CN105716464B - The application method of gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern - Google Patents
The application method of gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern Download PDFInfo
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- CN105716464B CN105716464B CN201610039869.6A CN201610039869A CN105716464B CN 105716464 B CN105716464 B CN 105716464B CN 201610039869 A CN201610039869 A CN 201610039869A CN 105716464 B CN105716464 B CN 105716464B
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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
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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
- 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
Abstract
Gas solid chemical reaction regenerative apparatus of the present invention based on segmentation exothermic heat of reaction pattern, accumulation of heat reactor, heat transfer fluid channels, reaction feed channel and several air accumulators including being filled with accumulation of heat reactant, each air accumulator is connected to accumulation of heat reactor respectively by reacting feed channel, and it is provided in the reaction feed channel at each air accumulator gas inlet and outlet and controls the valve that the air accumulator gas passes in and out, the heat transfer fluid channels are the sandwich passage being arranged on accumulation of heat reactor wall surface and/or for across the heat exchange pipeline of accumulation of heat inside reactor.Device of the present invention can weaken the fluctuation of heat exchanging fluid outlet temperature during Btu utilization, improve the thermal efficiency of regenerative apparatus, and simplify apparatus structure.
Description
Technical field
The invention belongs to gas solid chemical reaction accumulation of heat fields, and in particular to a kind of gas-solid based on segmentation exothermic heat of reaction pattern
Chemically react regenerative apparatus and its application method.
Background technology
Main heat accumulation method is sensible heat accumulation of heat at present, but its energy density is relatively low.Although latent-heat storage energy density is larger,
But the thermal coefficient of latent heat storage material is relatively low, causes that its heat transfer property in the application of hold over system is poor, heat storage efficiency is low.Heat
The energy density highest of chemical heat accumulation, and need not keep the temperature, heat loss it is small, have great application prospect.Wherein, carbonate
It decomposes, metal oxide decomposes and the gas solid state reaction heat storage technologies such as decomposition of metal hydrides are easy with reactants separate
The advantages of, it is ideal chemical heat accumulation method.ZL200710045622.6 discloses that " gas solid chemical reaction heat storage utilizes
Method and device ", the reaction gas discharged during heat accumulation in this method need to condense storage, needed during heat release by
Heat-producing chemical reaction is contacted with solid reactant after reaction gas evaporation after condensation, additional heat, and device need to be provided
It is complicated.In addition, existing gas solid chemical reaction hold over system heat output is unstable, heat exchanging fluid outlet temperature in exothermic process
The fluctuation of degree is larger, it is difficult to meet with thermal field the needs of closing (Paskevicius M, Sheppard DA, Williamson K,
Buckley CE.Metal hydride thermal heat storage prototype for concentrating
solar thermal power[J].Energy,2015,88:469-477.).By establishing metal hydride hold over system
Mathematical model, analog result affect its business and answer it has also been found that heat exchanging fluid outlet temperature is not perfectly flat steady during heat release
With (Bao ZW, Yang FS, Zhang ZX.Theoretical investigation of high temperature
thermal energy storage system using metal hydrides[C].The 5th International
Conference on Applied Energy,Pretoria,South Africa,Jul 1-4,2013.)。
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of based on the curing of segmentation exothermic heat of reaction pattern
Reaction regenerative apparatus and its application method is learned, to weaken the fluctuation of heat exchanging fluid outlet temperature during Btu utilization, improves and stores
The thermal efficiency of thermal, and simplify apparatus structure.
Gas solid chemical reaction regenerative apparatus of the present invention based on segmentation exothermic heat of reaction pattern, including interior filling accumulation of heat are anti-
Accumulation of heat reactor, heat transfer fluid channels, reaction feed channel and several air accumulators of object are answered, each air accumulator is by reacting feed channel
It is connected to respectively with accumulation of heat reactor, and is provided in the reaction feed channel at each air accumulator gas inlet and outlet and controls the gas storage
Tank gas disengaging valve, the heat transfer fluid channels be the sandwich passage being arranged on accumulation of heat reactor wall surface and/or for across
The heat exchange pipeline of accumulation of heat inside reactor.
The above-mentioned gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern, the heat exchanging fluid pipeline are snakelike
Structural tube, helical structure pipe, helicitic texture pipe or fin structure pipe.
The above-mentioned gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern, the air accumulator are 2~8 sizes
Identical air accumulator.
