CN109182841A - It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously - Google Patents
It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously Download PDFInfo
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- CN109182841A CN109182841A CN201811333685.6A CN201811333685A CN109182841A CN 109182841 A CN109182841 A CN 109182841A CN 201811333685 A CN201811333685 A CN 201811333685A CN 109182841 A CN109182841 A CN 109182841A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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Abstract
There is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously the invention discloses a kind of.According to weight percent, the ingredient of the alloy are as follows: Bi:4.0-4.5wt.%, In:0.4-0.5wt.%, Be:0.01-0.02wt.%, Pb:3.5-3.8wt.%, Al:18.0-18.5wt.%, Y:0.1-0.2wt.%, Si:2.0-2.2wt.%, B:0.2-0.3wt.%, surplus are zinc.The material provides a kind of based on the materialogy solution for being different from eutectic alloy energy storage, the technical problem that can be faced efficiently against current energy storage field for alloy energy storage field.It can not only make it possible that latent heat treatment on a large scale, can also realize great Social benefit and economic benefit while greatly promoting heat storage capacity.
Description
Technical field
The present invention relates to technical field of alloy, specifically, being related to a kind of kirsite.
Background technique
The various energy can be converted into thermal energy, be stored in the form of heat to be converted into power output when needed
Or it directly uses.Thus, heat accumulation is very important one kind in energy storage.Pass through heat-storage medium during heat accumulation for solar energy
The energy storages such as heat, biomass chemical energy are in heat storage medium.Hair is transferred heat to by heat exchanger when needing to discharge
Motor workmanship, produces electricl energy.It is also possible to need by load, the steam of high temperature is provided for heating.
From the point of view of the development path of heat-storage technology, traditional technology is before centuries with regard to being carried out with media such as water and rocks
Heat accumulation.This technology is known as sensible heat heat accumulation, and feature is that there is no phase transformations at work for heat-storage medium, and heat filling rate is low, nothing
Method meets large-scale energy storage demand.And phase-change thermal storage, that is, phase transition process heat release is utilized, not only storage density is high, but also
Heat release temperature controls in narrow range, conducive to the control of heat source temperature.Either sensible heat heat accumulation or latent heat heat accumulation,
All there is boundless application prospect in industry and civil field.Phase-change thermal storage technology can effectively solve energy resource supply in the time
Discontinuous problem spatially is the effective way river for improving efficiency of energy utilization.In solar energy, electric power and industrial exhaust heat
Time to peak section is adequately stored thermal energy, for industry, the demand in civil and military field.It can be used for solving thermal energy
The contradiction of supply and demand mismatch is the important technology for improving efficiency of energy utilization and protecting environment.
Phase-change thermal storage can be divided into solid-solid, the phase-change thermal storage of solid-liquid and solid-gas three types.Although being related to gaseous phase
It is very big to become heat collecting system latent heat of phase change, but inevitably along with the generation of bulk gas in phase transition process, thus to molten
The volume of body and pressure-resistant performance requirement are high.So the heat accumulating of solid-gas class hardly results in extensively during actual heat accumulation
Use, and the heat accumulating of solid-solid and solid-liquid is ideal selection scheme.Simultaneously in view of solid-solid phase-change energy-storage material
Latent heat of phase change is smaller, and the heat storage efficiency of unit volume is low, thus most commonly used in engineer application is solid-liquid type
Phase-change heat-storage material.
Solid-liquid phase change energy storage material is divided into low temperature, in mild high-temperature phase-change heat storage material.Wherein, temperature is lower than 80 degree
The fields such as building energy conservation and solar water heating system belong to low temperature phase change heat accumulation.Temperature is higher than 300 degree of solar energy thermal-power-generating system
System, the demand of high-temperature residual heat recovery system etc. make high-temperature phase-change heat storage material belong to high-temperature phase-change heat storage type.Temperature between
The research of medium temperature phase-change heat-storage material between 80-300 degree and applying compares less, and relevant material and industrialization are also
The most popular direction of industrial circle at present.
Heat absorption when using alloy melting carries out the stored energy application that heat accumulation belongs to solid-liquid type, but heat accumulation alloy
Research and application start from the 1980s.The heat accumulation alloy developed at present is mainly aluminium alloy, and the material thermal conductivity it is big,
Thermostabilization is preferably, phase transformation volume change is small, storage density is larger, is a kind of preferable high-temperature metal base phase change heat storage material.This
Outside, magnesium-based energy storage material has also obtained faster development due to having excellent chemical compatibility with iron pipe in recent years.These phase transformations
The design concept of material is to seek the alloy of eutectic composition, and suction is controlled using the constancy of eutectic point alloy graining temperature
Heat-exothermic temperature spot, so that energy storage can be carried out in lesser temperature section.This thinking is also embodied in have been obtained at present
Widely applied aluminium base, on the alloy systems such as magnesium-based.
