CN105222477B - A kind of low-melting-point nano Molten Salt Heat Transfer heat storage medium and preparation method - Google Patents
A kind of low-melting-point nano Molten Salt Heat Transfer heat storage medium and preparation method Download PDFInfo
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Abstract
A kind of low-melting-point nano Molten Salt Heat Transfer heat storage medium and preparation method, belong to physics heat transfer technical field of energy storage in new and high technology.It is made up of low melting point fused salt mixt with Nanocomposites；The low melting point fused salt mixt is mainly made up of potassium nitrate, sodium nitrate, calcium nitrate and lithium nitrate；The nano-particle is the nano-particle of metal oxide or nonmetal oxide.New low-melting-point nano fused salt fusing point prepared by the present invention is in 80 130 DEG C, decomposition temperature at 600 DEG C or so, and relative to low melting point fused salt mixt, larger change does not occur for its use temperature range, but its specific heat is significantly improved, increase rate about 10% 60%.
Description
Technical field
The present invention relates to a kind of formula of the fused salt mixt for high temperature heat transfer accumulation of heat, belong to physics in new and high technology and pass
Hot technical field of energy storage.
Background technology
Because solar energy thermal-power-generating can be combined with inexpensive large-scale heat storage technology, it is possible to provide stable high-quality electricity
Can, overcome wind-force and photovoltaic plant due to can not large-scale use battery and cause poor quality of transmitting electricity, power network is impacted big
The defects of, it is considered to be one of most promising generation mode in renewable energy power generation, it is possible to as main force's energy in future
Source.
At present, in the trough type solar power generation field of technology maturation, commercialization power station is using conduction oil as heat transfer
Medium, this causes, and power station large-scale installation cost is high, operating temperature is low, system pressure is big, reliability is low, heat conduction life of oil
It is short, cost is high, finally can only achieve 14% annual generating efficiency.
Tower-type solar thermal power generating system is typically using vapor or air as heat-transfer working medium.Vapor and air high temperature
The shortcomings of lower heat transfer coefficient is low and uneven, system pressure is very high, this largely reduces the reliability of system, improves
System investments and later maintenance cost.
Fused salt has many advantages, such as use temperature range is big, and system pressure is low, and unit cost is low, and hot property is excellent, because
This is used as heat transfer heat storage medium using suitable fuse salt, can effectively lift the performance of solar heat power generation system.Specific body
Now：First, fuse salt operating temperature is higher by 100 DEG C or so compared with media such as conduction oils so that system generating efficiency is improved；
Secondly as pressure (10-20 air of the operating pressure (about 2 atm highers) of fuse salt far below media such as conduction oils
Pressure) so that the reliability of solar heat power generation system is improved；3rd, using fuse salt as heat transfer heat storage medium, with high
Warm conduction oil is compared, and the life-cycle can be brought up to more than 20 years by 2 years or so, price can be down to by ten thousand yuan/ton of 2-3 10,000 yuan/ton with
Under；4th, fuse salt accumulation of heat is the Main Means for solving the problems, such as solar energy thermal-power-generating accumulation of heat.
Fused salt is applied as heat transfer heat storage medium in solar heat power generation system.Current fused salt it is main
Shortcoming be fusing point compared with high (130-230 DEG C), specific heat is small, thermal conductivity is low.At present, KNO has been developed3-NaNO3-LiNO3-Ca
(NO3)2Molten salt system, its fusing point solve the problems, such as that fused salt fusing point is higher at 90 DEG C or so.
The content of the invention
The technical problems to be solved by the invention are to improve the specific heat of low melting point fused salt mixt, so as to strengthening system accumulation of heat energy
Power and heat transfer efficiency, reduce solar energy thermal-power-generating and industrial accumulation of heat cost.
In order to solve the above-mentioned technical problem, the present invention provides a kind of new low-melting-point nano Molten Salt Heat Transfer heat storage medium, its
It is characterised by：It is made up of low melting point fused salt mixt with Nanocomposites；The low melting point fused salt mixt is mainly by nitric acid
Potassium, sodium nitrate, calcium nitrate and lithium nitrate composition；The nano-particle is the nanoparticle of metal oxide or nonmetal oxide
Son.
The low melting point fused salt mixt, the mass percentage content of each composition are respectively：18-20wt% calcium nitrate, 50-
55wt% potassium nitrate, 9-10wt% sodium nitrate, 18-20wt% lithium nitrates.
