CN104610927A - Low-melting-point mixed fused salt heat storage and heat transfer material and preparation method thereof - Google Patents
Low-melting-point mixed fused salt heat storage and heat transfer material and preparation method thereof Download PDFInfo
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- CN104610927A CN104610927A CN201510056440.3A CN201510056440A CN104610927A CN 104610927 A CN104610927 A CN 104610927A CN 201510056440 A CN201510056440 A CN 201510056440A CN 104610927 A CN104610927 A CN 104610927A
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
Abstract
The invention discloses a low-melting-point mixed fused salt heat storage and heat transfer material and belongs to the technical field of physical heat transfer and energy storage. The components and content of the low-melting-point mixed fused salt heat storage and heat transfer material are as follows: 6-10wt% of NaNO3, 30-47wt% of KNO3, 3-10wt% of NaCl and 37-61wt% of Ca(NO3)2; Ca(NO3)2 can be replaced with LiNo3 or LiNo3 is added at the same time; 5-10wt% of any one of Li2SO4, Na2SO4 and K2SO4 can further be added, so as to obtain the fused salt mixed with a plurality of components. The invention further provides a preparation method of the low-melting-point mixed fused salt heat storage and heat transfer material. The melting point of the mixed fused salt disclosed by the invention is about 80-115 DEG C, the melting point is about 105-140 DEG C lower than that of Solar Salt, and the thermal decomposition temperature reaches 562-595 DEG C. The preparation process of the fused salt is simple, the working temperature range is wide, and the volatilization of components is reduced under long-time operation, so the fused salt is an excellent low-melting-point mixed fused salt heat storage and heat transfer material.
Description
Technical field
The present invention relates to physics heat transfer technical field of energy storage, particularly a kind of low melting point fused salt mixt heat accumulation heat-transfer matcrial and preparation method thereof.
Background technology
The energy shortage of our times various countries, energy problem rises to strategic issue.Sun power is one of renewable energy source of most economical most environmental protection.Extensive focus utilization sun power mainly solar energy generation technology.
Current solar electrical energy generation mainly contains two kinds of modes: photovoltaic generation and photo-thermal power generation.Photovoltaic generation utilizes solar panel directly sunlight to be converted to voltage and current, but it is comparatively large by lighting conditions, is especially subject to the restriction of cloudy day, night and sleety weather.And photo-thermal power generation utilizes huge sun glasses luminous energy to be converged at any to change heat energy into, very high temperature is produced with huge heat energy at this point, again with heat-transfer matcrial by the thermal energy conduction of this point out, then produce the water vapor of High Temperature High Pressure through vapour generator, water vapor pushing turbine generates electricity.
Photo-thermal power generation equipment de-sign is configured with heat storage units, is filled with heat accumulating in heat storage units, so as by daytime abundance solar energy store, then in the time of night, cloudy day and sleet, continue generating.Therefore photo-thermal power generation technology is the main flow of the extensive power generation applications of sun power from now on.Technical study through decades accumulates, and the cost of photo-thermal power generation reduces greatly in recent years, and developed country generates electricity by way of merging two or more grid systems as the U.S., Spain etc. have successfully realized large-scale commercial photo-thermal, and China has also built a collection of experimental photo-thermal power generation power station.
In order to reduce costs, heat accumulating and the heat-transfer matcrial of the application of photo-thermal power generation factory generally adopt commaterial.Heat accumulation heat transfer technology is one of three large core technologies of solar light-heat power-generation factory, and its cost generally accounts for 1/3rd of gross investment.Solar energy power plant adopts sensible heat mode heat energy storage, namely by the heating and cooling heat energy storage of heat accumulating.When the specific heat capacity of heat accumulating and quality certain, the variation range of material temperature is larger, and its heat energy stored is also more, and this just requires that the heat decomposition temperature of heat accumulating is more high better.The heat decomposition temperature of material is higher, and the temperature range of its application is wider, and particularly for solar energy thermal-power-generating station, the heat decomposition temperature of heat accumulating determines the temperature of the water vapour of generation, and the temperature of water vapour directly has influence on the generating efficiency of steam turbine.