The above-mentioned gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern, the accumulation of heat reactant are metallic hydrogen
One kind in compound, metal oxide, carbonate.MgH can be selected in the hydride2、Mg2NiH4、LaNi4.7Al0.3H6In one
Kind, PbO can be selected in the oxide2、Co3O4、MnO2In one kind, MgCO can be selected in the carbonate3、CaCO3、FeCO3In
One kind.Since the reaction in accumulation of heat reactant heat-accumulating process is reversible, accumulation of heat reactant has following two types of feed：
The first type of feed：Direct filling metal hydride, metal oxide or carbonate.To make the utilization of heat more
Thoroughly (i.e. gas-solid synthetic reaction carries out more thorough) needs to fill a certain amount of accumulation of heat reactant correspondence in accumulation of heat reactor
Reaction gas.
Second of type of feed：Filling metal hydride, metal oxide or carbonate will occur in heat-accumulating process
The corresponding reaction solid of reaction and reaction gas, as indirect accumulation of heat reactant.It needs to make reaction solid and reaction gas after filling
Synthetic reaction first occurs in accumulation of heat reactor and generates corresponding metal hydride, metal oxide or carbonate as storage for body
Thermal response object.MgH can such as be loaded2Corresponding Mg and H2, Mg2NiH4Corresponding Mg2Ni and H2, LaNi4.7Al0.3H6It is corresponding
LaNi4.7Al0.3And H2, PbO2Corresponding PbO and O2, Co3O4Corresponding CoO and O2, MnO2Corresponding Mn2O3And O2, MgCO3It is corresponding
MgO and CO2, CaCO3Corresponding CaO and CO2, FeCO3Corresponding FeO and CO2。
The above-mentioned gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern, the accumulation of heat reactor are that tubular type is anti-
Answer one kind in device, tank reactor, plate-type reactor, disc type reactor.
The application method of gas solid chemical reaction regenerative apparatus of the present invention based on segmentation exothermic heat of reaction pattern, in use
The gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern is stated, steps are as follows：
(1) storage of heat
The valve being arranged in the reaction feed channel of air accumulator import and export is opened, accumulation of heat reactant is heated, its decomposition is made
For reaction solid and reaction gas, reaction gas enters air accumulator by reacting feed channel, close after reaction air accumulator into
The valve being arranged in the reaction feed channel in exit；
(2) utilization of heat
The valve being arranged in the reaction feed channel of an air accumulator import and export is opened, the reacting gas stream in air accumulator is made
It returns in accumulation of heat reactor and releases heat with reacting solid contact and react, the heat of releasing passes through in heat transfer fluid channels
Heat exchanging fluid heat exchange is used；After reaction gas in the air accumulator releases, the reaction of the air accumulator import and export is closed
The valve being arranged in feed channel opens the valve being arranged in the reaction feed channel of next air accumulator import and export, makes air accumulator
In reaction gas flow back into accumulation of heat reactor to react and release heat, the heat of releasing passes through in heat transfer fluid channels
Heat exchanging fluid heat exchange is used；So discharge one by one in the reaction gas to accumulation of heat reactor in air accumulator with to react solid anti-
It answers, completes the release and utilization of heat.
In gas solid chemical reaction heat accumulation method and device of the present invention based on segmentation exothermic heat of reaction pattern, the gas
Gu stage of reaction number (i.e. the number of air accumulator) is usually 2~8.Institute's sublevel hop count more at most exothermic process is more steady, but
So that system is more complicated.The size of air accumulator and accumulation of heat reactor is according to demand in the loadings and regenerative apparatus of accumulation of heat reactant
Heat and specific accumulation of heat reactant heat storage capacity determine, can specifically calculate by the following method.
When using the first type of feed, the accumulation of heat reactant quality, the reaction gas constitution of filling that are loaded into reactor
Amount, air accumulator total measurement (volume) are determined by following formula：
(1) the accumulation of heat reactant quality loaded：
In formula, mrFor accumulation of heat reactant quality (kg)；Q is demand heat (J)；M is the molal weight of accumulation of heat reactant
(kg/mol)；ψ is reaction conversion ratio, sets ψ=0.6~0.9；Δ H is that gas-solid reaction is hot (J/mol).
(2) the reaction gas quality filled：
In formula, mgTo need the reaction gas quality (kg) filled；ω is the reaction gas of generation after accumulation of heat reactant decomposes
Body and the mass ratio for reacting solid；TaAnd TdThe respectively reactor operation temperature of regenerative apparatus heat accumulation and exothermic process；peq(Ta)
And peq(Td)Respectively in TaAnd TdAt a temperature of gas-solid reaction balance pressure (Pa).