The nano-particle species is SiO2、Al2O3、TiO2, one or more in MgO nano-particles, particle diameter 5-
60nm。
The nano-particle is the 0.5%-5% of the new low-melting-point nano fused salt gross mass.
Present invention also offers the preparation method of new low-melting-point nano Molten Salt Heat Transfer heat storage medium, comprise the following steps：
(1) low melting point fused salt mixt is put into Muffle furnace and is heated to molten condition；
(2) nano-particle is proportionally added into the low melting point fused salt mixt of melting, natural cooling obtains after stirring
To new low-melting-point nano fused salt.
Described low melting point fused salt mixt is mainly made up of potassium nitrate, sodium nitrate, lithium nitrate and calcium nitrate；The nanoparticle
Son is metal or the nano-particle of nonmetal oxide.
In the low melting point fused salt mixt system, the mass percentage content of each composition is respectively：18-20wt% nitric acid
Calcium, 50-55wt% potassium nitrate, 9-10wt% sodium nitrate, 18-20wt% lithium nitrates.
The nano-particle species is SiO2、Al2O3、TiO2, MgO nano-particles, particle diameter 5-60nm.
Nano-particle is added in the 0.5%-5% of low-melting-point nano fused salt gross weight ratio in the step (2)；
Magnetic agitation 50-70min, rotating speed 300-600r/min described in the step (2).
This low-melting-point nano fused salt of the invention is applied in industrial accumulation of energy and solar light-heat power-generation.
The beneficial effects of the present invention are：
1st, the new low-melting-point nano fused salt fusing point that prepared by technical solution of the present invention is relatively low, and (melting range is：80—130
DEG C), the higher (decomposition temperature scope of decomposition temperature：570-690 DEG C), it is applied in solar heat power generation system, will be dropped significantly
The cost of low heat transfer hold over system, simplify system initial launch program, it is not necessary to which special firing equipment prevents the jelly of fused salt
It is stifled, add the security and stability of whole system.
2nd, compared with low melting point fused salt mixt system, specific heat has bright new low-melting-point nano fused salt prepared by technical solution of the present invention
Aobvious to improve, heat transfer heat storage capacity is good, can be widely applied to solar light-heat power-generation technical field.
Brief description of the drawings
Fig. 1 SiO2The DSC curve of low-melting-point nano fused salt.
(low melting point salt：SiO2Nano-particle=99wt%:1wt%)
Fig. 2 SiO2The TG curves of low-melting-point nano fused salt.
Fig. 3 SiO2The ratio heating curve of low-melting-point nano fused salt.
Fig. 4 Al2O3The DSC curve of low-melting-point nano fused salt.
(low melting point salt：Al2O3Nano-particle=99wt%:1wt%)
Fig. 5 Al2O3The TG curves of low-melting-point nano fused salt.
Fig. 6 Al2O3The ratio heating curve of low-melting-point nano fused salt.
Fig. 7 TiO2The DSC curve of low-melting-point nano fused salt.
(low melting point salt：TiO2Nano-particle=99wt%:1wt%)
Fig. 8 TiO2The TG curves of low-melting-point nano fused salt.
Fig. 9 TiO2The ratio heating curve of low-melting-point nano fused salt.
Embodiment
The present invention provides a series of low-melting-point nano fused salts for being used as the heat storage medium that conducted heat in solar heat power generation system and matched somebody with somebody
Side, the formula are mainly made up of low melting point fused salt mixt with Nanocomposites, and wherein low melting point fused salt mixt is mainly by nitre
Sour potassium, sodium nitrate, lithium nitrate and calcium nitrate composition；The nano-particle is the nano-particle of metal or nonmetal oxide.Institute
State in low melting point fused salt mixt system, the mass percentage content of each composition is respectively：18-20wt% calcium nitrate, 50-55wt%
Potassium nitrate, 9-10wt% sodium nitrate, 18-20wt% lithium nitrates.The nano-particle species is SiO2、Al2O3、TiO2, MgO receives
Rice corpuscles, particle diameter 5-60nm.The fusing point of low melting point fused salt mixt is at 90 DEG C or so, and decomposition temperature is higher than 600 DEG C, and it is in liquid
When specific heat be 1.5-1.6J/ (g.k) left and right.After nano-particle being added in low melting point fused salt mixt, its fusing point and decomposition temperature
Do not change, but specific heat can improve a lot.
