CN109595831A - A kind of heat chemistry energy storage method - Google Patents
A kind of heat chemistry energy storage method Download PDFInfo
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- CN109595831A CN109595831A CN201710922442.5A CN201710922442A CN109595831A CN 109595831 A CN109595831 A CN 109595831A CN 201710922442 A CN201710922442 A CN 201710922442A CN 109595831 A CN109595831 A CN 109595831A
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Abstract
The invention discloses a kind of heat chemistry energy storage method, includes the following steps: that high-valence state metal oxide absorbs thermal energy, reduction reaction occurs, generate lower valency metal oxide；The lower valency metal oxide absorbs thermal energy, and reforming reaction occurs with carbonaceous material, generates metal simple-substance and synthesis gas；Oxidation reaction occurs for the metal simple-substance, generates high-valence state metal oxide, discharges thermal energy.Present invention utilizes the modes of metal oxide energy storage complementary with carbonaceous material, by external heat sources such as solar energy with the storage of chemical energy form stable, and according to user demand, external stable heating.Method of the invention not only reduces the reaction temperature of metal oxide in heat chemistry thermal energy storage process, improves energy storage density, and prepares hydrogen using metal simple-substance under mild reaction conditions while realizing and provide multiple forms of energy to complement each other and the cascade utilization of the chemical energy of carbonaceous material.
Description
Technical field
The present invention relates to heat chemistry technical field of energy storage more particularly to a kind of heat chemistry energy storage methods.
Background technique
Energy conversion rate and efficiency are improved, carbon dioxide is reduced and pollutant emission is that China realizes energy-saving and emission-reduction and can hold
The key subjects of continuous development strategy.Currently, the energy that can be utilized includes luminous energy, mechanical energy, electric energy, chemical energy and thermal energy,
Other forms energy can be utilized by way of thermal energy, in addition, 90% in global energy budget be around heat conversion,
Transmission and storage.Therefore, the comprehensive effective use for developing heat-storage technology progress thermal energy is most important.Heat accumulating is not only to can be again
The raw energy (wind energy, solar energy etc.) thermal and power system is of great significance, and can be solved in the way of high-temperature residual heat
The lower problem of the thermal efficiency in industrial production.
By taking solar energy as an example, global solar radiation amount about 1.7 × 1017W, wherein China account for about 1% (1.8 ×
1015W is equivalent to 1.9 trillion tons of mark coal/years), it is 680 times of the current year total energy consumption in China, solar energy contains huge open
Send out potentiality.But solar energy energy-flux density is relatively low, and energy fluctuation is bigger, and carrying cost is high, parallel network power generation is such as used,
Again bigger to the impact of power grid, these problems always affect the further development and utilization of solar energy.Solar energy thermal-power-generating can
To utilize cheap energy storage technology, the output of stable electric generation power not only can be used as basic load power supply, but also can be used as peak regulation electricity
Source, therefore solar energy thermal-power-generating will have great potential in future.
Energy storage technology can be generally divided into sensible heat energy storage, hidden heat energy storage and heat chemistry energy energy storage according to energy storage mode.Sensible heat
Energy storage is not change physical form by temperature promotion for thermal energy storage, and energy storage density is lower, common sensible heat energy storage
Material has sandstone, fuse salt etc..And hidden heat energy storage is stored energy by phase transition forms, and heat is absorbed needed for the general heat of transformation
Measure larger, therefore hidden heat energy storage density ratio sensible heat energy storage is high, and common latent heat storage material has phase-change metal.And utilize chemical energy
Solar energy is stored and not only makes energy storage density high, an order of magnitude higher than sensible heat energy storage, and can be with room temperature for a long time
Storage, is readily transported.Common heat chemistry energy storage material have carbonate, metal oxide, metal hydride, ammonia, organic matter and
Hydroxide etc..
The research for the high temperature solar heat chemical energy storage carried out at present is common mostly for the purpose of producing clean fuel hydrogen
Have metal oxide two-step hydrolysis hydrogen manufacturing, since first step metal oxide thermal decomposition and reduction required temperature is higher, usually exist
It is 1500 DEG C or so, very high to solar energy heat collector requirement, cause heat loss larger.Also with metal oxide oxidation also
It is also the emphasis studied at present that original reaction, which carries out heat chemistry energy storage,.When metal oxide is heated, reduction reaction occurs,
Heat is absorbed, oxygen is discharged, heat is stored in the form of chemical energy.When heat release, the metal oxide and oxygen of reduction are anti-
It answers, discharges heat, the chemical energy of storage is externally released with form of thermal energy.High temperature solar energy-storage system design at present is single,
Only consider a kind of thermal chemical reaction, reaction condition is harsher, and stored energy form is single, and economy and applicability are still to be tested, limitation
Its commercialization is promoted.