(3) total measurement (volume) of air accumulator：
In formula, VcFor the total measurement (volume) (m of air accumulator3)；RgFor gas constant (J/ (kg*K))；TcFor reaction gas in air accumulator
The mean temperature (K) of body；TaAnd TdThe respectively reactor operation temperature of regenerative apparatus heat accumulation and exothermic process；peq(Ta)With
peq(Td)Respectively in TaAnd TdAt a temperature of gas-solid reaction balance pressure (Pa).
When using second of type of feed, the reaction solid masses, reaction gas quality and the gas storage that are loaded into reactor
The total measurement (volume) of tank is determined by following formula：
(1) the reaction solid masses loaded：
In formula, msFor reaction solid masses (kg)；Q is demand heat (J)；M is reaction solid molal weight (kg/mol)；
ψ is reaction conversion ratio, sets ψ=0.6~0.9；Δ H is that gas-solid reaction is hot (J/mol).
(2) the reaction gas quality filled：
In formula, mgTo need the reaction gas quality (kg) filled；msFor reaction solid masses (kg)；ω reacts for accumulation of heat
After object decomposes, the reaction gas of generation and the mass ratio for reacting solid；TaAnd TdRespectively regenerative apparatus heat accumulation and exothermic process
Reactor operation temperature；peq(Ta)And peq(Td)Respectively in TaAnd TdAt a temperature of gas-solid reaction balance pressure (Pa).
(3) total measurement (volume) of air accumulator：
In formula, VcFor the total measurement (volume) (m of air accumulator3)；ω be accumulation of heat reactant decompose after, the reaction gas of generation with react
The mass ratio of solid；RgFor gas constant (J/ (kg*K))；TcFor the mean temperature (K) of air accumulator reaction gases；TaAnd TdPoint
Not Wei regenerative apparatus heat accumulation and exothermic process reactor operation temperature；peq(Ta) and peq(Td) it is respectively in TaAnd TdAt a temperature of
Gas-solid reaction balance pressure (Pa).
Btu utilization process total run time need to be determined according to heat demand.Total operating time divided by number of stages obtain every
The volume in a section of reaction time, each air accumulator passes through air accumulator total measurement (volume) VcDivided by number of stages is calculated.
Compared with prior art, the invention has the advantages that：
1, regenerative apparatus of the present invention is provided with multiple air accumulator storage reaction gas, and heat is being discharged to (profit
With) process opens air accumulator one by one that the reaction gas in air accumulator is made to react solid reaction with accumulation of heat reactor, by gas-solid
Reaction process is divided into multistep so that heat release is gentler, and the variation of heat exchanging fluid outlet temperature is small and steady, reduces heat profit
With the fluctuation of heat exchanging fluid outlet temperature in the process, the stability of heat output is improved, so as to preferably adaptation thermal field
The demand of conjunction.
2, heat storage device structure of the present invention is simple, easy to operate.
Description of the drawings
Fig. 1 is the structural schematic diagram of regenerative apparatus of the present invention.
In figure, 1-accumulation of heat reactor, 2-accumulation of heat reactants, 3-heat transfer fluid channels, 4-reaction feed channels, 5-1-
First air accumulator, the second air accumulators of 5-2-, 5-3-third air accumulator, 6-valves.
Specific implementation mode
The gas solid chemical reaction of the present invention based on segmentation exothermic heat of reaction pattern is stored below by specific implementation mode
Thermal and its application method are described further.
Embodiment 1
The structure of regenerative apparatus described in this example as shown in Figure 1, by be filled with accumulation of heat reactant 2 accumulation of heat reactor 1,
Heat transfer fluid channels 3, reaction feed channel 4, the first air accumulator 5-1, the second air accumulator 5-2 and third air accumulator 5-3 compositions, each
Air accumulator is connected to accumulation of heat reactor respectively by reacting feed channel, and an inlet and outlet are arranged in accumulation of heat reactor, with three gas storage
Three reaction feed channels of the inlet and outlet connection of tank are connected to after being intersected at one with the inlet and outlet of accumulation of heat reactor, each air accumulator
The valve 6 for controlling air accumulator gas disengaging is provided in the reaction feed channel of import and export, the accumulation of heat reactor is autoclave
Reactor, the heat transfer fluid channels are the heat exchange pipeline across accumulation of heat inside reactor, and the heat exchanging fluid pipeline is in accumulation of heat
The part of inside reactor is helix tube.
