CN103134213A - Method for converting and storing solar energy with low-hydration magnesium chloride as energy storage working medium - Google Patents
Method for converting and storing solar energy with low-hydration magnesium chloride as energy storage working medium Download PDFInfo
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- CN103134213A CN103134213A CN2013100775316A CN201310077531A CN103134213A CN 103134213 A CN103134213 A CN 103134213A CN 2013100775316 A CN2013100775316 A CN 2013100775316A CN 201310077531 A CN201310077531 A CN 201310077531A CN 103134213 A CN103134213 A CN 103134213A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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Abstract
The invention aims at providing a method for converting and storing solar energy with low-hydration magnesium chloride as an energy storage working medium and relates to effective utilization of magnesium in salt lakes and storage and conversion of solar energy. The method particularly includes: in the periods when solar radiation is sufficient in the daytime, the solar radiation is received through a flat solar thermal collector, heat is transferred to a one-time dehydration fluidized bed loaded with bischofite (MgCl2 6H2O), the temperature of the bed is increased to the dehydration temperature, then the MgCl2 6H2O loses the crystal water to form the low-hydration magnesium chloride (MgCl2 4H2O), conversion from the solar energy to chemical energy is achieved, and water vapor generated by the reaction is delivered to a steam turbine set to generate electricity; and in the nighttime or when the solar radiation is insufficient, the water vapor is enabled to enter the dehydration fluidized bed where the low-hydration magnesium chloride is stored, under the condition that the temperature and the partial pressure of the water vapor are controlled, the low-hydration magnesium chloride is enabled to be subjected to hydration reaction, the number of crystal water molecules is increased to form MgCl2 6H2O again, absorption (hydration) heat is released, the conversion from chemical energy to thermal energy is achieved, and the released heat is transferred to a heat preservation water tank so as to generate water vapor to drive the steam turbine set to generate electricity.
Description
Technical field
The invention belongs to salt lake magnesium resource utilization and energy storage and conversion field, the absorption/desorption process that is specifically related to hydrated magnesium chloride carries out sun transformation of energy and storage.
Background technology
Existing energy storage technology can be divided into the sensible heat energy storage, three kinds of modes of latent heat of phase change energy storage and chemical energy storage [Yu Xiaofu, Zhang Zhengguo, Wang Shiping. composite heat storage material progress [J]. new forms of energy, 1999,21 (9): 35-38].Sensible heat energy storage technology device is simple, and cost is lower, but energy storage density is lower, and the output temperature fluctuation is excessive; Hidden heat energy storage energy storage density is higher, and heat accumulation, the approximate isothermal of heat release process are separated out problem but fail to solve well cold-peace always; The energy storage density of chemical energy storage mode is large, and the working medium One's name is legion can be selected according to different operating modes, has good development prospect.wherein, application absorption type system carries out energy storage and receives increasing concern, its principle is: the employing low grade heat energy is driving force, utilize that in solid-gas reversible chemical reaction process, heat energy transforms with absorption potential energy technology [the Wu Huijun that realizes energy storage mutually, Wang Shengwei, Zhu Dongsheng.Effects of impregnating variables on dynamic sorption characteristics and storage properties of composite sorbent for solar heat storage[J] .Solar Energy, 2007, 81 (7): 864-871].On this basis, can utilize the temperature of chemisorbed salt and the response characteristic of pressure variation to build a kind of heat chemistry Temp .-changing adsorption technology, energy storage and efficient utilization of low grade heat energy are combined, for the utilization of low-grade heat source energy provides a kind of good thinking [Ma Liang, Wang Ruzhu, Li Tingxian. the cold and hot composite energy storage research of heat chemistry absorption thermode that low grade heat energy drives. Refrigeration Technique .2011,3,34-38].
Contain a large amount of magnesium chlorides in China's salt lake bittern, as the accessory substance that extracts potash fertilizer, 1 ton of potash fertilizer of every production, 10 tons of magnesium chlorides of by-product, annual newly-increased discharging magnesium is amounted to into bischofite and is reached 3,000 ten thousand tons, long-term accumulation is not utilized effectively, and a large amount of magnesium enter circulation and final abandoned, cause the waste of superior resources and serious environmental problem.