As increasingly maturation, the application value of hot energy storage of hot generation technology also will further show.According to it is current into
Exhibition estimation, arrives the year two thousand twenty bottom, and the installation scale of China's fuse salt heat accumulation will be expected to reach 1.8 gigawatts, and large-scale application will be general
All over realization.The problems such as future, China's renewable energy power generation installation specific gravity will increasingly increase, and renewable energy power generation fluctuation is big
Also it will be further exacerbated by.This patent is exactly the constraint in order to get rid of current energy storage alloy design concept, provides a kind of be different from altogether
The materialogy solution of peritectic alloy.Namely propose it is a kind of carried out using liquid phase spinodal decomposition effect sensible heat and latent heat storage
The efficient solutions of heat.The implementation and industrialization of the material can not only improve the energy storage density of alloy on a large scale, also must
Great social effect and economic benefits will be obtained.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of while having sensible heat and latent heat heat accumulation 200-
300 degree are used kirsite.
To achieve the goals above, the present invention adopts the following technical scheme:
It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously.By weight percentage, the group of alloy becomes
Bi:4.0-4.5wt.%,In:0.4-0.5wt.%,Be:0.01-0.02wt.%,Pb:3.5-3.8wt.%,Al:18.0-
18.5wt.%, Y:0.1-0.2wt.%, Si:2.0-2.2wt.%, B:0.2-0.3wt.%, surplus are zinc.
Above-mentioned one kind has sensible heat and latent heat heat accumulation 200-300 degree kirsite, the including (protection of following smelting step simultaneously
Under the conditions of): the melting in crucible electrical resistance furnace by the raw material as above matched, wherein active element is added in the form of intermediate alloy;
It is protected in fusion process using graphite crucible and argon gas；Crucible forms alloy melt after being heated to 500-600 degree, and utilizes electromagnetism
Agitation effects are sufficiently stirred 15 minutes or so;Alloy melt is cast to after 400 degree of heat preservations stand 15 minutes waterglass or
Casting and forming is carried out in graphite jig.
Compared with prior art, the invention has the following beneficial effects:
(1) sensible heat and latent heat are two different energy storage modes, and wherein sensible heat is absorbed in the case where the state of phase is constant
Heat, and latent heat is the release of the heat due to caused by phase transformation.Traditional energy storage alloy design concept is limited to eutectic alloy, thus
The release of latent heat is completed near eutectic temperature.With the rapid progress of process of industrialization, the effect of existing energy-storage system
Rate and capacity are no longer satisfied existing challenging needs.Meanwhile demand of the people to the high-grade energy it is increasing this
Status is but also a kind of latent heat heat accumulation scheme different from eutectic point is badly in need of in heat accumulation field.This patent be for this purpose and
One kind of proposition carries out the materialogy of heat accumulation alloy design based on Two Liquid Phases (namely utilizing the spinodal decomposition effect of liquid phase)
Solution.
(2) design principle that this patent is illustrated using Fig. 1 and Fig. 2, using multi-element alloy system.It now sketches such as
Under:
(A) traditional heat accumulation alloy was as shown in Figure 1, exothermic during being multi-element eutectic alloy graining process facies evolution and being somebody's turn to do show
It is intended to.?Temperature range alloy is complete liquid phase,Temperature range is complete solid phase, in T*It is total to when temperature
Crystalline substance transformation.Thus existWithTemperature range, alloy is that energy storage is carried out in a manner of sensible heat, and in T*Temperature alloy is with latent
Hot mode carries out energy storage.Since the energy that latent heat is released is greater than the energy that sensible heat is released, in T in exotherm in Fig. 1*Nearby go out
Existing peak value；
(B) the novel heat accumulation alloy that this patent proposes is as shown in Fig. 2, be to have the multicomponent alloy of liquid phase spinodal decomposition type feature solidifying
Gu process facies evolution and exothermic schematic diagram during this.?Temperature range alloy is the completely mutual mutual solvent of liquid (liq),
?Temperature range alloy has occurred spinodal decomposition and generates two kinds of liquid phases (liq1 and liq2),Two kinds of liquid of temperature range
Phase (liq1 and liq2) is solidified respectively,For the temperature range solidified completely.In T*Multicomponent alloy has occurred when temperature
Constant reaction (temperature is constant).Thus existWithArea, alloy are that energy storage is carried out in a manner of sensible heat,WithArea
Alloy carries out energy storage with latent heat and sensible heat two ways, in T*Temperature alloy carries out energy storage in a manner of latent heat.Since latent heat is put
Energy out is greater than the energy that sensible heat is released, thus exotherm exists in Fig. 2WithThere is wide in range heat release in temperature range
Peak value；
Comparison diagram 1 and Fig. 2 can be seen that the exothermic peak temperature section of eutectic alloy is narrow, and only narrow near eutectic temperature
The heat release in a manner of latent heat of narrow temperature section, and the liquid phase spinodal decomposition type alloy exothermic peak temperature section that this patent proposes is wide
It is general, andWithLarge-scale heat release is carried out continuously in such a way that latent heat and sensible heat discharge simultaneously in entire temperature range.