Thermal Power Engineering, especially solar energy thermal-power-generating factory need the heat accumulation heat-transfer fluid of broad operating temperature range.The fused salt heat accumulation heat-transfer matcrial of commercial applications common is at present Solar salt (60wtwt%NaNO
3+ 40wtwt%KNO
3) fused salt mixt system, its use temperature scope is: 220-600 DEG C.Its shortcoming is that fusing point is relatively too high, thus in use easily solidifies and blocking pipe causes danger.If prevent thisly to solidify danger, just need additionally to lay a large amount of temperature-sensing probe and electrically heated utility appliance, cause the maintenance operation expense in construction costs and later stage significantly to rise.Excellent fused salt heat accumulation heat-transfer matcrial needs to have very wide maintenance and stablizes liquid operating temperature range, desirable heat accumulation heat-transfer matcrial should keep stable liquid state and not decompose within the scope of room temperature to 600 DEG C, if temperature is more than 600 DEG C, water vapor starts to become unstable, and the corrodibility of steel pipeline is strengthened, the more important thing is that fused salt also can significantly increase the corrodibility of steel pipeline.In addition, in Industrial processes, often will preheat reaction member or be shifted in time by unnecessary heat, this also needs heat accumulation heat-transfer fluid.Therefore, have the heat accumulation heat-transfer matcrial of the wider operating temperature range of more low melting point in the urgent need to development of new, this is significant and practical value industrially.
At present, progressively develop both at home and abroad to the development research of fused salt mixt, domestic technique level and research also need to deepen continuously, to catch up with foreign level.Grandson Lee's equality is for finding ternary system NaCl – KCl – MgCl
2minimum fusing point done the experiment of more than 36 times; Wang Taowei finds ternary system Li
2cO
3– Na
2cO
3– K
2cO
3minimum fusing point done the experiment of more than 36 times; Raade etc. are for obtaining LiNO
3– NaNO
3– KNO
3– CsNO
3– Ca (NO
3)
2the eutectic point of Quinary system tests more than 5000 part of surprising molten salt sample.As can be seen here, adopt traditional repeatedly parallel laboratory test method to find heat accumulation heat-transfer matcrial and incite somebody to action very time and effort consuming, its efficiency is very low, if select suitable thermodynamical model and its phasor of theoretical prediction, its minimum fusing point and corresponding composition is found according to phasor, carry out experimental verification to this composition point again to test its real fusing point or combination and predict the outcome to do and verify and screen on a small quantity, this will save a lot of medicine and time.
In addition, because carbonate is relative all very high with single salt of fluorochemical and the fusing point of mixture, muriatic corrodibility is very large, thus current international mainstream technology utilizes mixed nitrate melting salt system heat accumulation to conduct heat, this is because nitric acid fused salt has, specific heat capacity is large, high thermal conductivity, high energy storage density, suitable density, the advantage such as low viscosity and low-steam pressure.But also there is the defects such as fusing point is high, thermostability general, use operating temperature range narrow in current available fused salt formula, cannot meet the high demand of photo-thermal power generation technology, other Thermal Power Engineering actual productions.
Summary of the invention
For above-mentioned deficiency, the object of the invention is to, a series of low melting point fused salt mixt heat accumulation heat-transfer matcrials providing low melting point, high thermal stability, operating temperature range wide and preparation method thereof.
The present invention for the adopted technical scheme that achieves the above object is:
A kind of low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is characterized in that, it is made up of the component of following mass percent: comprise 6-10wt%NaNO
3, 30-47wt%KNO
3, 3-10wt%NaCl, 37-61wt%Ca (NO
3)
2.
A kind of low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is characterized in that, it is made up of the component of following mass percent: 14-25wt%NaNO
3, 50-55wt%KNO
3, 3-8wt%NaCl, 22-25wt%LiNO
3.
A kind of low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is characterized in that, it is made up of the component of following mass percent: 6-10wt%NaNO
3, 48-54wt%KNO
3, 3-8wt%NaCl, 3-9wt%LiNO
3, 28-35wt%Ca (NO
3)
2.
Further, aforementioned low melting point fused salt mixt heat accumulation heat-transfer matcrial, can also be added with 5-10wt%Li
2sO
4, Na
2sO
4or K
2sO
4in any one.
Further, a kind of aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 20wt%NaNO
3, 50wt%KNO
3, 5wt%NaCl, 25wt%LiNO
3.
Further, a kind of aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 10wt%NaNO
3, 30wt%KNO
3, 8wt%NaCl, 52wt%Ca (NO
3)
2.
Further, a kind of aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 7wt%NaNO
3, 50wt%KNO
3, 3wt%NaCl, 9wt%LiNO
3, 31wt%Ca (NO
3)
2.