Magnesium chloride has been applied to many industrial circles such as metallurgy, building materials and weaving as a kind of basic industrial chemicals.But compare the bischofite that the potassium discharging is proposed in the salt lake every year, magnesium resource utilizes total amount very limited.At present butter is mainly concentrated on CaCl as the research that adsorbent is used for chemical energy storage
2, LiCl, SrCl
2, BaCl
2Deng.CaCl
2Due to inexpensive and stable, normal and NH
3Form CaCl
2/ NH
3Working medium is to being applied to the chemical heat pump system, realize to solar energy solar thermal utilization [Lin Guiping, Yuan Xiugan. the application of chemical heat pump system in solar thermal utilization. solar energy journal .1996,17 (1): 93-97].Professor Ding Jing of Zhongshan University utilizes anhydrous LiCl to be adsorbent, and the aqueous vapor in absorbed air can change the air of humidity 90% into 10% dry air, and the approximately 20 ° of C that can elevate the temperature, and reaches the purpose to room air heating and dehumidifying.But lithium metal and compound thereof belong to rare strategic resources, and be too high as the cost of adsorbing medium, limited its large-scale application.Anhydrous MgCl
2Have extremely strong water absorbing capacity, yet, the anhydrous MgCl of one side
2Be difficult to preparation (complex manufacturing, cost high), it very easily absorbs water on the other hand, and is very unstable, has increased operation and has preserved difficulty.
As adsorbent, (water) process discharges and the mode of storage power belongs to the chemisorbed energy storage by adsorbing with low hydrated magnesium chloride, and the heat that adsorption reaction discharges is called heat of adsorption.
Magnesium dichloride hexahydrate (bischofite) is the most stable existence form of magnesium chloride hydrated salt under room temperature, and it can resolve (dehydration) process along with temperature raises, and progressively changes low hydrated magnesium chloride into, and its dehydration needs heat absorption.If provide the energy with solar energy, at MgCl
26H
2Absorb solar energy when O resolves, reach dehydration (2H
2O or 4H
2O) temperature, obtain low hydrated magnesium chloride, then to hang down hydrated magnesium chloride as energy storage working medium, discharge or store heat after absorbing high temp steam, again the heat (heat of adsorption) that discharges is converted to other forms of energy, will opens up chemical energy storage that a solar energy utilization and large chemical industry of inorganic salt utilization of resources the be coupled new way with power conversion (use of staggering the time energy).The storage density of this system can reach 573kJ/kg, higher than the heat chemistry absorption thermode (NaBr-NH of the people such as Wang Ruzhu research and development
3As energy storage working medium) energy storage density 258kJ/kg[Ma Liang, Wang Ruzhu, Li Tingxian. the cold and hot composite energy storage research of heat chemistry absorption thermode that low grade heat energy drives. Refrigeration Technique .2011,3,34-38], have good practical prospect.Have not yet to see and utilize hydrated magnesium chloride as energy storage working medium, solar energy to be transformed and the report that stores.
Summary of the invention
The purpose of this invention is to provide and a kind ofly solar energy is transformed and stores as chemisorbed energy storage working medium with low hydrated magnesium chloride.This technology is the effective utilization to salt lake magnesium resource bischofite.
Solar energy is transformed and stores as chemisorbed energy storage working medium with low hydrated magnesium chloride, concrete steps are as follows:
The time utilization flat-plate solar heat collector of solar light irradiation abundance receives the irradiation of sunshine by day, and heat is imported in the primary dewatering ebullated bed that bischofite is housed, and makes temperature increase to 120 in bed～180 ° C, at this moment MgCl
26H
2O loses the crystallization water and generates low hydrated magnesium chloride MgCl
24H
2O,, realize that solar energy arrives chemical conversion of energy, and will react the water vapour that generates and output to Steam Turbine and generate electricity; When night or solar radiation when inadequate, water vapour is entered have the dehydration ebullated bed of low hydrated magnesium chloride, control temperature at 25～110 ° of C and steam partial pressure 1.013 * 10
2～1.560 * 10
5Under the condition of Pa, make low hydrated magnesium chloride generation hydration reaction, increase hydration number, regenerate MgCl
26H
2O discharges absorption (hydration) heat, realizes chemical energy to the transformation of heat energy, and the heat of release reaches attemperater, produces the generating of water vapour pushing turbine group.