Summary of the invention
It is an object of the invention to for existing heat chemistry energy storage technology it is in the form of a single, to the chemical reaction in thermal energy storage process
It is required that the deficiencies of stringent, at high cost, propose a kind of heat chemistry energy storage method of metal oxide energy storage complementary with carbonaceous material.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of heat chemistry energy storage method, includes the following steps: that high-valence state metal oxide absorbs thermal energy, hair
Raw reduction reaction, generates lower valency metal oxide；The lower valency metal oxide absorbs thermal energy, and weight occurs with carbonaceous material
Whole reaction generates metal simple-substance and synthesis gas.
Heat chemistry energy storage method provided by the present invention further includes hot release process, and it is anti-that oxidation occurs for the metal simple-substance
It answers, generates high-valence state metal oxide, discharge thermal energy.
Oxidation reaction occurs for the metal simple-substance, and the mode for generating high-valence state metal oxide can be with are as follows: metal simple-substance with
Exothermic oxidation reaction occurs for oxygen, generates high-valence state metal oxide；Or: exothermic reaction occurs for metal simple-substance and water,
Hydrogen and lower valency metal oxide are generated, exothermic oxidation reaction occurs for the lower valency metal oxide and oxygen of generation,
Generate high-valence state metal oxide.
In above-mentioned heat chemistry thermal energy storage process provided by the present invention, the thermal energy is the electric energy of solar energy, abandonment abandoning light
The thermal energy of conversion or the thermal energy of high-temperature residual heat.
Metallic element in the high-valence state metal oxide, lower valency metal oxide and elemental metals be selected from iron, manganese,
One or more of cobalt, copper, barium, antimony, chromium, tin and cadmium.
The carbonaceous material include one of derivative of coal, petroleum, natural gas, biomass and above-mentioned substance or
It is a variety of.
In addition, the synthesis gas generated in above-mentioned energy storage or heat release reaction process is used for chemical industry synthesis raw material or work
For guarantee fuel, the hydrogen is for chemical industry synthesis raw material or as guarantee fuel.
In heat chemistry energy storage method provided by the present invention, high-valence state metal oxide is by external heat source fire-bar
Under part, heat is absorbed, discharges oxygen, reduction reaction occurs, thermal energy is stored in lower valency metal oxide in the form of chemical energy
In the middle.Under external heat source heating condition, with carbonaceous material reforming reaction occurs for the lower valency metal oxide, generates simple substance
Metal and synthesis gas containing carbon monoxide and hydrogen, the reforming reaction are the strong endothermic reaction, further will be extraneous
The thermal energy of heat source is stored in the reaction product in the form of chemical energy.
In further heat release reaction, metal simple-substance reacts the metal oxide for directly generating high-valence state with oxygen,
Heat, external heat supply are discharged simultaneously；Or metal simple-substance reacts with water and generates hydrogen and lower valency metal oxide, it will be a part of
Chemical energy storage releases a part of thermal energy supply outside need in hydrogen, then lower valency metal further with oxygen
Solid/liquid/gas reactions generate high-valence state metal oxide, release heat, supply outside need.
During above-mentioned energy storage and heat release, metal oxide energy storage complementary with carbonaceous material, by external heat source to change
Energy form stable storage is learned, according to user demand, external stable heating eliminates the fluctuation of thermal energy (especially solar energy).?
When high-valence state metal oxide is reduced to lower valency metal oxide, required temperature is relatively low, at 1000 DEG C or so；And into
Lower valency metal oxide is reduced to elemental metals by one step, and then temperature will generally reach 1500 DEG C or more.If utilizing solar energy etc.
Energy heats will cause bigger radiation loss to the temperature, while require the material of reactor and manufacture high.And this hair
Bright that reforming reaction occurs using carbonaceous material and lower valency metal oxide, then the temperature for reacting required reduces, at 1000 DEG C
Even hereinafter, the requirement to reactor is greatly reduced.The reaction simultaneously is the endothermic reaction, and thermal energy is deposited in the form of chemical energy
It stores up in the elemental metals and synthesis gas that reaction generates.