Further, a kind of aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 15wt%NaNO
3, 50wt%KNO
3, 4wt%NaCl, 23wt%LiNO
3, 8wt%Na
2sO
4.
Further, a kind of aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 6wt%NaNO
3, 50wt%KNO
3, 6wt%NaCl, 3wt%LiNO
3, 30wt%Ca (NO
3)
2, 5wt%Na
2sO
4.
A preparation method for aforesaid low melting point fused salt mixt heat accumulation heat-transfer matcrial, is characterized in that, comprise the steps:
(1) anhydrous single salt is prepared:
By NaNO
3, KNO
3, NaNO
2, KNO
2, Na
2sO
4grind to form 50-200 object fine particle in advance with NaCl, in 120 DEG C of prebakes 12 hours in Electric heat oven, then be warmed up to 200 DEG C of oven dry 12 hours, put into loft drier for subsequent use;
By its LiNO
3with Ca (NO
3)
2grind to form 50-200 object fine particle in advance, in Electric heat oven in 80 DEG C of prebakes 12 hours to slough the crystal water that may contain, then be warmed up to 130 DEG C and dry 12 hours; By the LiNO after process
3loft drier is put into for subsequent use after drying 12 hours at 220 DEG C, and the Ca (NO after process
3)
2loft drier is put into for subsequent use after drying 12 hours at 250 DEG C;
(2) low melting point fused salt mixt heat accumulation heat-transfer matcrial is prepared:
The anhydrous single salt of step (1) prepared is mixed according to each formula, well-type electric furnace is put into after mechanical stirring is even, make fused salt mixt premelt 2 hours at 200 DEG C, then at fused salt being warmed up to 300 DEG C, mechanical stirring 30 minutes, pulverize after cooling and grind to form 50-200 object fine powder, be kept in loft drier, be heat accumulation heat-transfer medium material.
Compared with prior art, tool has the following advantages in the present invention:
1, the fused salt mixt product prepared of technical scheme of the present invention, its fusing point is about 80-115 DEG C, relative to Solar Salt, its fusing point reduces nearly 105-140 DEG C, and its heat decomposition temperature reaches 562-595 DEG C, and comparing its fusing point of existing fused salt mixt has reduction in various degree, significantly reduce the cost of total system, improve the security of system, stability, obtain wider operating temperature range, improve generating efficiency;
2, the component of fused salt mixt provided by the invention in use can not volatilize, not adhere to wall etc., and effectively can reduce under the longer operating time and reduce the loss of component, production cost is low, and good economy performance, is better than the formula of existing fused salt; The corrodibility of formulation product of the present invention to equipment significantly reduces;
3, preparation method's rational technology of the present invention, preparation process are simple, cost is low, can be mass-produced, product of the present invention can be applicable in solar heat power generation system, can also be applied in other Industrial processes that often will preheat reaction member or be shifted in time by unnecessary heat;
4, test result of the present invention is accurate, experimentation accurate, effectively saves experimental drug, provides cost savings, obtain best optimized fused salt formula.
Above-mentioned is the general introduction of invention technical scheme, and below in conjunction with accompanying drawing and embodiment, the present invention will be further described.
Accompanying drawing explanation
Fig. 1 is the DSC graphic representation of low melting point fused salt mixt heat accumulation heat-transfer matcrial;
(mass ratio is 20wt%NaNO
3+ 50wt%KNO
3+ 5wt%NaCl+25wt%LiNO
3)
Fig. 2 is the TG graphic representation of low melting point fused salt mixt heat accumulation heat-transfer matcrial;
(mass ratio is 20wt%NaNO
3+ 50wt%KNO
3+ 5wt%NaCl+25wt%LiNO
3)
Fig. 3 is the DSC graphic representation of low melting point fused salt mixt heat accumulation heat-transfer matcrial;
(mass ratio is 10wt%NaNO
3+ 30wt%KNO
3+ 8wt%NaCl+52wt%Ca (NO
3)
2)
Fig. 4 is the DSC graphic representation of low melting point fused salt mixt heat accumulation heat-transfer matcrial;
(mass ratio is 7wt%NaNO
3+ 50wt%KNO
3+ 3wt%NaCl+9wt%LiNO
3+ 31wt%Ca (NO
3)
2)
Fig. 5 is the TG graphic representation of low melting point fused salt mixt heat accumulation heat-transfer matcrial.