The chemical equation that said process occurs is as follows:
Wherein process (2) is subject to the impact of steam partial pressure and temperature.When keeping temperature-resistant, steam partial pressure is larger, and the rate of water absorption of magnesium chloride hydrate is faster, and when system temperature raise, it is just larger that required steam partial pressure is carried out in reaction.
The present invention's device flow chart used comprises: flat-plate solar heat collector, attemperater, stop valve, pressure measuring instruments, primary dewatering ebullated bed as shown in Figure 1.Above equipment all connects with pipeline.
Below in conjunction with device, above-mentioned solar energy conversion and storage process are introduced
In the time period of solar light irradiation abundance: China's Qinghai Salt Lake is regional, north latitude 30-40 degree, at 10 in morning Beijing time is to point in afternoons 4, carry out energy storage, close stop valve (4), utilize flat-plate solar heat collector (1) to receive the irradiation of sunshine, conduct heat in the primary dewatering ebullated bed (6) that bischofite is housed, make temperature increase to 120 in bed～180 ° C, at this moment MgCl
26H
2O loses the crystallization water and generates low hydrated magnesium chloride (MgCl
24H
2O), open simultaneously stop valve (5), the water vapour that output-response generates realizes that solar energy arrives chemical conversion of energy, the water vapour pushing turbine group that produces can be generated electricity; When inadequate, close stop valve (5) when night or solar radiation, open stop valve (4), make the water vapour in attemperater (2) enter primary dewatering ebullated bed (6), control temperature at 25～110 ° of C and steam partial pressure 1.013 * 10
2～1.560 * 10
5Pa makes low hydrated magnesium chloride generation hydration reaction, increases hydration number, regenerates MgCl
26H
2O, and discharge absorption (hydration) heat, realize chemical energy to the transformation of heat energy, the heat of release reaches pond 3, produces the generating of water vapour pushing turbine group.The area of described flat-plate solar heat collector is 1-20 square metre.
The average intensity of illumination that solar irradiation is mapped to ground is 1000W/m
2, the enthalpy change △ of reaction (1)
rH
m=115.24kJ/mol, the per day efficient of ordinary flat solar thermal collector is 50～60%, therefore gets as calculated, under unit interval and unit are condition, flat-plate solar collector can make 3.1～3.8kg MgCl
26H
2The O dehydration becomes MgCl
24H
2O, namely flat-plate solar collector is 3.1～3.8kg/ (hm to the efficient of dewatering bischofite reaction
2).
The present invention has following remarkable advantage:
1. take low hydrated magnesium chloride as chemisorbed energy storage working medium, solar energy conversion and storage are had no bibliographical information
2. there is abundant salt lake magnesium resource in China, and resource reserve is large, so raw material is easy to get, cost is low, is fit to large-scale application;
3.. utilize abundant solar energy resources as input energy sources, green economy, pollution-free, meeting can source clean, recycling aim;
4. desorption/the adsorption process of hydrated magnesium chloride is reversible, and dehydration/hydrated product can be recycling; Realization is staggered the time with energy, effectively solves the unbalanced problem of solar energy supply and demand.
Description of drawings
Fig. 1 transforms and the storage device flow chart solar energy as chemisorbed energy storage working medium with low hydrated magnesium chloride; Wherein: 1-flat-plate solar heat collector, 2-attemperater, 3-attemperater, 4-stop valve, 5-stop valve, 6-primary dewatering ebullated bed.
The specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but not as the present invention being done the foundation of any restriction.Device in an embodiment as shown in Figure 1.