The specific preparation process of new low-melting-point nano fused salt is as follows：
Potassium nitrate, sodium nitrate, lithium nitrate and calcium nitrate are formed into KNO by the mass percentage content of each composition3-NaNO3-
LiNO3-Ca(NO3)2Molten salt system, heating stirring are uniformly put into Muffle furnace and are heated to molten condition.
Nano-particle is proportionally added into the new low-melting-point nano molten salt system of step (1) melting, stirred using magnetic force
Mix device and stir molten mixture 50-70min, natural cooling after stirring, obtain uniform and stable new low-melting-point nano and melt
Salt.
Embodiment 1
This kind of low-melting-point nano fused salt is by 99wt% low melting points salt and 1wt%SiO2Nano-particle forms, wherein the eutectic
Select salt to be made up of 55wt% potassium nitrate, 9wt% sodium nitrate, 18wt% lithium nitrates and 18wt% calcium nitrate, SiO2Nanoparticle seed
Footpath is 20nm.Using the fusing point of DSC (differential canning calorimetry) test analysis low-melting-point nano fused salt, pass through TG (thermogravimetric) points
Its decomposition temperature is analysed, its specific heat is analyzed using DIN51007 standard methods.As a result show, its fusing point is 114.1 DEG C, decomposition temperature
For 604 DEG C, specific heat is about 1.8-2.0J/g.k during the formula low-melting-point nano fused salt liquid.Fig. 1 is the DSC curve of the sample.
Fig. 2 is the TG curves of the sample.Fig. 3 is the specific heat test result of the sample.
Compared with pure low melting point fused salt mixt, the formula low-melting-point nano fused salt fusing point improves about 20 DEG C, and decomposition temperature is not
Vary widely, there is wider use temperature range.
For pure low melting point fused salt mixt in liquid, specific heat is about 1.5-1.7J/g.k, at 250 DEG C, the formula low melting point
Nanometer molten salt is relative to pure low melting point fused salt mixt, specific heat increase by 24%.
Embodiment 2
This kind of low-melting-point nano fused salt is by 99wt% low melting points salt and 1wt%Al2O3Nano-particle forms, wherein the eutectic
Select salt to be made up of 55wt% potassium nitrate, 9wt% sodium nitrate, 18wt% lithium nitrates and 18wt% calcium nitrate, Al2O3Nanoparticle seed
Footpath is 20nm.As a result show, its fusing point is 108.8 DEG C, and decomposition temperature is 595 DEG C, during the formula low-melting-point nano fused salt liquid
Specific heat is about 2.4-2.6J/g.k.Fig. 4 is the DSC curve of the sample.Fig. 5 is the TG curves of the sample.Fig. 6 is the ratio of the sample
Thermal test result.
Compared with pure low melting point fused salt mixt, the formula low-melting-point nano fused salt fusing point improves about 20 DEG C, and decomposition temperature is not
Vary widely, there is wider use temperature range compared with pure low melting point fused salt mixt.
For pure low melting point fused salt mixt in liquid, specific heat is about 2.4-2.6J/g.k, at 250 DEG C, the formula low melting point
Nanometer molten salt is relative to pure low melting point fused salt mixt, specific heat increase by 55%.
Embodiment 3
This kind of low-melting-point nano fused salt is by 99wt% low melting points salt and 1wt%TiO2Nano-particle forms, wherein the eutectic
Select salt to be made up of 55wt% potassium nitrate, 9wt% sodium nitrate, 18wt% lithium nitrates and 18wt% calcium nitrate, TiO2Nanoparticle seed
Footpath is 20nm.As a result show, its fusing point is 112.2 DEG C, and decomposition temperature is 579 DEG C, during the formula low-melting-point nano fused salt liquid
Its specific heat is about 1.6-1.9J/g.k.Fig. 7 is the DSC curve of the sample.Fig. 8 is the TG curves of the sample.Fig. 9 is the sample
Specific heat test result.
Compared with pure low melting point fused salt mixt, the formula low-melting-point nano fused salt fusing point improves about 20 DEG C, and decomposition temperature is omited
There is reduction, but still be that there is wider use temperature range.
At 300 DEG C, the formula low-melting-point nano fused salt is relative to pure low melting point fused salt mixt, specific heat increase by 10%.
The scope of the present invention is not limited to above-described embodiment, and the technology deformation that every foundation the technology of the present invention principle is done is equal
Fall into the protection category of the present invention.
