51. redistributing the heat exchanger; 52. an auxiliary heater.
Detailed Description
The present application is described in further detail below with reference to figures 1-4.
Example 1
The comprehensive heat management system of the large alkaline electrolytic water hydrogen production device is shown in figure 1 and comprises an alkaline electrolytic water hydrogen production unit 1, a heat recovery unit 3, a heat redistribution unit 5, a gas phase treatment unit 2 and a liquid phase circulation unit 4.
The alkaline electrolyzed water hydrogen production unit 1 includes an electrolytic bath 11 and a rectifier transformer 12 electrically connected to the electrolytic bath 11. An anode chamber and a cathode chamber are arranged in the electrolytic bath 11, wherein alkali liquor is stored in the anode chamber and the cathode chamber, and the anode chamber and the cathode chamber are separated by an ion diaphragm. The rectifier transformer 12 is used for electrifying the electrolytic bath 11 to electrolyze the alkali liquor in the electrolytic bath 11.
The gas phase processing unit 2 includes a hydrogen gas-liquid separator 21, an oxygen gas-liquid separator 22, a hydrogen gas post-processing device 23, and an oxygen gas post-processing device 24.
A hydrogen extraction pipe section 25 is connected between the electrolytic cell 11 and the hydrogen gas-liquid separator 21, the hydrogen extraction pipe section 25 is connected with the hydrogen gas-liquid separator 21 and the electrolytic cell 11, the gas phase extraction of the hydrogen gas-liquid separator 21 is communicated with the hydrogen gas post-treatment device 23, and the liquid phase extraction of the hydrogen gas-liquid separator 21 is led to the liquid phase circulation unit 4. The mixed gas phase (mixed with alkali liquid mist) produced by electrolyzing hydrogen in the electrolytic bath 11 enters a hydrogen gas-liquid separator 21 along a hydrogen producing pipe section 25, the separated gas phase enters a hydrogen gas post-treatment device 23, and the separated liquid phase enters a liquid phase circulation unit 4.
An oxygen gas extraction pipe section 26 is connected between the electrolytic cell 11 and the oxygen gas-liquid separator 22, and the oxygen gas extraction pipe section 26 is connected with the oxygen gas-liquid separator 22 and the electrolytic cell 11. The gas-phase produced from the oxygen gas-liquid separator 22 is communicated with the oxygen post-treatment device 24, and the liquid-phase produced from the oxygen gas-liquid separator 22 is led to the liquid-phase circulation unit 4. The mixed gas phase (mixed with alkali liquid mist) extracted by electrolyzing oxygen in the electrolytic bath 11 enters the oxygen gas-liquid separator 22 along the oxygen extraction pipe section 26, the separated gas phase enters the oxygen post-treatment device 24, and the separated liquid phase enters the liquid phase circulation unit 4.
The heat recovery unit 3 comprises a hydrogen heat recovery heat exchanger 31 mounted on the hydrogen production pipe section 25 and an oxygen heat recovery heat exchanger 32 mounted on the oxygen production pipe section 26.
The hot fluid inlet and outlet of the hydrogen heat recovery heat exchanger 31 are connected with the hydrogen extraction pipe section 25, and the material in the hydrogen extraction pipe section 25 enters the hydrogen gas-liquid separator 21 after passing through the hydrogen heat recovery heat exchanger 31.
The hot fluid inlet and outlet of the oxygen heat recovery heat exchanger 32 are connected with the oxygen extraction pipe section 26, and the materials in the oxygen extraction pipe section 26 pass through the oxygen heat recovery heat exchanger 32 and then enter the oxygen gas-liquid separator 22.
The heat recovery unit 3 further comprises a comprehensive heat exchanger 33, a cold fluid outlet of the hydrogen heat recovery heat exchanger 31 and a cold fluid outlet of the oxygen heat recovery heat exchanger 32 are connected to a hot fluid inlet of the comprehensive heat exchanger 33, a hot fluid outlet of the comprehensive heat exchanger 33 is connected with a comprehensive heat exchange splitter 34, and a cold fluid inlet of the hydrogen heat recovery heat exchanger 31 and a cold fluid inlet and a cold fluid outlet of the oxygen heat recovery heat exchanger 32 are connected to the downstream of the comprehensive heat exchange splitter 34.
