CN110822967B - Integral structure for adsorption type thermochemical energy storage and building heating - Google Patents

Integral structure for adsorption type thermochemical energy storage and building heating Download PDF

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CN110822967B
CN110822967B CN201910943177.8A CN201910943177A CN110822967B CN 110822967 B CN110822967 B CN 110822967B CN 201910943177 A CN201910943177 A CN 201910943177A CN 110822967 B CN110822967 B CN 110822967B
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CN110822967A (en
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曾敏
李威
王秋旺
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Xian Jiaotong University
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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
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D11/00—Central heating systems using heat accumulated in storage masses
    • F24D11/006—Central heating systems using heat accumulated in storage masses air heating system
    • F24D11/007—Central heating systems using heat accumulated in storage masses air heating system combined with solar energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D11/00—Central heating systems using heat accumulated in storage masses
    • F24D11/006—Central heating systems using heat accumulated in storage masses air heating system
    • F24D11/009—Central heating systems using heat accumulated in storage masses air heating system with recuperation of waste heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D2200/00—Heat sources or energy sources
    • F24D2200/14—Solar energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D2200/00—Heat sources or energy sources
    • F24D2200/16—Waste heat
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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    • Y02A30/60—Planning or developing urban green infrastructure
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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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

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Abstract

The invention discloses an integral structure for adsorption type thermochemical energy storage and building heating, which comprises a gas main inlet section, a valve, a gas inlet branch pipe section, an energy storage reaction bed, a gas outlet branch pipe section, a gas main outlet section, a steering valve, a gas outdoor outlet section, a gas indoor outlet section and a pipeline heat insulation layer. Each section of the reaction bed is composed of solid reactant filling materials, and the periphery of the pipeline is covered by heat insulation materials so as to reduce the heat loss in the reaction process. The invention comprises the gas conveying pipeline and the energy storage reaction bed, not only reduces the space volume of the heat storage and supply device, avoids the problems of local excessive adsorption and deliquescence of solid reactants, insufficient reaction and the like, is beneficial to improving the heat and mass transfer effect in the gas-solid reaction process, but also directly combines the heat storage unit with the gas conveying pipeline, has simple and reliable device and improves the feasibility of chemical heat storage in building heating or heat supply.

Description

Integral structure for adsorption type thermochemical energy storage and building heating
Technical Field
The invention relates to the technical field of thermochemical energy storage and building heating, in particular to an integral structure for adsorption thermochemical energy storage and building heating.
Background
Energy sources are the material basis for human activities. The continuous development and utilization of energy sources promote the development of human civilization. With the increasing severity of the energy crisis problem, various measures for energy conservation and emission reduction are being developed and applied continuously. Among the energy consumption of the prior art, the energy consumption of buildings is the most remarkable, and accounts for 1/3 of the total national energy consumption. Efficient storage and conversion of heat is essential for more reasonable and efficient use of energy. Compared with sensible heat and latent heat storage, the thermochemical heat storage has higher energy storage density, can be used for seasonal heat storage, has extremely low heat loss, has a great application prospect, and is becoming a research hotspot of the chemical industry at present. The solar energy or the high-temperature waste heat in industrial production is converted into chemical energy for storage by combining a thermochemical heat storage means, and the chemical energy is released and utilized in the form of heat energy when heat is needed in cold seasons, so that the solar energy and the high-temperature waste heat are particularly suitable for the field of building energy conservation. The principle of thermochemical heat storage is based on reversible chemical reactions with the absorption or release of energy during the reaction.