(mass ratio is 7wt%NaNO
3+ 50wt%KNO
3+ 3wt%NaCl+9wt%LiNO
3+ 31wt%Ca (NO
3)
2)
Embodiment
The invention provides a series of low melting point fused salt mixt heat accumulation heat-transfer matcrial, it is made up of the component of following mass percent: 6-10wt%NaNO
3, 30-47wt%KNO
3, 3-10wt%NaCl, 37-61wt%Ca (NO
3)
2; Or 14-25wt%NaNO
3, 50-55wt%KNO
3, 3-8wt%NaCl, 22-25wt%LiNO
3; Or 6-10wt%NaNO
3, 48-54wt%KNO
3, 3-8wt%NaCl, 3-9wt%LiNO
3, 28-35wt%Ca (NO
3)
2; On the basis of aforementioned three kinds of formulas, 5-10wt%Na can also be added further
2sO
4, K
2sO
4or Li
2sO
4in any one, and then obtain multiple low melting point fused salt mixt heat accumulation heat-transfer matcrial.
After tested, the fusing point of this low melting point fused salt mixt heat accumulation heat-transfer matcrial is about 80-115 DEG C, and heat decomposition temperature is 562-595 DEG C.
Serial low melting point fused salt mixt heat accumulation heat-transfer matcrial of the present invention is prepared according to the mass ratio of aforementioned setting, and concrete preparation method is:
(1) anhydrous single salt is prepared: by NaNO
3, KNO
3, NaNO
2, KNO
2, Na
2sO
4grind to form 50-200 object fine particle in advance with NaCl, in 120 DEG C of prebakes 12 hours in Electric heat oven, then be warmed up to 200 DEG C of oven dry 12 hours, put into loft drier for subsequent use; By its LiNO
3with Ca (NO
3)
2grind to form 50-200 object fine particle in advance, in Electric heat oven in 80 DEG C of prebakes 12 hours to slough the crystal water that may contain, then be warmed up to 130 DEG C and dry 12 hours; By the LiNO after process
3loft drier is put into for subsequent use after drying 12 hours at 220 DEG C, and the Ca (NO after process
3)
2loft drier is put into for subsequent use after drying 12 hours at 250 DEG C;
(2) low melting point fused salt mixt heat accumulation heat-transfer matcrial is prepared: mixed according to each formula by the anhydrous single salt of step (1) prepared, mechanical stirring is even, make fused salt mixt premelt 2 hours at 200 DEG C, then at fused salt being warmed up to 300 DEG C, mechanical stirring 30 minutes, pulverize after cooling and grind to form 50-200 object fine powder, be kept in loft drier, be heat accumulation heat-transfer medium material.
The LiNO that the present invention uses
3, NaNO
3, KNO
3, Ca (NO
3)
24H
2o, NaNO
2be the pure medicine of commercially available general analysis with NaCl, purify without the need to recrystallization during use; Due to NaNO
3, KNO
3, NaNO
2place with the single salt normal temperature of NaCl etc. 4 kinds and absorb water hardly in atmosphere, use after can drying at 120 DEG C; The water absorbability of anhydrous nitric acid lithium and anhydrous nitric acid calcium is very strong, and anhydrous nitric acid lithium has commodity salt to sell, but it is easy to absorption steam aloft and forms bulk, should grind oven dry before using; And anhydrous nitric acid calcium seldom has commodity selling, common is the Ca (NO being with crystal water
3)
24H
2o, use last as point 2 step drying and dewaterings, first dry 12 hours lesser temps 80 DEG C, then dry 12 hours at 250 DEG C; According to the weight of the weighted each single salt of formula rate, ground and mixed is even, generally melting and heat preservation several hours at high temperature 300 DEG C, to make it mix, use mechanical stirring 30 minutes, Blending Efficiency of Blending is better.