A heat exchange medium circulates between the comprehensive heat exchanger 33 and the hydrogen heat recovery heat exchanger 31, and a heat exchange medium circulates between the comprehensive heat exchanger 33 and the hydrogen heat recovery heat exchanger 31.
As shown in fig. 2, the integrated heat exchanger 33 is a dividing wall type heat exchanger, which may be one of a shell-and-tube type heat exchanger and a plate type heat exchanger, and here, a jacketed type heat exchanger is taken as an example, and the integrated heat exchanger 33 adopts a parallel flow or a counter flow depending on the load of the integrated heat exchanger 33.
The integrated heat exchanger 33 includes a shell 331 located at the outside, a tube bundle 332 located in the shell, and end sockets 333 installed at both ends of the shell 331.
The housing 331 is hollow and cylindrical, and the side surface thereof is provided with a cold fluid inlet 334 and a cold fluid outlet 335 which are communicated with the inside, and the cold fluid inlet 334 and the cold fluid outlet 335 are cold fluid inlets and outlets of the comprehensive heat exchanger 33.
The number of the end sockets 333 is two, the end sockets are respectively fixed at two ends of the shell 331 in a sealing manner, and the two end sockets 333 are provided with pipe orifices. The two pipe orifices are distributed as a hot fluid outlet 336 and a hot fluid inlet 337, and the hot fluid outlet 336 and the hot fluid inlet 337 are hot fluid inlets and outlets of the integrated heat exchanger 33.
And a plurality of tube plates 338 are fixed in the shell 331 and perpendicular to the length direction of the shell 331, and the tube plates 338 are distributed at intervals along the length direction of the shell 331. The number of tube sheets 338, the number of heat exchange through tubes 3321 and the diameter of heat exchange through tube 3321 are determined according to the load of the integrated heat exchanger 33, and in the drawings, the number of tube sheets 338, the number of heat exchange through tubes 3321 and the diameter of heat exchange through tube 3321 are only illustrated for the convenience of clearly showing the structure of the integrated heat exchanger 33.
The two tube plates 338 seal ports at two ends of the shell 331, the tube bundle 332 includes a plurality of heat exchange through tubes 3321, the heat exchange through tubes 3321 are parallel to the shell 331, two ends of the heat exchange tubes penetrate through the shell plates, inner spaces of the two end sockets 333 are communicated with inner spaces of the heat exchange through tubes 3321 to form a heat exchange space for hot fluid flowing in the comprehensive heat exchanger 33, and a heat exchange space for cold fluid flowing in the comprehensive heat exchanger 33 is formed between the inner side of the shell 331 and the outer side of the heat exchange through tubes 3321.
The integrated heat exchanger 33 further includes a plurality of heat storage bins 339, the number of the heat storage bins 339 is determined according to the load requirement of the integrated heat exchanger 33, the heat storage bins 339 are tubular, and the heat storage bins 339 are located inside the shell 331 and are fixed on the tube plate 338 in a penetrating manner.
As shown in figure 3, one end of the heat storage bin 339 is closed, the other end is connected with a coaxial piston tube 3391, and a pressure-variable piston 3392 is connected in the piston tube 3391 in a sealing and sliding manner. The heat storage bin 339 stores heat storage medium, and the heat storage medium is one or both of a dissolution enthalpy variant and a phase change material. The phase change material absorbs heat, is converted from a solid to a liquid, is an amorphous material, and is a mixed aliphatic hydrocarbon wax with the glass transition temperature range of 70-90 at this time. The dissolution enthalpy variant is a mixture of a dissolution enthalpy change material and a saturated solution of the dissolution enthalpy change material, which releases heat during dissolution, such as calcium nitrite, cesium hydroxide, and the like. The heat storage medium in the heat storage bin 339 is a mixed material of a dissolution enthalpy variant and a phase-change material.