Thus the design concept of this patent is while expanding the temperature range that heat is discharged in a manner of latent heat, but also alloy energy storage is imitated
Rate has great increase.
(3) alloy melt inevitably occurs oxidation after ingress of air and changes alloying component, not only causes phase
The change of temperature can also cause the decaying of latent heat of phase change.The ability for measuring alloy melt resistance to oxidation can use surface film oxide
Consistency measure, be defined as (oxide volume/metal volume).For traditional kirsite melt, the skin covering of the surface
Consistency is 0.78, thus kirsite does not have good oxidation resistent susceptibility.The novel energy-storing kirsite of present patent application protection,
It is 1.20-1.25 that its surface, which forms protective film consistency,.The skin covering of the surface also has low surface tension, can be in the blown state
Completely in alloy melt surface spreading, play the role of completely cutting off external oxygen.In addition, the skin covering of the surface can also prevent melt
The high component of middle vapour pressure makes alloying component change because of the reason of volatilizing.In the actual engineering construction, when the storage
After thermalloy is packaged into thermal storage container and pipeline, even if welding portion has the gap, also due to bath surface film is excellent
Inhibiting effect and play a protective role to melt, the projected life of heat accumulation facility will not be made to have apparent change.
(4) spinodal decomposition can occur in the liquid state for the energy storage alloy, and temperature range is 279-290 degree, and the process
Sensible heat and latent heat of phase change are 20-25kJ/kg altogether.In addition, two kinds of liquid phases of spinodal decomposition can occur respectively in 260-279 degree
Solidification, and the sensible heat of the process and latent heat are 120-130 kJ/kg altogether.Thus in entire phase transition process (260-290 degree), close
The heat of gold in total is released to 140-155 kJ/kg.And the latent heat of traditional cocrystallizing type kirsite is generally the left side 100-110 kJ/kg
It is right.During carrying out phase-change thermal storage release in a manner of latent heat and sensible heat simultaneously due to the alloy, entire heat is substantially increased
Heat burst size and operating temperature section in cyclic process.In addition, the material has extraordinary thermal cycle effect, passing through
1000 times from the cyclic process of 260-290 degree, the phase transition temperature interval of the material improves 0.8-1.0 degree, and entire temperature
The heat release in degree section reduces 0.4-0.5%.Thus, which will not store up after for heat accumulation facility staff 5 years
Energy material has apparent performance degradation phenomenon.
Detailed description of the invention
Fig. 1 is facies evolution and heat release schematic diagram in multi-element eutectic alloy graining process.Wherein T is temperature, T*For the body
The eutectic temperature of system, H are the enthalpy of system, and Q indicates the heat that temperature-fall period is released.
Fig. 2 is facies evolution and heat release schematic diagram in Multiple liquid phase spinodal decomposition type alloy graining process.Wherein liq1 and
Liq2 is two kinds of liquid phase ingredients after liq spinodal decomposition, T*For the not temperature of the system.
