CN104846249B - Solar energy heating generating rare-earth and Mg metal hydride high-temperature heat-storage material - Google Patents
Solar energy heating generating rare-earth and Mg metal hydride high-temperature heat-storage material Download PDFInfo
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- CN104846249B CN104846249B CN201510237054.4A CN201510237054A CN104846249B CN 104846249 B CN104846249 B CN 104846249B CN 201510237054 A CN201510237054 A CN 201510237054A CN 104846249 B CN104846249 B CN 104846249B
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Abstract
The present invention provides a kind of solar energy heating generating rare earth magnesium metal hydride high-temperature heat-storage material, it is characterised in that its composition is: (Ce1‑yAy)Mgx, wherein one or both in A=Mn, Ca, Ti, B or two or more composition, 7≤x≤17,0 < y≤0.2.Compared with existing pure magnesium heat accumulating, the novel rare-earth magnesium heat accumulating of the present invention has following premium properties: activity function is significantly improved, and soak time substantially shortens；Inhaling hydrogen dynamic performance the best, hydrogen-absorption speed is fast, and hydrogen desorption kinetics performance is the most excellent, it is ensured that material of the present invention in use can be inhaled the most freely and put hydrogen, reaches the purpose of energy storage；Material of the present invention will be low than existing pure magnesium heat accumulating suction hydrogen platform pressure under synthermal, and at the maximum hydrogen-sucking amount of 400 DEG C close to MgH2Hydrogen-sucking amount, and platform hysteresis quality is little；There is good cyclic reversibility.
Description
Technical field
The present invention relates to solar energy heating generating heat accumulating, be specifically related to a kind of novel rare-earth-magnesium metal
Hydride heat accumulating.
Background technology
Solar energy heating generating is a kind of important clean energy resource, by reflecting mirror by solar light focusing to thermal-arrest
Device, heating heat conduction medium produces high-temperature high-pressure steam with water under high pressure heat exchange, and pushing turbine generates electricity.Solar energy
Thermal-arrest generating is identical with tradition thermal power generation principle, therefore can integrate with conventional thermal power station, and electric power can be straight
Connect grid-connected.In solar energy heating electricity generation system, heat storage is an important ingredient, and it is complete to power station
Weather continuous and stable electric generation, peak load cutting and reduction cost of electricity-generating play an important role.Heat accumulating is
The key of heat reservoir, improve the heat accumulation energy density of heat accumulating and operating temperature for improve generating efficiency and
Reduce cost of electricity-generating to be significant.Heat accumulating is of a great variety, can be generally divided into three major types: sensible heat, latent
Thermally and chemically react heat accumulating.Sensible heat heat accumulation is the thermal capacitance heat accumulation utilizing material itself, store exothermic process simple,
Technology maturation, low cost, but storage density is little, efficiency is low.Fuse salt is representational researching of sensible heat storage material,
There is higher use temperature (300-500 DEG C) and bigger thermal capacity (130kJ/kg).Latent heat heat accumulation is profit
By the heat effect in phase transition process, its storage density is higher, as metallic aluminium has higher latent heat of phase change (400kJ
/ kg) and phase transition temperature (661 DEG C).Chemical reaction heat storage inhales exothermic effect during utilizing reversible chemical, its
Energy storage density is the highest, such as metal-oxide and metal hydride heat reservoir.The wherein heat accumulation of metal hydride
Density, more than 1700-4000kJ/kg, is 10-30 times of fuse salt quantity of heat storage, is the 4-10 of phase-change heat-storage material
Times, there is obvious advantage.It addition, hydrogen bearing alloy suction hydrogen discharge reaction is reversible, can be recycled thousands of times, and
Without side reaction, temperature range is adjustable, non-corrosiveness, security of system, easily operation, equipment cost are relatively low, is reason
The heat-storing material thought.
The heat accumulation principle of metal hydride is to inhale the heat effect put during hydrogen, with hydrogen based on metal or alloy
Reaction discharges substantial amounts of heat during generating metal hydride, and absorbs when decomposition of metal hydrides puts hydrogen
Substantial amounts of heat.In terms of solar energy heating generating high-temperature heat-storage, mainly have studied tri-kinds of gold of Li, Ca, Mg
Belong to hydride.The energy storage density of Li and Ca metal hydride is the highest, is 2900kJ/kg and 4494kJ respectively
/ kg, operating temperature, between 900-1000 DEG C, may be used in the heat reservoir of tower type solar thermal-arrest generating.