As shown in the attached figure 1, the liquid phase circulation unit 4 comprises an alkali liquor circulation pipe section 41, the upstream of the alkali liquor circulation pipe section 41 is simultaneously connected with the liquid phase extraction of the hydrogen gas-liquid separator 21 and the liquid phase extraction of the oxygen gas-liquid separator 22, and the downstream of the alkali liquor circulation pipe section 41 is connected with the electrolytic bath 11.
The alkali liquor circulating pipe section 41 is provided with an alkali liquor filter 42 and an alkali liquor circulating pump 43 in sequence from the upstream gas phase processing unit 2 to the downstream electrolytic tank 11, and the alkali liquor separated by the hydrogen gas-liquid separator 21 and the oxygen gas-liquid separator 22 is circulated back to the electrolytic tank 11.
The heat redistribution unit 5 comprises a redistribution heat exchanger 51 and an auxiliary heater 52, wherein the redistribution heat exchanger 51 and the auxiliary heater 52 are both connected into the lye circulating pipe section 41, the redistribution heat exchanger 51 and the auxiliary heater 52 are both located downstream of the lye circulating pump 43, and wherein the redistribution heat exchanger 51 is located upstream of the auxiliary heater 52.
The cold fluid inlet and outlet of the redistribution heat exchanger 51 are connected with the alkali liquor circulating pipe section 41, the hot fluid inlet and outlet of the redistribution heat exchanger 51 are respectively connected with the cold fluid inlet and outlet of the comprehensive heat exchanger 33, and a heat exchange medium circulates between the redistribution heat exchanger 51 and the comprehensive heat exchanger 33, so that the comprehensive heat exchanger 33 heats the hot fluid of the redistribution heat exchanger 51, and then the redistribution heat exchanger 51 heats the circulating alkali liquor flowing through the redistribution heat exchanger 51.
Working procedure of example 1:
the hydrogen/oxygen produced by electrolysis in the electrolytic cell 11 is cooled by heat exchange in the hydrogen heat recovery heat exchanger 31/oxygen heat recovery heat exchanger 32, and then enters the hydrogen gas-liquid separator 21/oxygen gas-liquid separator 22 to separate gas and liquid phases. The other of the gas phase production leads to subsequent processing. The circulating lye extracted from the liquid phase is led to the liquid phase circulating unit 4 and is led to the electrolytic bath 11 along the lye circulating pipe section 41.
Meanwhile, the heat recovered by the hydrogen heat recovery heat exchanger 31/the oxygen heat recovery heat exchanger 32 is transferred to the cold fluid of the comprehensive heat exchanger 33 and the heat storage medium in the heat storage bin 339 through the heat exchange of the comprehensive heat exchanger 33.
The cold fluid of the comprehensive heat exchanger 33 heats the circulating alkali liquor in the redistribution heat exchanger 51 to preheat the circulating alkali liquor. And during the low-power work period of the electrolytic bath 11, the auxiliary heater 52 is used for assisting in preheating the circulating alkali liquor, and the preheating temperature of the circulating alkali liquor is maintained to meet the requirements of the technological parameters.
Adopt auxiliary heater 52 to circulate alkali lye heating in this embodiment, do not use the heat-storage bucket to store and outer heat transfer medium, avoid heat transfer medium to adopt the heat transfer pipeline, incorporate into the temperature fluctuation that original heat transfer pipeline arouses to and avoid supplementing new heat transfer medium after heat transfer medium draws, heat transfer medium incorporates into the problem that original heat transfer medium discharged after and stores, reduce the adverse effect factor of thermal management system job stabilization nature of synthesizing.
On the other hand, a closed heat storage bin 339 is arranged in the comprehensive heat exchanger 33, and the heat storage bin 339 is in contact with a heat exchange medium, so that the heat storage medium in the heat storage bin 339 exchanges heat with the heat exchange medium flowing in the comprehensive heat exchanger 33, and heat is stored in a phase change mode or a solute dissolving or separating mode. The heat storage medium stores energy at the initial working stage, and when the heat transfer temperature difference value of the integrated heater is reduced, the energy is released, the influence of the heat transfer efficiency reduction caused by the temperature difference value on the heating effect of the circulating alkali liquor is alleviated, the working stability of the integrated heat management system is improved, and the possibility of parameter error false alarm in the production process is reduced.