Inorganic hydrated salt/water vapor, inorganic salt/ammonia gas, metal hydroxide/water vapor and the like are common heat storage working medium pairs for adsorption type thermochemical energy storage at present. Particularly, some hydrated salts have the advantages of simple reaction principle, cheap or easy preparation of heat storage materials, low requirements on pressure and temperature in the reaction process, clean and harmless reaction products, no flammable and explosive risks and the like, so the hydrated salts are considered to be a heat storage mode with a good application prospect. Taking thermochemical energy storage reaction of hydrated salt/water vapor system as an example, reversible gas-solid reaction is used to store and release heat in the stages of heat storage (desorption) and heat release (adsorption). The reaction equation is as follows:
Figure BDA0002223481420000011
in the desorption heat storage stage of the hydrate salt, the hydrate salt is heated to generate crystal salt without water or with part of water molecules removed, and at the moment, the energy is stored in the desorbed salt bed in the form of chemical potential energy; the heat releasing (adsorbing) process is to utilize water vapor or wet cold air to react with the desorbed crystal salt, and the heat released in the adsorbing process is provided for users. Currently, hydrated salt chemical heat storage has proven to be reliable in building heating and heat recovery. The research shows that LiOH. H2O、Ba(OH)2·8H2O、LaCl3·7H2O、MgCl2·6H2O、CaCl2·6H2O、MgSO4·7H2O and SrBr2·6H2The O and other hydrated salts have higher heat storage density and are heat storage materials with great application prospect. However, hydrated salts present various problems during desorption or adsorption reactions. For example, a small thermal conductivity affects the heat transfer effect, resulting in a slow reaction process; the salt layer close to the water vapor inlet section is easy to excessively absorb water, deliquesce or agglomerate in the adsorption process, so that irreversible loss is caused, the heat storage density is reduced, the service life of materials is prolonged, deliquesced hydrated salt can corrode a reactor to a certain degree, and the salt layer far away from a steam inlet cannot be in full contact reaction with water vapor, so that the performance of the whole heat storage system is reduced.
Therefore, the reaction structure beneficial to adsorption type thermochemical energy storage is designed, and the problems of thermochemical materials in the heat storage process are solved, so that the heat and mass transfer effect in the reaction process and the performance of a heat storage system are improved, and the important point is particularly. The current research on adsorption thermochemical energy storage and utilization is only on a small scale in the laboratory and mainly focuses on the heat storage material itself and the reaction mechanism, while there is little research on the reaction structure unit and practical application demonstration. The invention patent application publication number is CN107289803A, named as: the patent of 'a college reactor for chemical energy storage of hydrate' proposes to divide the heat storage material into a plurality of reaction units by the fin, and the device simple structure, and it is convenient to dismantle, not only can effectively avoid the energy storage material excessively adsorb and the scheduling problem of deliquescence, has still improved heat transfer effect under the fin effect. However, the heat storage reactor is only suitable for a closed system for performing an adsorption reaction by using water vapor, and an additional steam evaporation system is required, thereby increasing the investment cost and the space required for use. In addition, the heat exchange fluid is in dividing wall type contact with the heat storage material, so that heat exchange loss exists. The invention patent application publication number is CN105571208A, named as: the patent of "adsorption bed structure" proposes an adsorption bed structure for refrigeration, which comprises a metal pipe and a metal mesh pipe sleeved together, wherein the metal pipe and the metal mesh pipe are coaxial, and an adsorbent is filled between the metal pipe and the metal mesh pipe for adsorbing a refrigerant flowing in the metal mesh pipe. The device realizes heat exchange between an external medium and a refrigerant through the unit pipe, and the filling density of the adsorbent is high. However, the adsorbent particles are still piled up together, and the problems of heat and mass transfer process blockage, uneven adsorption and the like still exist. Patent CN108548443A proposes a thermal chemical adsorption heat storage device, which stores solid heat storage material and reaction gas separately. In the heat storage stage, the device utilizes the absorbed solar heat to heat the heat storage material, and the steam desorbed from the material flows into the liquid storage tank for cold storage after being condensed; and in the heat release stage, gasified liquid is introduced into the reaction bed by utilizing the evaporation effect to perform adsorption heat release reaction, and the generated heat is supplied to a user after the action of the heat exchanger. The device is safe and reliable, has large heat storage density and is simple and convenient to operate. However, the device has complex system structure, multiple pipeline structures and higher maintenance and operation cost, and still fills the solid reactant in the same adsorber, so that the problems that the local excessive adsorption and deliquescence of the solid reactant are caused and other parts are not fully reacted and the like cannot be avoided.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, provides an integral structure for adsorption type thermochemical energy storage and building heating, and designs a thermochemical energy storage device which is simple and compact in structure and high in feasibility and is used for building heating. The technical solution for realizing the invention is as follows:
the utility model provides an integral structure for adsorption-type thermochemical energy storage and building heating, includes gaseous total entry section, the valve, and gaseous entry lateral duct section, energy storage reaction bed, gaseous export lateral duct section, gaseous total export section turn to the valve, and the export section is outdoor to the gas chamber, and the export section is indoor to the gas, pipeline insulating layer, bolt, screw hole. The gas inlet and outlet sections are cylindrical pipelines, and the total inlet section is used for connecting a dry hot air or wet cold air pipeline provided from the outside.