Embodiment one
Drop into 1 kg water chloromagnesite in primary dewatering ebullated bed 6, under solar radiation, use the bischofite in the flat-plate solar heat collector heating primary dewatering ebullated bed 6 of 10 square metres, irradiation time is 5 hours, and the temperature of controlling in primary dewatering ebullated bed 6 reaches 120 ° of C, in this process, close stop valve 4, open stop valve 5, derive the water vapour that reaction generates, this steam is used as generating; When intensity of sunshine is not enough (18 o'clock), close stop valve 5, open stop valve 4, pass into the water vapour in attemperater 2 in the primary dewatering ebullated bed 6, the water vapor pressure of controlling in primary dewatering ebullated bed 6 is 1.013 * 10
3Pa, temperature is 25 ° of C, and the heat of release reaches in attemperater 3, and the water vapour that produces is used for generating, and wherein the bischofite of 1 kilogram can produce the heat of 573KJ.
By the thermodynamics basic definition, under certain pressure, △
rH
m=∫ C
pDT, △
rS
m=∫ C
pDT/T calculates enthalpy change and entropy in the hydration reaction process.According to Thermodynamics Formulas △
rG
m=△
rH
m-T △
rS
m, can calculate the Gibbs free energy △ of magnesium chloride lower hydrate hydro-combination process
rG
m, by equation △
rG
m=△
rG
m o+ RTln (P
H2O)
-2, calculate corresponding steam partial pressure.Therefore, when temperature is 298.15K, steam partial pressure is 1.013 * 10
3Pa, the enthalpy change △ of reaction (2)
rH
mFor-116.399kJ/mol, and 1 kg water chloromagnesite generates MgCl
24H
2The amount of substance of O (n) is 4.926mol, therefore, and MgCl
24H
2O hydration reaction liberated heat is Q=n △
rH
m=573kJ.
Wherein, △
rH
mRefer to mole enthalpy of formation, the kJ/mol of unit; △
rS
mThe accurate mole Entropy Changes of index, the kJ/K of unit; C
pRefer to the constant pressure specific heat appearance, the J/ of unit (kgK); 298.15K under, MgCl
24H
2The C of O
p=57.6594J/ (kgK); T refers to reaction temperature, unit K; △
rG
mRefer to molar reactive gibbs free energy change value, the kJ/mol of unit; △
rG
m oThe accurate molar reactive gibbs free energy change of index value, the kJ/mol of unit; R refers to ideal gas constant, R=8.314Jmol
-1K
-1, P
H2OThe steam partial pressure that refers to reaction, the Pa of unit; Q refers to MgCl
24H
2O hydration reaction liberated heat, the kJ of unit; N refers to MgCl
24H
2The amount of substance of O, the mol of unit.
Embodiment two
Drop into 0.5 kg water chloromagnesite in primary dewatering ebullated bed 6, under solar radiation, use the bischofite in the flat-plate solar heat collector heating primary dewatering ebullated bed 6 of 8 square metres, irradiation time is 2 hours, and the temperature of controlling in primary dewatering ebullated bed 6 is 130 ° of C, in this process, close stop valve 4, open stop valve 5, derive the water vapour that reaction generates, this steam is used as generating; (19 o'clock), close stop valve 5 when intensity of sunshine is inadequate, opens stop valve 4, passes into the water vapour in attemperater 2 in the primary dewatering ebullated bed 6, and the water vapor pressure of controlling in primary dewatering ebullated bed 6 is 3.262 * 10
3Pa, temperature is 80 ° of C, and the heat of generation reaches in attemperater 3, and the water vapour of generation is used for generating, and wherein the bischofite of 0.5 kilogram can produce the heat of 285kJ.