Example 2
As shown in fig. 4, based on embodiment 1, the integrated thermal management system of a large alkaline electrolyzed water hydrogen production apparatus is different in that the heat recovery unit 3 in embodiment 2 further includes a hydrogen-side direct preheater 35 and an oxygen-side direct preheater 36. The gas phase processing unit 2 includes a feed liquid phase feed pipe, and is divided into a hydrogen side feed pipe 27 connected to the hydrogen gas-liquid separator 21 and an oxygen side feed pipe 28 connected to the oxygen gas-liquid separator 22.
The hydrogen side direct preheater 35 is installed and connected to the hydrogen extraction pipe section 25, and the hydrogen extracted from the electrolytic cell 11 flows through the hydrogen side direct preheater 35 and then enters the hydrogen heat recovery heat exchanger 31.
The upstream of the hydrogen side delivery pipe 27 is connected with the liquid phase extraction of the hydrogen gas-liquid separator 21, and the downstream thereof is connected with the top of the hydrogen side direct preheater 35, so that the circulating alkali liquor separated by the hydrogen gas-liquid separator 21 enters the hydrogen side delivery pipe 27 and directly contacts with the hydrogen extraction of the electrolytic cell 11 for heat exchange.
The oxygen side direct preheater 36 is similar to the hydrogen side direct preheater 35 and does not have a packed column, which is sized according to the scale of the oxygen gas output and the amount of the circulating alkali liquor. The oxygen side direct preheater 36 is installed and connected to the oxygen withdrawal tube section 26, and the oxygen withdrawal stream from the electrolysis cell 11 passes through the oxygen side direct preheater 36 and then enters the oxygen heat recovery heat exchanger 32.
The lower part of the oxygen side conveying pipe 28 is connected with the top of the oxygen side direct preheater 36, so that the circulating alkali liquor separated by the oxygen gas-liquid separator 22 enters the oxygen side conveying pipe 28 and is directly contacted with the oxygen of the electrolytic cell 11 for heat exchange,
meanwhile, the upstream of the alkali liquor circulating pipe section 41 is connected to the bottoms of the hydrogen side direct preheater 35 and the oxygen side direct preheater 36. The alkali liquor after heat exchange in the oxygen side direct preheater 36 and the hydrogen side direct preheater 35 flows through the alkali liquor filter 42, the redistribution heat exchanger 51 and the auxiliary heater 52 and enters the electrolytic bath 11.
Improved advantages of example 2: the circulating alkali liquor and the hydrogen extraction and the oxygen extraction are directly mixed for heat exchange, so that the temperature of the hydrogen and the oxygen is reduced, the temperature of the circulating alkali liquor is increased, and the heat recovery efficiency of the hydrogen/the oxygen is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A comprehensive heat management system of a large alkaline electrolytic water hydrogen production device comprises an alkaline electrolytic water hydrogen production unit (1), a heat recovery unit (3), a heat redistribution unit (5), a gas phase treatment unit (2) and a liquid phase circulation unit (4),
the alkaline electrolyzed water hydrogen production unit (1) comprises an electrolytic bath (11);
the gas phase treatment unit (2) comprises a hydrogen gas-liquid separator (21) and an oxygen gas-liquid separator (22);
a hydrogen gas production pipe section (25) is connected between the electrolytic cell (11) and the hydrogen gas-liquid separator (21), an oxygen gas production pipe section (26) is connected between the electrolytic cell (11) and the oxygen gas-liquid separator (22),
the method is characterized in that:
the heat recovery unit (3) comprises a comprehensive heat exchanger (33), a hydrogen heat recovery heat exchanger (31) arranged on the hydrogen extraction pipe section (25) and an oxygen heat recovery heat exchanger (32) arranged on the oxygen extraction pipe section (26);
a heat storage bin (339) which is in contact with a heat exchange medium is arranged in the comprehensive heat exchanger (33), the heat storage bin (339) is sealed and stores a heat storage medium, the heat storage medium comprises one or both of a dissolution enthalpy variant and a phase change material, and the dissolution enthalpy variant is a mixture of a dissolution enthalpy change material and a saturated solution of the dissolution enthalpy change material;