Compared with prior art, the invention has the following advantages that
1, reforming reaction is carried out using the metal oxide of carbonaceous material and lower valency, reduced in heat chemistry thermal energy storage process
The reaction temperature of metal oxide, improves energy storage density.
2, lower than metal oxide two-step method hydrogen manufacturing temperature using metal simple-substance generation hydrogen, reaction condition milder.
3, it realizes and provides multiple forms of energy to complement each other and the cascade utilization of the chemical energy of carbonaceous material, reactants and products diversification is fitted
Different applications is closed, energy utilization rate is improved, reduces cost.
Detailed description of the invention
Fig. 1 is the flow chart according to the heat chemistry energy storage example of the solar energy of embodiment 1；
Fig. 2 is the flow chart according to the heat chemistry energy storage example of the solar energy of embodiment 2；
Fig. 3 is the flow chart according to the heat chemistry energy storage example of the high-temperature residual heat of embodiment 3；
Fig. 4 is the flow chart according to the heat chemistry energy storage example of the high-temperature residual heat of embodiment 4.
Specific embodiment
Heat chemistry energy storage method provided by a specific embodiment of the invention includes the following steps: that high-valence state metal aoxidizes
Object absorbs thermal energy, and reduction reaction occurs, and generates lower valency metal oxide；The lower valency metal oxide absorbs thermal energy, with
Reforming reaction occurs for carbonaceous material, generates metal simple-substance and synthesis gas.
It further include hot release process, specifically in the heat chemistry energy storage method provided by a specific embodiment of the invention
For, i.e., oxidation reaction occurs for the described metal simple-substance, generates high-valence state metal oxide, discharges thermal energy.Above-mentioned metal simple-substance hair
Raw oxidation reaction, the mode for generating high-valence state metal oxide can be two kinds: metal simple-substance and oxygen generation oxidation heat liberation are anti-
It answers, generates high-valence state metal oxide；Or exothermic reaction occurs for metal simple-substance and water, generates hydrogen and the oxidation of lower valency metal
Object, the lower valency metal oxide and oxygen of generation occur exothermic oxidation reaction, generate high-valence state metal oxide.
In above-mentioned energy storage and heat release reaction process, synthesis gas and hydrogen generated for chemical industry synthesis raw material or
As guarantee fuel.
In the heat chemistry energy storage method provided by a specific embodiment of the invention, the thermal energy can for solar energy,
The thermal energy of the electric energy conversion of light or the thermal energy of high-temperature residual heat are abandoned in abandonment.The high-valence state metal oxide, the oxidation of lower valency metal
Metallic element in object and elemental metals can be selected from one or more of iron, manganese, cobalt, copper, barium, antimony, chromium, tin and cadmium.
The carbonaceous material may include one of derivative of coal, petroleum, natural gas, biomass and above-mentioned substance or more
Kind.
In first and second embodiments of the invention, a kind of heat chemistry energy storage example of solar energy is each provided,
Wherein metal oxide is with cobaltosic oxide (Co3O4) for, carbonaceous material is with methane (CH4) for.
In third and fourth embodiment of the invention, the heat chemistry energy storage for each providing a kind of high-temperature residual heat is real
Example, wherein metal oxide is with cobaltosic oxide (Co3O4) for, carbonaceous material is by taking biomass, coal (C) as an example.
Embodiment 1:
As shown in Figure 1, a kind of heat chemistry energy storage example of solar energy, wherein metal oxide is with cobaltosic oxide (Co3O4)
For, carbonaceous material is with methane (CH4) for.
High-valence state metal oxide Co3O4Reduction reaction occurs when by solar energy heating to 900-1000 DEG C, absorbs thermal energy,
Oxygen is discharged, generates the CoO of lower valency, as shown in reaction equation (1), thermal energy is stored in the form of chemical energy.
2Co3O4→6CoO+O2 (1)
The CoO and CH of the lower valency of generation4Reforming reaction occurs under the heating of solar energy, generates elemental metals Co, with
And contain carbon monoxide (CO) and hydrogen (H2) synthesis gas, as shown in reaction equation (2), absorb solar energy, transformation
For the storage of chemical energy form.