The diameter of the reaction bed part pipeline with two ends connected with the gas branch pipe section is not less than that of the branch pipe section pipeline. In order to improve the utilization rate of incoming flow gas and ensure that solid reactants fully react with the gas as far as possible, the diameter of the pipeline of the reaction bed is 1-4 times that of the pipeline of the branch pipe section.
The length of each reaction bed pipeline part is generally not more than 50cm, or the length is not more than 6 times of the diameter of the reaction bed pipeline, so that the mass transfer effect in the gas-solid reaction process and the circulation stability of the heat storage material are ensured.
The two ends of the reaction bed pipeline filled with the solid porous reactant are connected by bolts and can be detached so as to take materials and fill materials. In addition, all the pipelines and the periphery of the energy storage reaction bed unit are coated by heat insulation layers so as to reduce the heat loss in the reaction process.
The quantity of the reaction units can be selected by opening the number of the valves according to the indoor actually required heat load, and then the heat supply quantity is controlled.
The gas main outlet section is provided with a steering valve, and gas after reaction can be introduced indoors or outdoors through the steering action according to actual conditions and requirements. Generally, in the heat storage stage, hot air heats the solid reactant and then discharges the solid reactant and desorbed water vapor to the outdoor environment; in the heat release stage, the heat generated by the adsorption reaction is introduced into the room along with the air to heat the room.
The reaction bed units are operated in parallel, and the number and the size of the reaction bed units are determined according to the specific heat load scale required by the building heating room. The integral energy storage pipeline structure can be arranged in small-sized family users and large-sized building buildings by combining a solar heat collection device or a waste heat recovery device. The whole heat storage device is arranged on the wall of an indoor building as a pipeline, and has high flexibility and feasibility.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the integral structure for adsorption thermochemical energy storage and building heating divides the heat storage material into a plurality of reaction unit modules, the amount of reactants of each reaction unit is small, the problems of local deliquescence or agglomeration, insufficient reaction and the like caused by the fact that thermochemical materials such as hydrated salt or hydroxide are simply accumulated in a reaction container in the prior art are solved, and the complete reaction is facilitated.
(2) The integral structure for adsorption type thermochemical energy storage and building heating integrates the heat storage unit and the gas conveying pipeline into a whole, does not need an additional heat storage reactor and heat exchange equipment, and has simple and compact integral structure and low investment and maintenance cost.
(3) The integral structure for adsorption type thermochemical energy storage and building heating is characterized in that the gas flowing from the inlet is directly contacted with the reactant in the desorption heat storage stage or the adsorption heat release stage, so that the heat exchange is sufficient, and the heat efficiency of the reaction is improved.
(4) The invention relates to an integral structure for adsorption type thermochemical energy storage and building heating, which is combined with a solar heat collection device or a waste heat recovery device to arrange an integral energy storage pipeline structure on small-sized family users and large-sized building buildings. The whole heat storage device is arranged on the wall of an indoor building as a pipeline, and the size and scale of the structure of the device can be designed according to the size of the indoor space; for a specific space, the number of the reaction units can be selected by opening the number of the valves according to the current required heat load, and the heat supply amount is further controlled. The monolithic structure has high flexibility and feasibility.
The invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic view of an integrated structure for adsorption thermochemical energy storage and building heating according to the invention;
FIG. 2 is a two-dimensional schematic diagram of a single heat storage pipe unit of an integrated structure for adsorption thermochemical energy storage and building heating according to the present invention;
FIG. 3 is a perspective cross-sectional view of a single heat storage pipe unit of an integrated structure for adsorption thermochemical energy storage and building heating according to the present invention;
Detailed Description
Example 1:
referring to fig. 1, 2 and 3, an integrated structure for adsorption thermochemical energy storage and building heating comprises a gas main inlet 1, a valve 2, a gas inlet branch pipe section 3, an energy storage reaction bed 4, a gas outlet branch pipe section 5, a gas main outlet section 6, a steering valve 7, a gas chamber outer outlet section 8, a gas chamber outlet section 9, a pipeline heat insulation layer 10, a bolt 11 and a threaded hole 12. The gas inlet and outlet sections are cylindrical pipelines, and the total inlet section is used for connecting a dry hot air or wet cold air pipeline provided from the outside. The diameter of the reaction bed pipeline with two ends connected with the gas branch pipe section is not less than that of the branch pipe section pipeline. In order to improve the utilization rate of the incoming flow gas and ensure that the solid reactant fully reacts with the gas as much as possible, the diameter of the pipeline of the reaction bed is 1-4 times that of the pipeline of the branch pipe section; because the overlong porous reaction bed can block the outflow of desorbed steam in the heat storage process and the sufficient reaction of the steam in the inflow with reactants at the rear section of the reaction bed in the heat release process, and solid particles at the front section of the reaction bed can excessively adsorb and deliquesce, the length of each reaction bed pipeline part is generally not more than 50cm, or the length is not more than 6 times of the diameter of the reaction bed pipeline, so as to ensure better mass transfer effect in the gas-solid reaction process; threaded holes 12 are formed in two ends of a reaction bed pipeline filled with solid porous reactants and are connected through bolts 11, so that the reaction bed pipeline can be detached to take materials and fill materials; in addition, all the pipelines and the periphery of the energy storage reaction bed 4 unit are coated by a heat insulation layer 10 to reduce the heat loss in the reaction process; after the reacted gas is converged at the gas main outlet section 6, the gas can be selectively introduced into the room or the outside of the room according to the actual condition and the requirement after the action of a steering valve 7; the reaction bed units are operated in parallel, and the number and the size of the reaction bed units are determined according to the specific heat load scale required by the building heating room. The integral energy storage pipeline structure can be arranged in small-sized family users and large-sized building buildings by combining a solar heat collection device or a waste heat recovery device. The whole heat storage device is arranged on the wall of an indoor building as a pipeline, and the size and scale of the structure of the device can be designed according to the size of the indoor space; for a specific space, the number of the reaction units can be selected by opening the number of the valves according to the current required heat load, and the heat supply amount is further controlled. The monolithic structure has high flexibility and feasibility.
The invention relates to a working principle of an integral structure for adsorption type thermochemical energy storage and building heating, which comprises the following steps:
now with SrBr2·6H2The working process of the invention for storing and releasing energy of the integral structure for adsorption thermochemical energy storage and building heating is described by taking O hydrated salt as an example of the heat storage material. Experimental research shows that SrBr2·6H2O can be desorbed to a great extent at about 80-90 ℃, and the reversible reaction equation is as follows:
Figure BDA0002223481420000051
firstly, a heat storage process: the dry hot air heated by the solar air heat collector or the industrial waste heat device is conveyed by an external pipeline and flows in from a gas main inlet section 1 of the pipeline structure, the opened valve 2 conveys the hot air to each gas inlet branch pipe section 3 and then to the energy storage reaction bed 4, the salt hydrate is heated and then desorbed to generate steam, the temperature of the hot air after heating the reaction bed is reduced, and the mixed humid air formed by the steam and the dry air is converged at a gas main outlet section 6 and is discharged outdoors through a gas outdoor outlet section 8 under the action of a steering valve 7. The heat insulation layer 10 can reduce the heat loss and promote the desorption reaction. This process continues until the desorption reaction is complete (the temperature or humidity of the outlet section can be used as a criterion for determining whether the reaction is complete or not: if the temperature or humidity of the outlet gas is almost the same as that of the inlet gas, the reaction has been substantially complete). And finishing the desorption heat storage stage, wherein the stage is the process of converting heat energy into chemical potential energy.
Secondly, heat release process: when the indoor temperature is low and heat is needed to be obtained in winter or at night, cold air (capable of being pre-humidified) provided by the outside flows in from the gas main inlet section 1 of the reactor, water vapor in the air and the reaction bed 4 are subjected to hydration (adsorption) reaction after passing through the valve 2 and the inlet branch pipe section 3, the air is heated by the heat released by the reaction, and the heated air is converged at the gas main outlet section 6 and then is introduced into a room through the gas indoor outlet section 9 under the action of the diverter valve 7, so that the purpose of indoor heating is achieved. In addition, the number of the reaction units can be selected by opening the number of the valves according to the current required heat load, and then the heat supply amount is controlled.