Claims (2)
1. method that as chemisorbed energy storage working medium, solar energy is transformed and stores with low hydrated magnesium chloride, concrete steps are as follows:
By day the time period of solar light irradiation abundance, utilize flat-plate solar heat collector to receive the irradiation of sunshine, heat is imported in the primary dewatering ebullated bed that bischofite is housed, make temperature increase to 120 in bed～180 ° C, at this moment MgCl
26H
2O loses the crystallization water and generates low hydrated magnesium chloride MgCl
24H
2O,, realize that solar energy arrives chemical conversion of energy, and will react the water vapour that generates and output to Steam Turbine and generate electricity; When night or solar radiation when inadequate, water vapour is entered have the dehydration ebullated bed of low hydrated magnesium chloride, control temperature at 25～110 ° of C and steam partial pressure 1.013 * 10
2～1.560 * 10
5Under the condition of Pa, make low hydrated magnesium chloride generation hydration reaction, increase hydration number, regenerate MgCl
26H
2O discharges absorption (hydration) heat, realizes chemical energy to the transformation of heat energy, and the heat of release reaches attemperater, produces the generating of water vapour pushing turbine group;
Its chemical reaction process is as follows:
Wherein process (2) is subject to the impact of steam partial pressure and temperature, and when keeping temperature-resistant, steam partial pressure is larger, and the rate of water absorption of magnesium chloride hydrate is faster, and when system temperature raise, it is just larger that required steam partial pressure is carried out in reaction.
2. the method that solar energy is transformed and stores as chemisorbed energy storage working medium with low hydrated magnesium chloride according to claim 1, its concrete operations flow process is as follows:
Time period in the solar light irradiation abundance is carried out energy storage, close stop valve (4), utilize flat-plate solar heat collector (1) to receive the irradiation of sunshine, conduct heat in the primary dewatering ebullated bed (6) that bischofite is housed, make temperature increase to 120 in bed～180 ° C, at this moment MgCl
26H
2O loses the crystallization water and generates low hydrated magnesium chloride (MgCl
24H
2O), open simultaneously stop valve (5), the water vapour that output-response generates realizes that solar energy arrives chemical conversion of energy, the water vapour pushing turbine group that produces can be generated electricity; When inadequate, close stop valve (5) when night or solar radiation, open stop valve (4), make the water vapour in attemperater (2) enter primary dewatering ebullated bed (6), control temperature at 25～110 ° of C and steam partial pressure 1.013 * 10
2～1.560 * 10
5Pa makes low hydrated magnesium chloride generation hydration reaction, increases hydration number, regenerates MgCl
26H
2O, and discharge heat of adsorption, realize chemical energy to the transformation of heat energy, the heat of release reaches pond 3, produces the generating of water vapour pushing turbine group; The area of described flat-plate solar heat collector is 1-20 square metre.
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Cited By (8)
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|---|---|---|---|---|
| CN104650820A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Formula of chemical heat storage material for heat transfer |
| CN106014892A (en) * | 2016-07-13 | 2016-10-12 | 王晓岚 | Sustainable solar power generation process |
| CN107120628A (en) * | 2017-06-06 | 2017-09-01 | 上海海事大学 | A kind of thermal and electric two way system and its application method based on hydrated salt chemical heat accumulation |
| CN108643311A (en) * | 2018-05-29 | 2018-10-12 | 滨州学院 | Adsorptive heat-storage device |
| CN110079280A (en) * | 2019-05-29 | 2019-08-02 | 上海理工大学 | A kind of thermal energy storage material of binary hydrated salt |
| CN110822743A (en) * | 2019-11-20 | 2020-02-21 | 哈尔滨工业大学 | Continuous heat storage system based on photo-thermal moving bed |
| WO2020116167A1 (en) * | 2018-12-07 | 2020-06-11 | 愛知製鋼株式会社 | Solar thermal power generation system |
| CN111425865A (en) * | 2020-05-07 | 2020-07-17 | 孙素晶 | Efficient energy-saving device for garbage disposal |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104650820A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Formula of chemical heat storage material for heat transfer |
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| CN110822743A (en) * | 2019-11-20 | 2020-02-21 | 哈尔滨工业大学 | Continuous heat storage system based on photo-thermal moving bed |
| CN111425865A (en) * | 2020-05-07 | 2020-07-17 | 孙素晶 | Efficient energy-saving device for garbage disposal |
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