CN104806311B - Amino thermochemical energy-storage system - Google Patents
Amino thermochemical energy-storage system Download PDFInfo
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- CN104806311B CN104806311B CN201510116256.3A CN201510116256A CN104806311B CN 104806311 B CN104806311 B CN 104806311B CN 201510116256 A CN201510116256 A CN 201510116256A CN 104806311 B CN104806311 B CN 104806311B
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a kind of amino thermochemical energy-storage system, it carries out energy storage using amino thermochemical reversible reaction by the mutual conversion between electric energy, heat energy and chemical energy.This system mainly includes storage element, energy-storage units, releasing unit, heat-accumulator tank etc..During energy storage, ammonia occurs endothermic decomposition to react under catalyst action, then through overcompression, the energy of acceptance is stored in gaseous decomposition product nitrogen and hydrogen in the form of chemical energy and pressure energy；When releasing energy, make nitrogen and hydrogen that reverse thermal chemical reaction to occur under catalyst action, wherein stored chemical energy is changed into the release of high-grade heat energy and produces steam-electric power, and utilize reaction product gas expansion power generation.The system of the present invention has energy storage density height, efficiency high, environmentally friendly, the reliable feature of application it is adaptable to include all kinds power station in regenerative resource power station.
Description
Technical field
The present invention relates to energy storing technology field, particularly a kind of amino thermochemical energy-storage system.
Background technology
Enter 21 century, energy problem increasingly becomes the bottleneck of restriction global economic development.Coal, oil, natural gas etc.
The increasingly depleted of traditional fossil energy makes regenerative resource such as solar energy, wind energy receive the extensive concern of people.Electric power stores up
Can technology be unstable, the extensive key technology utilizing of batch (-type) regenerative resource, be also adjustment electrical network peak valley, improve electric power
System economy and the important means of stability.In current power energy storage technology, except running in large scale business system
Power station of drawing water and compressed air outside, heat chemistry energy storage technology provides a new way for power energy storage.
Heat chemistry energy storage technology is to realize the important and effective means of clean energy conversion, amino thermochemical energy storage system
System is more rising one kind.It utilizes reversible thermal chemical reaction, by electric energy, heat energy
Mutual conversion and chemical energy between carries out energy storage.Amino thermochemical energy-storage system except abundant raw material is cheap, can be round-the-clock
Beyond continuous energy supply, also there are the particular advantages not available for other energy storage technologies, such as energy storage density height, reversible reaction is easy to control
And no side reaction, technology maturation, application is reliable, store and separate simple etc., has good practical prospect.However, it is existing
Amino thermochemical energy-storage system still has some problems to need to solve, the such as long-term safety storage problem of hydrogen, nitrogen and liquefied ammonia；
System stored energy is less efficient, and scale is less；Harsher and incomplete conversion of reversible reaction condition etc..
Content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of amino thermochemical energy-storage system, it utilizes system
Flow process is innovated, and improves amino thermochemical energy-storage system performance it is adaptable to all kinds including regenerative resource power station
Power station.
The technical solution adopted in the present invention it is characterised in that：
A kind of amino thermochemical energy-storage system, including storage element, energy-storage units, releasing unit, heat-accumulator tank, its feature exists
In：
Described storage element includes compensator, low pressure liquid ammonia storage tank, pressure regulation compressor, gas cooler, high pressure gas storage
Tank, tap changer valve.It is differed from the storage of liquefied ammonia and hydrogen nitrogen with existing amino thermochemical energy-storage system
Separately, liquefied ammonia is stored in low pressure storage tank, and hydrogen nitrogen storage is in high pressure storage tank；Low pressure liquid ammonia storage tank pass through gas pipeline with
Compensator is connected, and is provided with pressure regulation compressor, gas cooler, tap changer valve it is ensured that stable (low pressure) of liquefied ammonia in the middle of pipeline
Storage.In low pressure liquid ammonia storage tank during reduced pressure, the hydrogen partial nitrogen in compensator after pressure regulation compressor compresses, through gas
The cooling of body cooler enters low pressure liquid ammonia storage tank；In low pressure liquid ammonia storage tank during pressure rise, tap changer valve is opened, portion therein
Hydrogen nitrogen is divided to enter in compensator.The cold flow side of gas cooler is recirculated cooling water or chilled water.
Described energy-storage units are included to ammonia pump, regenerator, ammonolysis craft heat accumulation reactor, low pressure compressor, high pressure compressor.