In one embodiment, SrBr is still used2·6H2The O-hydrated salt is taken as a heat storage material as an example, aiming at a heating room with the length, width and height of 5m multiplied by 4m respectively, an integral heat storage pipeline structure can be arranged along the wall surface of the room, the diameter D of a pipeline part of a reaction bed is 0.12m, the length L of the pipeline part of the reaction bed is 22cm, the pipe diameter D of a branch pipe at two ends of the pipeline structure is 0.05m, the whole pipeline structure is provided with N10 reaction bed units, and valves are all opened to operate. SrBr2·6H2Density of O hydrate salt rho 2390kg/M3, molar mass M0.3555 kg/mol, reaction bed porosity epsilon 0.6, reaction heat q 337kJ/mol, total mass of hydrate salt in all reaction beds:
Figure BDA0002223481420000052
the total heat stored for the desorption reaction is:
Figure BDA0002223481420000053
the heat can be used to heat the room when necessary. I.e. in theory 108117kJ of heat can be stored and supplied. Of course, the actual heat supply amount is generally slightly less than the value due to heat loss in the actual operation process and the like, but a better heat storage and heat supply effect can still be shown. And the simulation result shows that in the energy storage process, when the dry hot air flow rate u of each inlet branch pipe is 0.05m/s and the temperature T is 85 ℃, the model of the embodiment takes about 38h to complete the heat storage process, and then the total flow rate of the required hot air is:
Figure BDA0002223481420000061
namely, only the circulating hot air 134m with the temperature of 85 ℃ needs to be provided3The energy storage process can be completed, which is easy to achieve and feasible in practical application.
In conclusion, the integral structure for adsorption thermochemical energy storage and building heating is beneficial to improving the heat and mass transfer effects in the gas-solid reaction process, the heat storage unit is directly combined with the gas conveying pipeline, the device is simple and reliable, the feasibility and the flexibility are high, and the chemical heat storage can be well applied to building heating or heating.

Claims (3)

1. An integral structure for adsorption type thermochemical energy storage and building heating is characterized by comprising a gas main inlet section (1) for introducing air or other reaction gases, a valve (2) is opened, gas inlet branch pipe sections (3) for introducing flows into energy storage reaction units, an energy storage reaction bed (4) for performing heat storage and release reactions, a gas outlet branch pipe section (5) and a gas main outlet section (6) for allowing reacted gases to flow out, a steering valve (7) for changing the gas flow direction, a gas outdoor outlet section (8) and a gas indoor outlet section (9) for introducing the reacted gases into the outdoor and indoor, wherein the pipeline structures are cylindrical pipelines, and the gas main inlet section (1) is connected with an external pipeline for providing dry hot air or wet cold air;
the diameter of a unit pipeline of the reaction bed, the two ends of which are connected with the gas branch pipe sections, is not less than that of the branch pipe section pipeline, so that the utilization rate of incoming flow gas is improved, and solid reactants and gas are ensured to fully react, and the diameter of the pipeline of the reaction bed is 1-4 times that of the branch pipe section pipeline;
the length of each reaction bed pipeline part is not more than 50cm, or the length is not more than 6 times of the diameter of each reaction bed pipeline;
the reaction bed (4) units are operated in parallel, the number and the size of the reaction bed units are determined according to the heat load scale required by a building heating room, the integral energy storage pipeline structure is arranged on small-sized family users and large-sized building buildings by combining a solar heat collection device or a waste heat recovery device, and the whole heat storage device is arranged on the wall of an indoor building as a pipeline.
2. The monolithic structure for adsorption thermochemical energy storage and building heating according to claim 1, characterized in that the reaction bed tubes filled with solid porous reactants have screw holes (12) at both ends, are connected by bolts (11), can be disassembled for taking materials and filling materials, and moreover, all the tubes and the energy storage reaction bed (4) units are surrounded by a heat insulating layer (10) to reduce the heat loss during the reaction process.
3. The monolithic structure for absorption thermochemical energy storage and building heating according to claim 1, characterized in that the reacted gases are collected in the gas main outlet section (6), and after the action of the diverter valve (7), the gas flow is selectively introduced into the room or the outside according to the actual situation and need.
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