the hydrogen heat recovery heat exchanger (31) is connected with the oxygen heat recovery heat exchanger (32) in parallel;
the cold fluid outlet (335) of the hydrogen heat recovery heat exchanger (31) and the cold fluid outlet of the oxygen heat recovery heat exchanger (32) are connected to the hot fluid inlet of the comprehensive heat exchanger (33);
the liquid phase circulating unit (4) comprises an alkali liquor circulating pipe section (41), an alkali liquor circulating pump (43) is installed on the alkali liquor circulating pipe section (41), and the alkali liquor circulating pipe section (41) is connected with alkali liquor extracted from the liquid phase of the gas phase processing unit (2) and the electrolytic tank (11);
the heat redistribution unit (5) comprises a redistribution heat exchanger (51) and an auxiliary heater (52), wherein the redistribution heat exchanger (51) is arranged on the alkali liquor circulating pipe section (41), the redistribution heat exchanger (51) is positioned at the downstream of the alkali liquor circulating pump (43), a cold fluid inlet and a cold fluid outlet of the redistribution heat exchanger (51) are connected with the alkali liquor circulating pipe section (41), and a hot fluid inlet and a hot fluid outlet of the redistribution heat exchanger (51) are respectively connected with a cold fluid inlet and a cold fluid outlet of the comprehensive heat exchanger (33);
the auxiliary heater (52) is located downstream of the redistribution heat exchanger (51).
2. The integrated heat management system of a large alkaline electrolyzed water hydrogen production plant according to claim 1, characterized in that the heat storage bin (339) is positioned in a cold fluid flow cavity of the integrated heat exchanger (33).
3. The integrated thermal management system of a large alkaline electrolyzed water hydrogen production plant according to claim 1, wherein the heat storage bin (339) is a mixed material of a dissolution enthalpy variant and a phase change material.
4. The integrated thermal management system of a large alkaline electrolyzed water hydrogen production plant according to claim 1, characterized in that the heat recovery unit (3) further comprises a hydrogen side direct preheater (35) installed between the hydrogen heat recovery heat exchanger (31) and the electrolytic bath (11), an oxygen side direct preheater (36) installed between the oxygen heat recovery heat exchanger (32) and the electrolytic bath (11), the gas phase treatment unit (2) comprises a liquid phase conveying pipe for conveying a liquid phase separated from a gas phase, the downstream of the liquid phase conveying pipe is respectively connected with an oxygen side direct preheater (36) and a hydrogen side direct preheater (35), the gas phase and the liquid phase in the oxygen side direct preheater (36) and the hydrogen side direct preheater (35) are directly contacted for heat exchange, the oxygen side direct preheater (36) and the hydrogen side direct preheater (35) are also connected to the lye circulating pipe section (41) at the same time.
5. The comprehensive heat management system of the large alkaline electrolyzed water hydrogen production device according to claim 1, wherein the liquid-phase conveying pipe is divided into a hydrogen-side conveying pipe (27) connected with the hydrogen-gas-liquid separator (21) and an oxygen-side conveying pipe (28) connected with the oxygen-gas-liquid separator (22).
6. The integrated thermal management system of a large alkaline water electrolysis hydrogen production plant according to claim 4, characterized in that the oxygen side direct preheater (36) and the hydrogen side direct preheater (35) are packed towers.
7. The integrated thermal management system of a large alkaline electrolytic water hydrogen plant according to claim 1, 4 or 5, characterized in that the liquid phase circulation unit (4) further comprises a lye filter (42) located upstream of the lye circulation pump (43).
8. The comprehensive heat management system of the large alkaline electrolytic water hydrogen production plant according to claim 1, characterized in that a piston tube (3391) connected inside is arranged outside the heat storage bin (339), and a pressure-variable piston (3392) is connected in the piston tube (3391) in a sealing and sliding manner.
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