The present invention adopts the low melting point fused salt mixt heat accumulation heat-transfer matcrial of different components and proportioning gained, and its fusing point and heat decomposition temperature measure in the following manner:
1) fusing point test: the mensuration of fusing point can adopt temperature-rising method and cool-down method, according to existing bibliographical information and in conjunction with test of many times experience, find to use temperature-rising method to measure the fusing point of fused salt, the data of acquisition are more accurate.Conventional warm-down method and cooling curve method all inevitably run into molten salt system surfusion, and surfusion directly causes the melting point data that observes on the low side, general several degrees Celsius even tens degrees Celsius on the low side, and the melting point data that the measuring technology that heats up obtains is very accurate.The data acquisition of the present invention fusing point of Diamond Differential Scanning Calorimeter (DSC) the instrument test molten salt sample of PerkinElmer company of the U.S., adopt the standard aluminum crucible (band aluminium lid) that Perkin Elmer company provides, heat up with 10K/min, high pure nitrogen does sample protection gas, gas velocity is 20mL/min, and bell sweep gas is high pure nitrogen; The precision of this apparatus measures temperature reaches 0.01 DEG C, obtains melting point data accurately.
2) heat decomposition temperature measures:
Measure heat decomposition temperature and usually have two kinds of methods, one is dynamic TG method of testing, and the second is static muffle furnace method of testing.The temperature data accuracy that dynamic TG method of testing obtains is very high, and data precision at least reaches 0.1 DEG C, uses the TG curve of German NETZSCH STA 449C instrument test molten salt sample in this experiment, adopts Al
2o
3crucible, heats up with 10K/min, and sample protection gas is high-purity argon gas, and gas velocity is 20mL/min.
Principle of design of the present invention is mainly on the basis based on thermodynamical model prediction and calculation phasor, employing numerical computation method prepares a computer program, conveniently calculate the phasor of molten salt system by computer, find minimum fusing point and the formula composition of this system according to phasor.For ternary system and quaternary system, the method simple possible; For Quinary system, even more higher-dimension system, can predict on the basis of phasor in ternary and quaternary, Binding experiment " method of completing the square " finds optimum formula composition.The material composition point that last basis finds carries out preparation sample, adopts calorimetry method to carry out the mensuration of associated hot mechanical property, and then verifies that its fusing point and heat decomposition temperature are to obtain fused salt formula accurately.Be below concrete preferred forms:
Embodiment 1
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 20wt%NaNO
3, 50wt%KNO
3, 5wt%NaCl, 25wt%LiNO
3; Analyze after tested, its fusing point is 110 DEG C, heat decomposition temperature is 595 DEG C.Be illustrated in figure 1 the DSC curve of this sample; Fig. 2 is the TG curve of this sample.
Relative to Solar Salt, the fusing point of this product reduces nearly 110 DEG C, and its use temperature scope is 110-595 DEG C, obtains wider use temperature scope.
Embodiment 2
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 14wt%NaNO
3, 55wt%KNO
3, 8wt%NaCl, 23wt%LiNO
3, analyze after tested, its fusing point be 108 DEG C, heat decomposition temperature is 592 DEG C.
Embodiment 3
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 25wt%NaNO
3, 50wt%KNO
3, 3wt%NaCl, 22wt%LiNO
3, analyze after tested, its fusing point be 111 DEG C, heat decomposition temperature is 596 DEG C.
Embodiment 4
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 10wt%NaNO
3, 30wt%KNO
3, 8wt%NaCl, 52wt%Ca (NO
3)
2, analyze after tested, its fusing point be 115 DEG C, heat decomposition temperature is 570 DEG C.Be illustrated in figure 3 the DSC curve of this sample.
Embodiment 5
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 6wt%NaNO
3, 47wt%KNO
3, 10wt%NaCl, 37wt%Ca (NO
3)
2, analyze after tested, its fusing point be 112 DEG C, heat decomposition temperature is 572 DEG C.
Embodiment 6
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 6wt%NaNO
3, 30wt%KNO
3, 3wt%NaCl, 61wt%Ca (NO
3)
2, analyze after tested, its fusing point be 110 DEG C, heat decomposition temperature is 575 DEG C.
Embodiment 7
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 7wt%NaNO
3, 50wt%KNO
3, 3wt%NaCl, 9wt%LiNO
3, 31wt%Ca (NO
3)
2; Analyze after tested, its fusing point is 80 DEG C, heat decomposition temperature is 562 DEG C.Be illustrated in figure 4 the DSC curve of this sample; Fig. 5 is the TG curve of this sample.
Embodiment 8
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 10wt%NaNO
3, 54wt%KNO
3, 5wt%NaCl, 3wt%LiNO
3, 28wt%Ca (NO
3)
2, analyze after tested, its fusing point be 82 DEG C, heat decomposition temperature is 570 DEG C.