Specific embodiment
Embodiment 1
It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously.By weight percentage, the group of alloy becomes
Bi:4.0wt.%,In:0.4wt.%,Be:0.01wt.%,Pb:3.5wt.%,Al:18.0wt.%,Y:0.1wt.%,Si:
2.0wt.%, B:0.2wt.%, surplus are zinc.Above-mentioned one kind has sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously, wraps
Include following smelting step (under protective condition): the melting in crucible electrical resistance furnace by the raw material as above matched, wherein active element with
The form of intermediate alloy is added;It is protected in fusion process using graphite crucible and argon gas；Crucible is formed after being heated to 500-600 degree
Alloy melt, and be sufficiently stirred 15 minutes or so using electromagnetic agitation effect;Alloy melt is stood 15 minutes in 400 degree of heat preservations
After be cast in waterglass or graphite jig and carry out casting and forming.
The alloy melt surface can be generated one layer of fine and close protective film and play the role of completely cutting off external oxygen.The energy storage
Spinodal decomposition can occur in the liquid state for alloy, and temperature range is 281-285 degree, and the sensible heat of the process and latent heat of phase change are altogether
21kJ/kg.In addition, two kinds of liquid phases of spinodal decomposition can solidify respectively in 265-281 degree, and the sensible heat of the process and
Latent heat is 124 kJ/kg altogether.Thus in entire phase transition process (265-285 degree), the heat of alloy in total is released to 145 kJ/
kg.And the latent heat of traditional cocrystallizing type kirsite is generally 100-110 kJ/kg or so.In addition, the material has extraordinary heat
Ringing have passed through 1000 times from the cyclic process of 265-285 degree, and the phase transition temperature interval of the material improves 0.8
Degree, and the heat release of entire temperature range reduces 0.5%.Thus, the alloy for after heat accumulation facility staff 5 years not yet
Energy storage material, which can be gone out, apparent performance degradation phenomenon.
Embodiment 2
It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously.By weight percentage, the group of alloy becomes
Bi:4.5wt.%,In:0.5wt.%,Be:0.02wt.%,Pb:3.8wt.%,Al:18.5wt.%,Y:0.2wt.%,Si:
2.2wt.%, B:0.3wt.%, surplus are zinc.Above-mentioned one kind has sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously, wraps
Include following smelting step (under protective condition): the melting in crucible electrical resistance furnace by the raw material as above matched, wherein active element with
The form of intermediate alloy is added;It is protected in fusion process using graphite crucible and argon gas；Crucible is formed after being heated to 500-600 degree
Alloy melt, and be sufficiently stirred 15 minutes or so using electromagnetic agitation effect;Alloy melt is stood 15 minutes in 400 degree of heat preservations
After be cast in waterglass or graphite jig and carry out casting and forming.
The alloy melt surface can be generated one layer of fine and close protective film and play the role of completely cutting off external oxygen.The energy storage
Spinodal decomposition can occur in the liquid state for alloy, and temperature range is 284-290 degree, and the sensible heat of the process and latent heat of phase change are altogether
24kJ/kg.In addition, two kinds of liquid phases of spinodal decomposition can solidify respectively in 262-284 degree, and the sensible heat of the process and
Latent heat is 128kJ/kg altogether.Thus in entire phase transition process (262-290 degree), the heat of alloy in total is released to 152kJ/
kg.And the latent heat of traditional cocrystallizing type kirsite is generally 100-110 kJ/kg or so.In addition, the material has extraordinary heat
Ringing have passed through 1000 times from the cyclic process of 262-290 degree, and the phase transition temperature interval of the material improves 0.9
Degree, and the heat release of entire temperature range reduces 0.4%.Thus, the alloy for after heat accumulation facility staff 5 years not yet
Energy storage material, which can be gone out, apparent performance degradation phenomenon.
Embodiment 3
It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously.By weight percentage, the group of alloy becomes
Bi:4.2wt.%,In:0.4wt.%,Be:0.01wt.%,Pb:3.6wt.%,Al:18.2wt.%,Y:0.1wt.%,Si:
2.1wt.%, B:0.2wt.%, surplus are zinc.Above-mentioned one kind has sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously, wraps
Include following smelting step (under protective condition): the melting in crucible electrical resistance furnace by the raw material as above matched, wherein active element with
The form of intermediate alloy is added;It is protected in fusion process using graphite crucible and argon gas；Crucible is formed after being heated to 500-600 degree
Alloy melt, and be sufficiently stirred 15 minutes or so using electromagnetic agitation effect;Alloy melt is stood 15 minutes in 400 degree of heat preservations
After be cast in waterglass or graphite jig and carry out casting and forming.