The metal hydride of Mg is most widely paid close attention to as heat accumulating, and its main advantage is that storage density is high
(2800kJ/kg), aboundresources low price, safe and reliable, it is most important that its operating temperature is fitted
In will the heat accumulation temperature (400-500 DEG C) of business-like groove type solar heat build-up electricity generation system.Mg Base Metal
The concept that hydride stores heat for solar energy thermal-power-generating was just suggested in the seventies in last century, not only ground
Study carefully the Mg hydrogen storage material key property as thermal energy storage, and develop high-temperature heat accumulation system prototype, and
It is applied in solar heat power generation system.The subject matter that Mg heat accumulating exists is that operating temperature is low,
Platform pressure height, dynamic performance is poor.
Summary of the invention
It is an object of the invention to provide a kind of novel rare-earth and Mg heat accumulating, its operating temperature, plateau pressure
Pure Mg heat accumulating all it is substantially better than with dynamic performance.
A kind of solar energy heating generating rare-earth and Mg metal hydride high-temperature heat-storage material, component atoms ratio is:
(Ce1-yAy)Mgx, wherein one or both in A=Mn, Ca, Ti, B or two or more composition, 7
≤ x≤17,0 < y≤0.2.Operating temperature interval is 250 DEG C-750 DEG C.
The preparation method of described solar energy heating generating rare-earth and Mg metal hydride high-temperature heat-storage material is to use
Prepared by machine-alloying or induction melting, the alloy cooling time-division commonly solidifies, directional solidification and rapid solidification three
The mode of kind.
Use machine-alloying high energy ball mill used when preparing or planetary ball mill, need at argon or helium
Atmosphere is carried out.
Compared with existing pure magnesium heat accumulating, the novel rare-earth of the present invention-magnesium heat accumulating has a following premium properties:
Activity function is significantly improved, and soak time substantially shortens；Inhale hydrogen dynamic performance the best, inhale hydrogen speed
Rate is fast,；Hydrogen desorption kinetics performance is the most excellent, it is ensured that material of the present invention in use can be certain
Under the conditions of freely inhale put hydrogen, reach the purpose of energy storage；Material of the present invention than existing pure magnesium heat accumulating in equality of temperature
Suction hydrogen platform pressure under Du will be low, and at the maximum hydrogen-sucking amount of 400 DEG C close to MgH2Hydrogen-sucking amount, and flat
Platform hysteresis quality is little；There is good cyclic reversibility.
Accompanying drawing illustrates:
Fig. 1 is according to embodiment the two rare-earth and Mg metal hydride high-temperature heat-storage material (Ce0.9Ti0.1)
Mg12(Ce0.8Mn0.2)Mg12Activation curve.
Fig. 2 is according to embodiment the two rare-earth and Mg metal hydride high-temperature heat-storage material (Ce0.9Ti0.1)Mg12
(Ce0.8Mn0.2)Mg12Dynamic isotherms of hydrogen absorption.
Fig. 3 is according to embodiment the two rare-earth and Mg metal hydride high-temperature heat-storage material (Ce0.9Ti0.1)Mg12
(Ce0.8Mn0.2)Mg12Hydrogen desorption kinetics curve.
Fig. 4 is according to rare-earth and Mg metal hydride high-temperature heat-storage material ((Ce a kind of described in embodiment0.9Ti0.1)Mg12
PCT curve.
Fig. 5 is according to embodiment the two rare-earth and Mg metal hydride high-temperature heat-storage material (Ce0.9Ti0.1)Mg12
(Ce0.8Mn0.2)Mg12Circulating and reversible linearity curve.
Detailed description of the invention
The purity preparing the raw material reguline metal used by sample is above 99.8%, prepares two kinds by certain proportioning
Alloy (Ce1-yAy)Mgx(wherein A=Ti, x=12, y=0.1) and (Ce1-mAm)Mgx(wherein A=Mn,
X=12, m=0.2).The alloy made uses the method for machinery powder process to crush, and crosses the sieve of 200 mesh, obtains
The powder of 200 mesh is placed in glove box storage.
Sample must activate before testing.Weighing some grams of powder and put in reactor, after sealing, evacuation is (true
Reciprocal of duty cycle is higher than 10-2Pa), it is then charged with the hydrogen of certain pressure, then evacuation is flushed with hydrogen, 2～3 times repeatedly, with clearly
Wash pipeline.With the heating by electric cooker of precise temperature control and strictly control temperature of reactor, when reaching 400 DEG C, it is filled with one
The pure hydrogen (3～6MPa) of constant-pressure, after inhaling hydrogen after a while, then evacuation, heating, put hydrogen and lead to hydrogen again.