CoO+CH4→Co+CO+2H2 (2)
Equation (1) and (2) are thermal energy storage process.
Elemental metals Co reacts the Co for generating high-valence state with oxygen3O4, and a large amount of thermal energy (800-900 DEG C) is released, according to
It needs to supply the external world, as shown in reaction equation (3).
3Co+2O2→Co3O4 (3)
Equation (3) is hot release process.
In addition, equation (2) synthesis gas generated is for storing, according to user demand, and the external heat supply of oxygen combustion, together
The corresponding chemical products of Shi Zuowei Material synthesis.
Embodiment 2:
As shown in Fig. 2, a kind of heat chemistry energy storage example of solar energy, wherein metal oxide is with cobaltosic oxide (Co3O4)
For, carbonaceous material is with methane (CH4) for.
High-valence state metal oxide Co3O4Reduction reaction occurs when by solar energy heating to 900-1000 DEG C, absorbs thermal energy,
Oxygen is discharged, generates the CoO of lower valency, (with embodiment 1) as shown in reaction equation (1), thermal energy is stored in the form of chemical energy.
The CoO and CH of the lower valency of generation4Reforming reaction occurs under the heating of solar energy, generates elemental metals Co, and contain one
Carbonoxide (CO) and hydrogen (H2) synthesis gas, (with embodiment 1) as shown in reaction equation (2), absorb solar energy, turn
Become the storage of chemical energy form.Equation (1) and (2) are thermal energy storage process.
Elemental metals Co and water (H2O it) reacts, generates the CoO and H of lower valency2, while the process is released a part of thermal energy and is supplied
To the external world, as shown in equation (4).The CoO of generation is further reacted with oxygen, is discharged amount of heat (800-900 DEG C), according to need
Outside is supplied, as shown in reactional equation (5).
Co+H2O→CoO+H2 (4)
6CoO+O2→2Co3O4 (5)
Equation (4) and (5) are hot release process.
In addition, equation (5) H generated2And equation (2) synthesis gas generated is for storing, according to user's needs,
With the external heat supply of oxygen combustion, while as the corresponding chemical products of Material synthesis.
Embodiment 3:
As shown in figure 3, a kind of heat chemistry energy storage example of high-temperature residual heat, wherein metal oxide is with cobaltosic oxide
(Co3O4) for, carbonaceous material is by taking biomass, coal (C) as an example.
High-valence state metal oxide Co3O4Reduction reaction occurs when being heated to 900-1000 DEG C by high-temperature residual heat, absorbs heat
Can, oxygen is discharged, generates the CoO of lower valency, as shown in reaction equation (6), thermal energy is stored in the form of chemical energy.
2Co3O4→6CoO+O2 (6)
Reforming reaction occurs under the heating of high-temperature residual heat for the CoO and C of the lower valency of generation, generates elemental metals Co and one
Carbonoxide (CO) absorbs high-temperature residual heat as shown in reaction equation (7), is changed into the storage of chemical energy form.
CoO+C→Co+CO (7)
Equation (6) and (7) are thermal energy storage process.
Elemental metals Co reacts the Co for generating high-valence state with oxygen3O4, and release a large amount of thermal energy (800 DEG C -900 DEG C), root
It is extraneous according to needing to supply, as shown in reaction equation (8).
3Co+2O2→Co3O4 (8)
Equation (8) is hot release process.
In addition, equation (7) carbon monoxide generated (CO) is for storing, it is external with oxygen combustion according to user demand
Heat supply, while as the corresponding chemical products of Material synthesis.
Embodiment 4:
As shown in figure 4, a kind of heat chemistry energy storage example of high-temperature residual heat, wherein metal oxide is with cobaltosic oxide
(Co3O4) for, carbonaceous material is by taking biomass, coal (C) as an example.
High-valence state metal oxide Co3O4Reduction reaction occurs when being heated to 900-1000 DEG C by high-temperature residual heat, absorbs heat
Can, oxygen is discharged, generates the CoO of lower valency, (with embodiment 3) as shown in reaction equation (6), thermal energy is deposited in the form of chemical energy
Storage.Reforming reaction occurs under the heating of high-temperature residual heat for the CoO and C of the lower valency of generation, generates the oxidation of elemental metals Co and one
Carbon (CO) absorbs high-temperature residual heat (with embodiment 3) as shown in reaction equation (7), is changed into the storage of chemical energy form.Equation
Formula (6) and (7) are thermal energy storage process.