The alloy melt surface can be generated one layer of fine and close protective film and play the role of completely cutting off external oxygen.The energy storage
Spinodal decomposition can occur in the liquid state for alloy, and temperature range is 279-285 degree, and the sensible heat of the process and latent heat of phase change are altogether
21kJ/kg.In addition, two kinds of liquid phases of spinodal decomposition can solidify respectively in 268-279 degree, and the sensible heat of the process and
Latent heat is 125kJ/kg altogether.Thus in entire phase transition process (268-285 degree), the heat of alloy in total is released to 146 kJ/
kg.And the latent heat of traditional cocrystallizing type kirsite is generally 100-110 kJ/kg or so.In addition, the material has extraordinary heat
Ringing have passed through 1000 times from the cyclic process of 268-285 degree, and the phase transition temperature interval of the material improves 0.8
Degree, and the heat release of entire temperature range reduces 0.4%.Thus, the alloy for after heat accumulation facility staff 5 years not yet
Energy storage material, which can be gone out, apparent performance degradation phenomenon.
Claims (2)
1. a kind of have sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously；According to weight percent, the ingredient of the alloy
Are as follows: Bi:4.0-4.5wt.%, In:0.4-0.5wt.%, Be:0.01-0.02wt.%, Pb:3.5-3.8wt.%, Al:18.0-
18.5wt.%,Y:0.1-
0.2wt.%, Si:2.0-2.2wt.%, B:0.2-0.3wt.%, surplus are zinc.
2. a kind of according to claim 1 have sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously, it is characterised in that
Including following smelting step (under protective condition): the melting in crucible electrical resistance furnace by the raw material as above matched, wherein active element
It is added in the form of intermediate alloy;It is protected in fusion process using graphite crucible and argon gas；Crucible is heated to shape after 500-600 degree
It is sufficiently stirred 15 minutes or so at alloy melt, and using electromagnetic agitation effect;Alloy melt is stood 15 points in 400 degree of heat preservations
It is cast to after clock in waterglass or graphite jig and carries out casting and forming.
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| CN201811333685.6A CN109182841A (en) | 2018-11-09 | 2018-11-09 | It is a kind of that there is sensible heat and latent heat heat accumulation 200-300 degree kirsite simultaneously |
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| CN103243236A (en) * | 2013-04-22 | 2013-08-14 | 江苏新亚特钢锻造有限公司 | High-toughness wear-resistant zinc alloy containing fine crystalline grains and preparation process for same |
| KR20130121295A (en) * | 2012-04-27 | 2013-11-06 | 김석환 | Zink-magnesium alloy with improved hardness and tensile strength |
| CN106399755A (en) * | 2016-12-12 | 2017-02-15 | 福州大学 | Environmental-friendly zinc-aluminum damping alloy and preparation method thereof |
| CN107164655A (en) * | 2017-06-02 | 2017-09-15 | 成都莱达机械电子有限公司 | A kind of Zn-base alloy for being used to manufacture multi-stage pressure reducers valve body |
| CN108330324A (en) * | 2018-05-21 | 2018-07-27 | 广州宇智科技有限公司 | New zinc magnesium-based galvanizing by dipping spends Mg-In-Ni kirsites with no zinc |
| CN108396198A (en) * | 2018-06-12 | 2018-08-14 | 广州宇智科技有限公司 | No zinc spends rub resistance K-S-B allumens used for hot dip galvanizing and processing technology |
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2018
- 2018-11-09 CN CN201811333685.6A patent/CN109182841A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130121295A (en) * | 2012-04-27 | 2013-11-06 | 김석환 | Zink-magnesium alloy with improved hardness and tensile strength |
| CN103243236A (en) * | 2013-04-22 | 2013-08-14 | 江苏新亚特钢锻造有限公司 | High-toughness wear-resistant zinc alloy containing fine crystalline grains and preparation process for same |
| CN106399755A (en) * | 2016-12-12 | 2017-02-15 | 福州大学 | Environmental-friendly zinc-aluminum damping alloy and preparation method thereof |
| CN107164655A (en) * | 2017-06-02 | 2017-09-15 | 成都莱达机械电子有限公司 | A kind of Zn-base alloy for being used to manufacture multi-stage pressure reducers valve body |
| CN108330324A (en) * | 2018-05-21 | 2018-07-27 | 广州宇智科技有限公司 | New zinc magnesium-based galvanizing by dipping spends Mg-In-Ni kirsites with no zinc |
| CN108396198A (en) * | 2018-06-12 | 2018-08-14 | 广州宇智科技有限公司 | No zinc spends rub resistance K-S-B allumens used for hot dip galvanizing and processing technology |
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