Claims (5)
- A kind of 1. low-melting-point nano Molten Salt Heat Transfer heat storage medium, it is characterised in that：It is by low melting point fused salt mixt and nano-particle It is combined；The low melting point fused salt mixt is mainly made up of potassium nitrate, sodium nitrate, calcium nitrate and lithium nitrate；The nanoparticle Son is metal oxide or the nano-particle of nonmetal oxide；The low melting point fused salt mixt, the mass percentage content of each composition are respectively：18-20wt% calcium nitrate, 50-55wt% nitre Sour potassium, 9-10wt% sodium nitrate, 18-20wt% lithium nitrates.
- 2. according to a kind of low-melting-point nano Molten Salt Heat Transfer heat storage medium of claim 1, it is characterised in that：The nano-particle species For SiO2、Al2O3、TiO2, one or more in MgO nano-particles, particle diameter 5-60nm.
- 3. according to a kind of low-melting-point nano Molten Salt Heat Transfer heat storage medium of claim 1, it is characterised in that：The nano-particle is institute State the 0.5%-5% of low-melting-point nano fused salt gross mass.
- 4. preparing the method according to any one low-melting-point nano Molten Salt Heat Transfer heat storage medium described in claim 1-3, its feature exists In：Comprise the following steps：（1）Low melting point fused salt mixt is put into Muffle furnace and is heated to molten condition；（2）Nano-particle is proportionally added into the low melting point fused salt mixt of melting, natural cooling obtains low after stirring Fusing point nanometer molten salt heat transfer heat storage medium.
- 5. according to the method for claim 4, it is characterised in that step（2）Middle magnetic agitation 50-70min, rotating speed 300- 600r/min。
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| CN105838338A (en) * | 2016-04-25 | 2016-08-10 | 碧城（上海）新能源科技有限公司 | Nano mixed molten salt heat transfer and storage medium and preparation method thereof |
| CN106010468A (en) * | 2016-06-22 | 2016-10-12 | 黄毅 | Low-melting-point mixed molten salt as heat transfer and storage medium |
| CN106281254A (en) * | 2016-07-21 | 2017-01-04 | 北京工业大学 | A kind of two end number mixing Molten Salt Heat Transfer heat storage medium |
| CN106854457A (en) * | 2016-12-22 | 2017-06-16 | 华东理工大学 | A kind of polynary high-performance passes thermal storage and energy accumulation fused salt mixt and preparation method thereof |
| CN109777365B (en) * | 2019-01-29 | 2020-10-02 | 云南科威液态金属谷研发有限公司 | Liquid metal composite phase change energy storage material and preparation method and application thereof |
| CN109735307A (en) * | 2019-02-22 | 2019-05-10 | 广州特种承压设备检测研究院 | A kind of modified chlorinated object fused salt and its preparation method and application |
| CN110791301A (en) * | 2019-10-31 | 2020-02-14 | 中国科学院青岛生物能源与过程研究所 | Heat transfer processing method for fusible metal heat carrier |
| CN111944488A (en) * | 2020-07-31 | 2020-11-17 | 华北电力大学 | Solid-solid phase change nanoparticle-based molten salt heat storage medium and preparation method thereof |
| CN114410280A (en) * | 2022-01-14 | 2022-04-29 | 北京工业大学 | Low-melting-point wide-temperature-range fused salt composite sizing phase-change material and preparation method thereof |
| CN114539987A (en) * | 2022-02-24 | 2022-05-27 | 中煤科工集团重庆研究院有限公司 | Fused salt formula suitable for gas heat storage oxidation heat supply process |
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| US7588694B1 (en) * | 2008-02-14 | 2009-09-15 | Sandia Corporation | Low-melting point inorganic nitrate salt heat transfer fluid |
| DE102011083735A1 (en) * | 2011-09-29 | 2013-04-04 | Siemens Aktiengesellschaft | Salt mixture as heat transfer and / or storage medium for solar thermal power plants, process for the preparation thereof |
| CN103881663B (en) * | 2013-02-19 | 2017-05-17 | 深圳市爱能森科技有限公司 | Multielement nitric acid nano-molten salt heat transfer and heat storage medium, preparation method and application thereof |
| CN103911121B (en) * | 2013-12-26 | 2017-05-17 | 深圳市爱能森科技有限公司 | Nanometer molten binary nitrate heat-transfer heat-storage medium and preparation method thereof |
| CN103289653B (en) * | 2013-04-24 | 2015-07-15 | 华北电力大学 | High-thermal-conductivity heat-storing nanometer-particle-mixed molten salt and preparation method thereof |
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