It is differed from using heat-accumulator tank to the heat producing in gas compression processes with existing amino thermochemical energy-storage system
Stored.In low pressure liquid ammonia storage tank, the liquefied ammonia of storage passes through pipeline via the cold flow side preheating entering regenerator to ammonia pump,
Then pass through pipeline and enter ammonolysis craft heat accumulation reactor；The hydrogen nitrogen producing in ammonolysis craft heat accumulation reactor passes through via pipeline
After the hot-fluid side heat release of regenerator, compensator is entered by gas piping；The outlet of compensator and the entrance of low pressure compressor
It is connected by pipeline, through high pressure is entered after the low pressure hot-fluid side heat release of heat-accumulator tank by gas piping after the compression of hydrogen nitrogen
Compressor, the hydrogen nitrogen after recompression is eventually entered into after the high-pressure heated fluid side heat release of heat-accumulator tank via gas piping
High pressure gas storage tank.
It is cold that described releasing unit includes regenerator, ammonia synthesis exothermic reactor, high pressure expansion machine, low-pressure expansion machine, process
Condenser, steam turbine, feed pump.It is anti-that its differing from existing amino thermochemical energy-storage system retains ammonia synthesis heat release
On the premise of answering device heat release generation water vapour to carry out Rankine cycle generating, mixed using ammonia synthesis reaction products gaseous ammonia, hydrogen, nitrogen
Close gas expansion to generate electricity, and make full use of the heat of storage in heat-accumulator tank.The outlet of high pressure gas storage tank and regenerator entrance phase
Even, the cold flow side preheating by regenerator for the hydrogen nitrogen, then enters ammonia synthesis exothermic reactor via gas piping；Ammino
Ammonia, hydrogen and nitrogen mixed gas that exothermic reactor produces are become to pass through the hot-fluid side heat release via regenerator for the gas piping
Enter high pressure expansion machine, it is swollen that the mixed gas after expansion enter low pressure via gas piping by the cold flow side heat absorption of heat-accumulator tank
Swollen machine；Low-pressure expansion machine outlet is connected with the entrance of process condenser by pipeline, and it is cold that the ammonia in mixed gas passes through process
The hot-fluid side of condenser is condensed into liquefied ammonia, enters low pressure liquid ammonia storage tank eventually through pipeline；Feed pump, process condenser, steam
Turbine is connected to form Rankine cycle by pipeline.The cold flow side of process condenser is recirculated cooling water or chilled water.
Described amino thermochemical energy-storage system, its ammonolysis craft heat accumulation inside reactor adopts wall to carry the micro- of catalysts
Channel design, using the fixed-bed structure of arrangement internally finned tube inside ammonia synthesis exothermic reactor；Ammonolysis craft heat accumulation reactor
Thermal source is electric heater unit, industrial waste heat, waste heat, solar energy or regenerative apparatus；The heat of release in ammonia synthesis exothermic reactor
Produce vapor through supporting heat exchanger to use for Rankine cycle generating.
Described amino thermochemical energy-storage system, it is provided with liquefied ammonia air relief valve to the pipeline between ammonia pump and regenerator；
The liquefied ammonia outlet of low pressure liquid ammonia storage tank is provided with liquefied ammonia switch valve；The gas outlet of high pressure gas storage tank is provided with gas open-close valve.
Described amino thermochemical energy-storage system, its heat-accumulator tank is heat-insulating container, and heat storage medium stores in a reservoir,
Mixed gas wherein with heat storage medium direct contact heat transfer or non-direct contact heat exchange, heat storage type be sensible heat accumulation of heat, latent heat
Accumulation of heat or mixed heat accumulation；During energy storage, heat-accumulator tank reclaims and stores the heat of compression of compressor generation, when releasing energy, heats inflated with low pressure
Mixed gas before machine.The heat storage medium adopting in heat-accumulator tank is the combination of one or more of：Water, paraffin, bio-oil,
No accumulation water of crystallization and salt, fuse salt, metal and its alloy, organic fatty acid, stone, rock or concrete.
Described amino thermochemical energy-storage system, its motor is with electrical network trough-electricity, wind-powered electricity generation, solar electrical energy generation, biology
Matter generates electricity what one or more power supply therein drove；Its compressor and decompressor are that load is controlled with rotating speed
Described amino thermochemical energy-storage system, its regenerator, gas cooler or process condenser be following a kind of or
Multiple combinations：Plate-fin, bushing type, shell-and-tube, jacket type, heat accumulating type, hybrid and immerse coil pipe type.