Embodiment 9
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 6wt%NaNO
3, 48wt%KNO
3, 8wt%NaCl, 3wt%LiNO
3, 35wt%Ca (NO
3)
2, analyze after tested, its fusing point be 83 DEG C, heat decomposition temperature is 578 DEG C.
Embodiment 10
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 15wt%NaNO
3, 50wt%KNO
3, 4wt%NaCl, 23wt%LiNO
3, 8wt%Na
2sO
4, analyze after tested, its fusing point be 85 DEG C, heat decomposition temperature is 592 DEG C.Comparative example 1-3 its add Na
2sO
4the fusing point of rear gained fused salt have dropped about 25 DEG C.
Embodiment 11
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 8wt%NaNO
3, 40wt%KNO
3, 5wt%NaCl, 37wt%Ca (NO
3)
2, 10wt%Li
2sO
4, analyze after tested, its fusing point be 83 DEG C, heat decomposition temperature is 589 DEG C.Comparative example 4-6 its add Li
2sO
4the fusing point of rear gained fused salt have dropped about 30 DEG C.
Embodiment 12
The low melting point fused salt mixt heat accumulation heat-transfer matcrial that the present embodiment provides, it is made up of the component of following mass percent: 6wt%NaNO
3, 50wt%KNO
3, 6wt%NaCl, 3wt%LiNO
3, 30wt%Ca (NO
3)
2, 5wt%K
2sO
4, analyze after tested, its fusing point be 82 DEG C, heat decomposition temperature is 590 DEG C.Comparative example 7-9 its add K
2sO
4fusing point and the heat decomposition temperature of rear gained fused salt all slightly raise.
The various embodiments described above, all adopt aforesaid method to prepare.
The present invention is not limited to above-mentioned embodiment; adopt raw material, the method identical or approximate with the above embodiment of the present invention; other low melting point fused salt mixt heat accumulation heat-transfer matcrials obtained according to the technology of the present invention principle and preparation method thereof, all within scope.
Claims (10)
1. a low melting point fused salt mixt heat accumulation heat-transfer matcrial, is characterized in that, it is made up of the component of following mass percent: 6-10wt%NaNO
3, 30-47wt%KNO
3, 3-10wt%NaCl, 37-61wt%Ca (NO
3)
2.
2. a low melting point fused salt mixt heat accumulation heat-transfer matcrial, is characterized in that, it is made up of the component of following mass percent: 14-25wt%NaNO
3, 50-55wt%KNO
3, 3-8wt%NaCl, 22-25wt%LiNO
3.
3. a low melting point fused salt mixt heat accumulation heat-transfer matcrial, is characterized in that, it is made up of the component of following mass percent: 6-10wt%NaNO
3, 48-54wt%KNO
3, 3-8wt%NaCl, 3-9wt%LiNO
3, 28-35wt%Ca (NO
3)
2.
4., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-3 Suo Shu, it is characterized in that, in its component, be also added with 5-10wt%Li
2sO
4, Na
2sO
4or K
2sO
4in any one.
5., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-4 Suo Shu, it is characterized in that, it is made up of the component of following mass percent: 20wt%NaNO
3, 50wt%KNO
3, 5wt%NaCl, 25wt%LiNO
3.
6., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-4 Suo Shu, it is characterized in that, it is made up of the component of following mass percent: by 10wt%NaNO
3, 30wt%KNO
3, 8wt%NaCl, 52wt%Ca (NO
3)
2.
7., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-4 Suo Shu, it is characterized in that, it is made up of the component of following mass percent: 7wt%NaNO
3, 50wt%KNO
3, 3wt%NaCl, 9wt%LiNO
3, 31wt%Ca (NO
3)
2.
8., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-4 Suo Shu, it is characterized in that, it is made up of the component of following mass percent: 15wt%NaNO
3, 50wt%KNO
3, 4wt%NaCl, 23wt%LiNO
3, 8wt%Na
2sO
4.
9., according to the low melting point fused salt mixt heat accumulation heat-transfer matcrial one of claim 1-4 Suo Shu, it is characterized in that, it is made up of the component of following mass percent: 6wt%NaNO
3, 50wt%KNO
3, 6wt%NaCl, 3wt%LiNO
3, 30wt%Ca (NO
3)
2, 5wt%Na
2sO
4.