Repeatedly inhale the activation processing putting hydrogen, make material particle size and stable performance and activity be restored.Fig. 1 is two kinds of conjunctions
The activation curve of gold.
Then the Dynamic isotherms of hydrogen absorption of two kinds of alloys is tested.Evacuation after activation, close sample valve and
Low pressure valve, is flushed with hydrogen to desirable pressure；Set sample quality, hydrogen pressure, volume, temperature etc. in test software to join
Number；While opening sample valve, make test software start working, obtain hydrogen-sucking amount versus time curve.
Fig. 2 is the Dynamic isotherms of hydrogen absorption of two kinds of alloys.
Inhale the hydrogen desorption kinetics curve of hydrogen two kinds of alloys of complete test.Hydrogen in sample valve is recorded after suction hydrogen is saturated
Pressure, closes sample valve, puts hydrogen to 0.1MPa (being evacuated to 10～3MPa)；Open sample valve, at certain for the moment
Between some record hydrogen pressure, close sample valve at once；Put rapidly hydrogen to 0.1MPa (being evacuated to 10～3MPa), beat
Drive sample valve, then at future time point record hydrogen pressure；Each step repeats above, and records each time point
Hydrogen pressure；According to each time point hydrogen pressure change calculations hydrogen desorption capacity, draw hydrogen desorption capacity versus time curve.Figure
3 is the hydrogen desorption kinetics curve of two kinds of alloys.
Sample after activation can carry out P-C-T test.At a temperature of Tr, the pressure Pr of record sample jar, closes
Close sample valve, open hydrogen valve and main valve, be pressurized to Pd, open the pressure P ' after sample valve record system balancingr,
The most i.e. complete the measurement of first on PCT curve；When subsequent point is measured, first close sample valve, given system
The P of systemdValue, the above P ' of a bitrValue is the Pr value of this point, opens sample valve, is somebody's turn to do after system balancing
The P ' of pointrValue, the most i.e. can get whole piece PCT curve；The test putting hydrogen process is similar with inhaling hydrogen process.Figure
4 is the PCT curve of one of which alloy.
Take two kinds of alloy powders, activated relief its inhale the most repeatedly and put hydrogen, record and follow every time
The maximum hydrogen-sucking amount of ring, in detection cyclic process, whether alloy powder has the loss of the biggest hydrogen-sucking amount.Circulation is total
Carry out altogether 500 times.Fig. 5 is the circulating and reversible linearity curve of two kinds of alloys.
Claims (1)
1. a solar energy heating generating preparation method for rare-earth and Mg metal hydride high-temperature heat-storage material, its
Being characterised by, its composition is: (Ce1-yAy)Mgx, the wherein one in A=Mn, Ca, Ti, B or two
Plant or two or more composition, 7≤x≤17,0 < y≤0.2；Operating temperature interval is 250 DEG C-750 DEG C；
Concrete employing machine-alloying or induction melting prepare rare-earth and Mg metal hydride high-temperature heat-storage material,
The alloy cooling time-division commonly solidifies, directional solidification and three kinds of modes of rapid solidification；
Use machine-alloying high energy ball mill used when preparing or planetary ball mill, need at argon or helium
Atmosphere is carried out.
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| FR2407169A1 (en) * | 1977-10-27 | 1979-05-25 | Raffinage Cie Francaise | PROCESS FOR PREPARING A HYDROGEN RESERVE AND APPLICATIONS OF THIS PROCESS. |
| CN1170950C (en) * | 2000-05-31 | 2004-10-13 | 南开大学 | Magnesium-base hydrogen storing alloy material |
| CN1212419C (en) * | 2002-04-10 | 2005-07-27 | 浙江大学 | Non-crystal rare-earht-Mg based hydrogen bearing alloy and its preparing process |
| CN1177075C (en) * | 2002-04-10 | 2004-11-24 | 浙江大学 | Non-crystal rare-earth and Mg base hydrogen bearing alloy and its preparing process |
| JP4828986B2 (en) * | 2006-03-30 | 2011-11-30 | 株式会社東芝 | Hydrogen storage alloy, hydrogen storage membrane and hydrogen storage tank |
| CN102392167B (en) * | 2011-11-17 | 2013-03-20 | 上海交通大学 | Magnesium-based hydrogen storage material with added rare earth element and preparation method thereof |
| CN104480363A (en) * | 2014-12-15 | 2015-04-01 | 苏州昊卓新材料有限公司 | Preparation method of high-ductility magnesium alloy |
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