Elemental metals Co and water (H2O it) reacts, generates the CoO and H of lower valency2, while the process is released a part of thermal energy and is supplied
To the external world, as shown in equation (9).The CoO of generation is further reacted with oxygen, is discharged amount of heat (800 DEG C -900 DEG C), according to
It needs to supply outside, as shown in reactional equation (10).
Co+H2O→CoO+H2 (9)
6CoO+O2→2Co3O4 (10)
Equation (9) and (10) are hot release process.
In addition, equation (10) H generated2And equation (7) synthesis gas generated is used to store, according to user's need
It wants, and the external heat supply of oxygen combustion, while as the corresponding chemical products of Material synthesis.
Claims (9)
1. a kind of heat chemistry energy storage method, which comprises the steps of:
High-valence state metal oxide absorbs thermal energy, and reduction reaction occurs, and generates lower valency metal oxide；
The lower valency metal oxide absorbs thermal energy, and reforming reaction occurs with carbonaceous material, generates metal simple-substance and synthesis gas.
2. heat chemistry energy storage method according to claim 1, which is characterized in that further include:
Oxidation reaction occurs for hot release process, the metal simple-substance, generates high-valence state metal oxide, discharges thermal energy.
3. heat chemistry energy storage method according to claim 2, which is characterized in that oxidation reaction occurs for the metal simple-substance,
Generate the mode of high-valence state metal oxide are as follows: exothermic oxidation reaction occurs for metal simple-substance and oxygen, generates high-valence state metal oxygen
Compound.
4. heat chemistry energy storage method according to claim 2, which is characterized in that oxidation reaction occurs for the metal simple-substance,
Generate the mode of high-valence state metal oxide are as follows: exothermic reaction occurs for metal simple-substance and water, generates hydrogen and lower valency metal oxygen
Compound, the lower valency metal oxide and oxygen of generation occur exothermic oxidation reaction, generate high-valence state metal oxide.
5. heat chemistry energy storage method according to any one of claim 1 to 4, which is characterized in that the thermal energy is the sun
Energy, abandonment abandon the thermal energy of the electric energy conversion of light or the thermal energy of high-temperature residual heat.
6. heat chemistry energy storage method according to any one of claim 1 to 4, which is characterized in that the high-valence state metal
Metallic element in oxide, lower valency metal oxide and elemental metals is selected from iron, manganese, cobalt, copper, barium, antimony, chromium, tin and cadmium
One or more of.
7. heat chemistry energy storage method according to any one of claim 1 to 4, which is characterized in that the carbonaceous material packet
Include one or more of the derivative of coal, petroleum, natural gas, biomass and above-mentioned substance.
8. heat chemistry energy storage method according to any one of claim 1 to 4, which is characterized in that the synthesis gas is used for
Chemical industry synthesis raw material or as guarantee fuel.
9. heat chemistry energy storage method according to claim 4, which is characterized in that the hydrogen for chemical industry synthesis raw material or
Person is as guarantee fuel.
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| CN110332837A (en) * | 2019-07-31 | 2019-10-15 | 西安热工研究院有限公司 | A kind of solar light-heat power-generation system and method based on metal oxide heat chemistry energy storage system |
| CN111023588B (en) * | 2019-11-22 | 2021-04-16 | 南京航空航天大学 | Solar energy coupling utilization system for heat collection chemical energy storage and hydrocarbon fuel preparation |
| CN113582240A (en) * | 2020-12-11 | 2021-11-02 | 浙江大学 | Thermochemical heat storage material, thermochemical heat storage module and preparation method |
| CN113606974A (en) * | 2020-12-11 | 2021-11-05 | 浙江大学 | Composite metal oxide thermochemical heat storage material, thermochemical heat storage module and preparation method |
| CN114623431A (en) * | 2022-03-21 | 2022-06-14 | 浙江大学 | Stable combustion peak regulation system and stable combustion peak regulation method |
| CN115011316A (en) * | 2022-06-07 | 2022-09-06 | 华中科技大学 | Optimization method for applying magnetic beads in coal fly ash to thermochemical heat storage |
| CN115818643A (en) * | 2022-12-09 | 2023-03-21 | 中南大学 | Thermochemical CO 2 Interactive double-fixed-bed device and process for chemical chain conversion |
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Application publication date: 20190409 |