Regenerative apparatus heat-accumulating process is using existing common solar heating system as heat source, and solar heating system is on daytime
Heat is obtained by focusing mirror sunlight, for this heat transfer to heat exchanging fluid, heat exchanging fluid is passed through storage after being heated to 390 DEG C
In the heat exchange pipeline of thermal reactor, the heating fluid as regenerative apparatus heat accumulation process.Used heat exchanging fluid is led for Tao Shi
Deep fat Dowtherm A.
Demand heat is 4.7MJ, and the temperature that need to be heated is 295 DEG C, Exotherm Time 3h.Set reaction conversion ratio as ψ=
0.8, using the first type of feed, select MgH2For accumulation of heat reactant, it is H to need the reaction gas filled2。
(1) MgH being loaded into reactor2Quality be：
Demand heat Q=4.7MJ, accumulation of heat reactant MgH2Molal weight M=0.026kg/mol, reaction conversion ratio ψ=
0.8；The hot Δ H=75000J/mol of gas-solid reaction (Chaise A, De Rango P, Marty P.Experimental and
Numerical study of a magnesium hydride tank.Int J Hydrogen Energy, 2010,35:
6311-22.)。
(2) the reaction gas H filled2Quality is：
According to the MgH of filling2Quality and Mg and H2The ratio between molal weight, MgH is calculated2Reaction gas after decomposition
It is ω=0.083 with the mass ratio of reaction gas.The temperature of heat exchanging fluid is 390 DEG C during heat accumulation, then heat accumulation process reaction
The operation temperature T of devicea=390 DEG C, the heating temperature of exothermic process demand is 295 DEG C, then the operation temperature of exothermic process reactor
Spend Td=295 DEG C.According to Ta、TdCheck in MgH under relevant temperature2The reaction of decomposition reaction balances pressure peq(Ta)=
1368100Pa, peq(Td)=154050Pa (Chaise A, De Rango P, Marty P.Experimental and
Numerical study of a magnesium hydride tank.Int J Hydrogen Energy, 2010,35:
6311-22.).Known mrData above is substituted into following formula, obtained by=2.0kg：
(3) total measurement (volume) of air accumulator：
Reaction gas H2Gas constant RgFor 4157J/ (kg*K), because being to store reaction gas at room temperature, therefore store up
The mean temperature of gas tank reaction gases is set as Tc=293K, the total measurement (volume) for related data substitution following formula being obtained hydrogen container are：
The hot time is used as needed, determines that regenerative apparatus Btu utilization run time is 3h.When being run according to Btu utilization
Between exothermic process is divided into 3 stages (dividing equally), the operating time in each stage is 1h, and each stage corresponds to a gas storage
Three air accumulators are arranged in tank altogether, then the volume of each air accumulator is 0.051m3。
The method for carrying out heat accumulation and Btu utilization using regenerative apparatus described in the present embodiment, steps are as follows：
(1) heat storing process：Accumulation of heat reactant is loaded into accumulation of heat reactor and fills reaction gas, is then opened every
The high temperature Tao Shi conduction oils for carrying out self-heat power are passed into accumulation of heat by the valve being arranged in the reaction feed channel of a air accumulator import and export
In spiral heat exchange tube in reactor, the heat of high temperature Tao Shi conduction oils passes to accumulation of heat reactant by the tube wall that exchanges heat, and makes storage
Thermal response object is decomposed into reaction solid and reaction gas after being heated, reaction gas enters air accumulator by reacting feed channel, instead
The valve being arranged in the reaction feed channel of each air accumulator import and export is closed after answering；
(2) utilization of heat：The valve being arranged in the reaction feed channel of the first air accumulator import and export is opened, the first storage is made
Reaction gas in gas tank flow back into accumulation of heat reactor and releases heat with reacting solid contact and react, and the heat of releasing is logical
It crosses heat transfer fluid channels and passes to heat exchanging fluid and be used.After first one third Btu utilization cycle of operation
(i.e. after 1h) closes the valve on the first air accumulator, opens the valve in the reaction feed channel of the second air accumulator import and export, make
Reaction gas in second air accumulator flow back into accumulation of heat reactor with react solid contact react release heat, releasing
Heat, which continues through heat transfer fluid channels and passes to heat exchanging fluid, to be used.After second one third cycle of operation
(i.e. after 2h) closes the valve on second air accumulator, is arranged in the reaction feed channel of opening third air accumulator import and export
Valve, make the reaction gas in third air accumulator flow back into accumulation of heat reactor with react solid contact react releasing heat
Amount, the heat of releasing, which continues through heat transfer fluid channels and passes to heat exchanging fluid, to be used.It is run in third one third
After end cycle (i.e. after 3h), the valve on third air accumulator is closed, Btu utilization process terminates.In this way, gas-solid reaction mistake
Journey is divided into three phases and gradually carries out so that exothermic process is more stable.