From technique scheme as can be seen that amino thermochemical energy-storage system of the present invention has the advantages that：
(1) adopt ammonia synthesis reaction product (N2、H2、NH3) expansion power generation and Rankine cycle generate electricity the mode combining, can
With the pressure energy of effectively utilizes gas, and using heat-accumulator tank, regenerator to the heat of compression in system, reaction pick up the heat, real
The comprehensive cascade utilization of existing energy, system effectiveness is significantly improved.
(2) by the way of double storage tanks, liquefied ammonia and hydrogen, nitrogen are separately stored in low pressure and high pressure storage tank, and profit
Keep the pressure stability of low pressure liquid ammonia storage tank with compensator, effectively increase stability and the safety of system, extensive for it
Application provides guarantee.
(3) ammonolysis craft heat accumulation inside reactor adopts wall to carry the MCA of catalysts, ammonia synthesis exothermic reaction
Using the fixed-bed structure of arrangement internally finned tube inside device, ongoing quick shifting heat release problem can be reacted with effectively solving, carry
High reaction conversion ratio.
Brief description
Fig. 1 is the amino thermochemical energy-storage system structural representation of the present invention.
Specific embodiment
For making the objects, technical solutions and advantages of the present invention become more apparent, develop simultaneously embodiment referring to the drawings, right
The present invention further describes.
The amino thermochemical energy-storage system of the present invention utilizes amino thermochemical reversible reaction.
In electric power low ebb, renewable energy power generation redundancy, ammonia is made to absorb heat under catalyst and high pressure effect by electrical heating
Decomposition reaction, then through overcompression, the energy of acceptance is stored in the form of chemical energy and pressure energy gaseous decomposition product nitrogen
In hydrogen；When peak of power consumption, renewable energy power generation are undesirable, then nitrogen and hydrogen are made in catalyst and high pressure
With the reverse thermal chemical reaction of lower generation, stored chemical energy in nitrogen and hydrogen is changed into the release of high-grade heat energy and produces steaming
Vapour generates electricity, and using the pressure energy expansion power generation in reaction product gas.
Embodiment：
Fig. 1 is the amino thermochemical energy-storage system embodiment 1 of the present invention.Including ammonolysis craft heat accumulation reactor 1, regenerator 2,
Compensator 3, pressure regulation compressor 4, gas cooler 5, low pressure liquid ammonia storage tank 6, to ammonia pump 7, low pressure compressor 8, motor 9, store
Hot tank 10, high pressure compressor 11, motor 12, high pressure gas storage tank 13, regenerator 14, ammonia synthesis exothermic reactor 15, high pressure
Decompressor 16, electromotor 17, low-pressure expansion machine 18, electromotor 19, process condenser 20, steam turbine 21, electromotor 22, process
Condenser 23, feed pump 24, liquefied ammonia switch valve 26, liquefied ammonia air relief valve 29, tap changer valve 35, gas open-close valve 46, pipeline
(25、27、28、30、31、32、33、34、36、37、38、39、40、41、42、43、44、45、47、48、49、50、51、52、53、
54th, 55,56,57,58) etc..Specific operation process is：
Low pressure compressor 8, high pressure compressor 11 are driven by motor (9,12), and the electric energy of motor can come from electricity more than needed
The renewable energy energy such as power or wind energy；High pressure expansion machine 16, low-pressure expansion machine 18, steam turbine 21 drive electromotor (17,19,
22) generate electricity.
In the energy storage stage, in low pressure liquid ammonia storage tank 6, the room temperature liquefied ammonia of storage, controls liquid by liquefied ammonia switch valve 26 with to ammonia pump 7
Ammonia is supplied.Liquefied ammonia switch valve 26 is opened, and low pressure room temperature liquefied ammonia is conveyed by ammonia pump 7, by the further blood pressure lowering of liquefied ammonia air relief valve 29,
Enter regenerator 2.In regenerator 2, it is changed into gaseous ammonia after the high-temperature hydrogen nitrogen heat exchange that room temperature liquefied ammonia is produced with ammonolysis craft, enters
Enter ammonolysis craft heat accumulation reactor 1.In ammonolysis craft heat accumulation reactor 1, electric heater unit is heated, electric energy be derived from electric power more than needed or
The regenerative resources such as wind energy.Under high temperature, catalysts conditions, ammonia endothermic decomposition becomes hydrogen nitrogen, high-temperature hydrogen nitrogen warp
After crossing regenerator 2 and room temperature liquefied ammonia heat exchange, enter compensator 3.Compensator 3 is connected by pipeline with low pressure liquid ammonia storage tank 6, pipeline
Centre is provided with pressure regulation compressor, gas cooler, tap changer valve, to keep the pressure in low pressure liquid ammonia storage tank 6 to keep constant.