10. a preparation method for the low melting point fused salt mixt heat accumulation heat-transfer matcrial that one of claim 1-9 is described, is characterized in that, comprise the steps:
(1) anhydrous single salt is prepared:
By NaNO
3, KNO
3, Na
2sO
4grind to form 50-200 object fine particle in advance with NaCl, in 120 DEG C of prebakes 12 hours in Electric heat oven, then be warmed up to 200 DEG C of oven dry 12 hours, put into loft drier for subsequent use; By its LiNO
3with Ca (NO
3)
2grind to form 50-200 object fine particle in advance, in Electric heat oven in 80 DEG C of prebakes 12 hours to slough the crystal water that may contain, then be warmed up to 130 DEG C and dry 12 hours; By the LiNO after process
3loft drier is put into for subsequent use after drying 12 hours at 220 DEG C, and the Ca (NO after process
3)
2loft drier is put into for subsequent use after drying 12 hours at 250 DEG C;
(2) fused salt mixt material is prepared:
The above anhydrous single salt prepared is mixed according to each formula, well-type electric furnace is put into after mechanical stirring is even, make fused salt mixt premelt 2 hours at 200 DEG C, then at fused salt being warmed up to 300 DEG C, mechanical stirring 30 minutes, pulverize after cooling and grind to form 50-200 object fine powder, be kept in loft drier, be heat accumulation heat-transfer medium material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419732A (en) * | 2015-12-09 | 2016-03-23 | 西安工程大学 | Method for preparing ternary nitric acid molten salt phase change heat storage material |
| CN106221678A (en) * | 2016-07-26 | 2016-12-14 | 中国科学院上海应用物理研究所 | The nitric acid fused salt of a kind of low melting point high heat-transfer performance and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58199880A (en) * | 1982-05-15 | 1983-11-21 | Nippon Stainless Steel Co Ltd | Molten salt bath for pickling |
| CN1323870A (en) * | 2000-05-15 | 2001-11-28 | 默克专利股份有限公司 | Method for prepn. of energy-saving composite material used for cold-strage or heat-storage |
| US7588694B1 (en) * | 2008-02-14 | 2009-09-15 | Sandia Corporation | Low-melting point inorganic nitrate salt heat transfer fluid |
| CN102533226A (en) * | 2011-12-15 | 2012-07-04 | 中山大学 | Nitrate molten salt heat transferring and reserving medium and preparation method and application thereof |
| CN103074040A (en) * | 2013-01-01 | 2013-05-01 | 北京工业大学 | Mixed molten salt as heat transfer and storage medium low in melting point |
| CN103680805A (en) * | 2012-09-12 | 2014-03-26 | Lg电子株式会社 | Ferrite magnet with salt and manufacturing method of the same |
-
2015
- 2015-02-03 CN CN201510056440.3A patent/CN104610927B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58199880A (en) * | 1982-05-15 | 1983-11-21 | Nippon Stainless Steel Co Ltd | Molten salt bath for pickling |
| CN1323870A (en) * | 2000-05-15 | 2001-11-28 | 默克专利股份有限公司 | Method for prepn. of energy-saving composite material used for cold-strage or heat-storage |
| US7588694B1 (en) * | 2008-02-14 | 2009-09-15 | Sandia Corporation | Low-melting point inorganic nitrate salt heat transfer fluid |
| CN102533226A (en) * | 2011-12-15 | 2012-07-04 | 中山大学 | Nitrate molten salt heat transferring and reserving medium and preparation method and application thereof |
| CN103680805A (en) * | 2012-09-12 | 2014-03-26 | Lg电子株式会社 | Ferrite magnet with salt and manufacturing method of the same |
| CN103074040A (en) * | 2013-01-01 | 2013-05-01 | 北京工业大学 | Mixed molten salt as heat transfer and storage medium low in melting point |
Non-Patent Citations (2)
| Title |
|---|
| JOSEPH A. RARD ， KIRK J. STAGGS ，S. DAN DAY，SUSAN A. CARROLL: "Boiling Temperature and Reversed Deliquescence Relative Humidity Measurements for Mineral Assemblages in the NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O System", 《J SOLUTION CHEM》 * |
| 魏高升等: "太阳能热发电系统相变储热材料选择及研发现状", 《中国电机工程学报》 * |
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| CN109821485A (en) * | 2019-04-11 | 2019-05-31 | 湖北科技学院 | The preparation method of phase-change thermal storage capsule for the regulation of dynamic lithium battery heat |
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