Claims (7)
1. a kind of application method of the gas solid chemical reaction regenerative apparatus based on segmentation exothermic heat of reaction pattern, which is characterized in that institute
State gas solid chemical reaction regenerative apparatus include it is interior filling accumulation of heat reactant (2) accumulation of heat reactor (1), heat transfer fluid channels (3),
Feed channel (4) and the identical air accumulator of 2~8 sizes are reacted, each air accumulator is reacted with accumulation of heat respectively by reacting feed channel
Device is connected to, and is provided with the valve for controlling air accumulator gas disengaging in the reaction feed channel at each air accumulator gas inlet and outlet
Door (6), the heat transfer fluid channels are the sandwich passage being arranged on accumulation of heat reactor wall surface and/or are in accumulation of heat reactor
The heat exchange pipeline in portion；Application method includes the following steps：
(1) storage of heat
The valve being arranged in the reaction feed channel of air accumulator import and export is opened, accumulation of heat reactant is heated, it is made to be decomposed into instead
It answers solid and reaction gas, reaction gas to enter air accumulator by reacting feed channel, closes air accumulator inlet and outlet after reaction
The valve being arranged in the reaction feed channel at place；
(2) utilization of heat
The valve being arranged in the reaction feed channel of an air accumulator import and export is opened, the reaction gas in air accumulator is made to flow back into
Heat is released with reacting solid contact and react in accumulation of heat reactor, and the heat of releasing passes through the heat exchange in heat transfer fluid channels
Fluid heat transfer is used；After reaction gas in the air accumulator releases, the reaction tracheae of the air accumulator import and export is closed
The valve being arranged on road is opened the valve being arranged in the reaction feed channel of next air accumulator import and export, is made in air accumulator
Reaction gas, which flow back into accumulation of heat reactor to react, releases heat, and the heat of releasing passes through the heat exchange in heat transfer fluid channels
Fluid heat transfer is used；So one by one discharge air accumulator in reaction gas to accumulation of heat reactor in react solid reaction,
Complete the release and utilization of heat.
2. the application method of the gas solid chemical reaction regenerative apparatus according to claim 1 based on segmentation exothermic heat of reaction pattern,
It is characterized in that the heat transfer fluid channels are serpentine configuration pipe, helical structure pipe, helicitic texture pipe or fin structure pipe.
3. the user of the gas solid chemical reaction regenerative apparatus according to claim 1 or claim 2 based on segmentation exothermic heat of reaction pattern
Method, it is characterised in that the accumulation of heat reactant is one kind in metal hydride, metal oxide, carbonate.
4. the application method of the gas solid chemical reaction regenerative apparatus according to claim 3 based on segmentation exothermic heat of reaction pattern,
It is characterized in that the metal hydride is MgH2、Mg2NiH4、LaNi4.7Al0.3H6In one kind.
5. the application method of the gas solid chemical reaction regenerative apparatus according to claim 3 based on segmentation exothermic heat of reaction pattern,
It is characterized in that the metal oxide is PbO2、Co3O4、MnO2In one kind.
6. the application method of the gas solid chemical reaction regenerative apparatus according to claim 3 based on segmentation exothermic heat of reaction pattern,
It is characterized in that the carbonate is MgCO3、CaCO3、FeCO3In one kind.
7. the user of the gas solid chemical reaction regenerative apparatus according to claim 1 or claim 2 based on segmentation exothermic heat of reaction pattern
Method, it is characterised in that the accumulation of heat reactor is in tubular reactor, tank reactor, plate-type reactor, disc type reactor
It is a kind of.
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| CN109470070A (en) * | 2017-09-08 | 2019-03-15 | 东南大学 | A kind of preparation of Lewis acid-base adducts object saturated solution and decomposition technique and its application |
| CN112844266A (en) * | 2021-01-15 | 2021-05-28 | 云南电网有限责任公司电力科学研究院 | Temperature control system and method for hydrogenation reactor |
| CN114838343B (en) * | 2022-03-21 | 2023-08-22 | 浙江大学 | Stable combustion peak regulation system and stable combustion peak regulation method |
| CN114673976B (en) * | 2022-03-21 | 2023-06-06 | 浙江大学 | Peak regulating system and method |
| CN114659025A (en) * | 2022-03-25 | 2022-06-24 | 海南天宇科技集团有限公司 | Hydrogen cylinder module with low-pressure alloy hydrogen storage bottle matched with medium-pressure hydrogen storage bottle |
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