Hydrogen nitrogen in compensator 3 enters heat-accumulator tank 10 after low pressure compressor 8 compression, and the heat of compression is stored in heat storage medium,
Then it is again introduced into heat-accumulator tank 10 after being compressed by high pressure compressor 11, the heat of compression is stored in heat storage medium, eventually enters into height
Pressure gas reservoir 13.
Release the energy stage, the high pressure hydrogen nitrogen of high pressure gas storage tank 13 storage, supply is controlled by gas open-close valve 46.Gas
Switch valve 46 is opened, and hydrogen nitrogen, after the high-temperature gas mixture body heat exchange that regenerator 14 is generated with ammonia synthesis reaction, enters ammino
Become exothermic reactor 15.In ammonia synthesis exothermic reactor 15, under high temperature, high pressure, catalysts conditions, hydrogen nitrogen is synthesized
Ammonia heat release.Water is delivered to ammonia synthesis exothermic reactor 15 absorbing reaction and is thermally generated water vapour by feed pump 24, by vapor wheel
After machine 21 acting generates electricity, it is condensed into water through process condenser 23 and goes successively in feed pump 24, whole process forms Rankine cycle.
Reaction generate high pressure-temperature ammonia, hydrogen, nitrogen mixed gas in regenerator 14 with room temperature hydrogen nitrogen heat exchange after, enter
High pressure expansion machine 16 expansion work.Then, mixed gas enter in heat-accumulator tank 10 after heat storage medium heating, entrance inflated with low pressure
Machine 18 expansion work.Mixed gas after expansion are changed into liquefied ammonia in process condenser 20 after circulating cooling water cooling, finally
Enter low pressure liquid ammonia storage tank 6.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spiritual and former in the present invention
Within then, any modification, equivalent substitution and improvement done etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of amino thermochemical energy-storage system, including energy-storage units, releasing unit, storage element, heat-accumulator tank（10）, its feature
It is：
Described storage element includes compensator（3）, pressure regulation compressor（4）, gas cooler（5）, low pressure liquid ammonia storage tank（6）, high
Pressure gas reservoir（13）, tap changer valve（31）, wherein,
Described compensator（3）In hydrogen nitrogen via pipeline enter pressure regulation compressor（4）, inflow gas are cold after compression
But device（5）Hot-fluid side, eventually through pipeline enter low pressure liquid ammonia storage tank（6）；
Described low pressure liquid ammonia storage tank（6）In hydrogen nitrogen by tap changer valve（31）Control can enter pressure regulation via pipeline
Tank（3）；
Described energy-storage units are included to ammonia pump（7）, regenerator（2）, ammonolysis craft heat accumulation reactor（1）, low pressure compressor（8）, high
Pressure compressor（11）, the first motor（9）, the second motor（12）, wherein,
Described low pressure liquid ammonia storage tank（6）The liquefied ammonia of middle storage passes through pipeline via to ammonia pump（7）Enter regenerator（2）Cold
Fluid side, then enters ammonolysis craft heat accumulation reactor by pipeline（1）；
Described ammonolysis craft heat accumulation reactor（1）The hydrogen nitrogen of middle generation passes through regenerator via pipeline（2）Hot fluid
Behind side, compensator is entered by gas piping（3）；
Described compensator（3）Outlet and low pressure compressor（8）Entrance pass through pipeline be connected, hydrogen nitrogen compression after warp
Heat-accumulator tank is passed through by gas piping（10）Low pressure hot-fluid side, subsequently enter high pressure compressor（11）In, hydrogen after compression
Nitrogen passes through heat-accumulator tank via gas piping（10）High-pressure heated fluid side, eventually through pipeline enter high pressure gas storage tank
（13）；
Described low pressure compressor（8）By the first motor（9）Drive, high pressure compressor（11）By the second motor（12）Drive
Dynamic；
Described releasing unit includes regenerator（14）, ammonia synthesis exothermic reactor（15）, high pressure expansion machine（16）, low-pressure expansion machine
（18）, the first process condenser（20）, the second process condenser（23）, steam turbine（21）, feed pump（24）, the first electromotor
（17）, the second electromotor（19）, the 3rd electromotor（22）, wherein,
Described high pressure gas storage tank（13）Outlet and regenerator（14）Entrance is connected, and high pressure hydrogen nitrogen flows through regenerator
（14）Cold flow side, then by pipeline enter ammonia synthesis exothermic reactor（15）；
Described ammonia synthesis exothermic reactor（15）The ammonia that produces, hydrogen and nitrogen mixed gas pass through gas piping via
Regenerator（14）Hot-fluid side enter high pressure expansion machine（16）, the mixed gas after expansion are via gas piping by heat-accumulator tank
（10）Cold flow side after enter low-pressure expansion machine（18）；
Described low-pressure expansion machine（18）Pipeline and the first process condenser are passed through in outlet（20）Entrance be connected, mixed gas
In ammonia pass through the first process condenser（20）Hot-fluid side be condensed into liquefied ammonia, eventually through pipeline enter low pressure liquefied ammonia storage
Tank（6）；
Described second process condenser（23）, steam turbine（21）, feed pump（24）Connected by pipeline and form Rankine cycle；
Described first electromotor（17）By high pressure expansion machine（16）Drive, the second electromotor（19）By low-pressure expansion machine（18）
Drive, the 3rd electromotor（22）By steam turbine（21）Drive.
2. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described ammonolysis craft heat accumulation reactor
（1）The internal MCA carrying catalysts using wall, ammonia synthesis exothermic reactor（15）Inside is using arrangement inner fin
The fixed-bed structure of pipe.
3. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described low pressure liquid ammonia storage tank（6）Logical
Cross pipeline and compensator（3）It is connected, in the middle of pipeline, be provided with pressure regulation compressor（4）, gas cooler（5）, tap changer valve
（31）, to keep low pressure liquid ammonia storage tank（6）In pressure stability.
4. amino thermochemical energy-storage system according to claim 1 it is characterised in that described to ammonia pump（7）And regenerator
（2）Between pipeline be provided with liquefied ammonia air relief valve（29）；Described low pressure liquid ammonia storage tank（6）Liquefied ammonia outlet be provided with liquefied ammonia switch valve
（26）；Described gas reservoir（13）Gas outlet be provided with gas open-close valve（46）.
5. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described heat-accumulator tank（10）Protect for adiabatic
Warm container, heat storage medium store in a reservoir, mixed gas wherein with heat storage medium direct contact heat transfer or non-direct contact
Heat exchange, heat storage type is sensible heat accumulation of heat, latent-heat storage or mixed heat accumulation；During energy storage, heat-accumulator tank（10）Reclaim and store low pressure pressure
Contracting machine（8）, high pressure compressor（11）The heat of compression producing, when releasing energy, heats low-pressure expansion machine（18）Front mixed gas.
6. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described gas cooler（5）, first
Process condenser（20）, the second process condenser（23）Cold flow side be recirculated cooling water or chilled water.
7. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described ammonia synthesis exothermic reactor
（15）The heat of middle release produces vapor through supporting heat exchanger and uses for Rankine cycle generating.
8. amino thermochemical energy-storage system according to claim 1 is it is characterised in that described ammonolysis craft heat accumulation reactor
（1）Thermal source be electric heater unit, industrial waste heat, waste heat, solar energy or regenerative apparatus；Described first motor（9）, second electricity
Motivation（12）, it is to be driven with electrical network trough-electricity, wind-powered electricity generation, solar electrical energy generation, biomass power generation one or more power supply therein
Motor.
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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 |
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| CN114738069B (en) * | 2022-04-11 | 2023-07-21 | 中国科学院工程热物理研究所 | Energy storage power generation system and energy storage power generation method |
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| JP2004099359A (en) * | 2002-09-09 | 2004-04-02 | Yukio Wakahata | Energy supply system using hydrogen energy and various systems as its applied patterns |
| CN1632438A (en) * | 2004-12-22 | 2005-06-29 | 华南理工大学 | Amino thermochemical high temperature energy storage method and apparatus therefor |
| CN102061950B (en) * | 2010-10-25 | 2014-09-10 | 陈海文 | Device for capturing CO2 from flue gas by ultralow temperature generation joint cryogenic medium-pressure method |
| JP5999322B2 (en) * | 2011-06-03 | 2016-09-28 | 戸田工業株式会社 | Power generation system |
| CN103075250B (en) * | 2012-11-08 | 2015-02-11 | 暨南大学 | Method for generating by graded use of cold energy of liquefied natural gas |
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