CN104804712B - The metal chloride fused salt material and preparation method of a kind of high heat conduction and application - Google Patents
The metal chloride fused salt material and preparation method of a kind of high heat conduction and application Download PDFInfo
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- CN104804712B CN104804712B CN201510134557.9A CN201510134557A CN104804712B CN 104804712 B CN104804712 B CN 104804712B CN 201510134557 A CN201510134557 A CN 201510134557A CN 104804712 B CN104804712 B CN 104804712B
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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 the metal chloride fused salt material and preparation method of a kind of high heat conduction and application.The metal chloride fused salt material of the high heat conduction consists of the following composition：Metal magnesium powder 0.05~2%, calcium chloride 98~99.95%.The present invention stirs by the way that metal magnesium powder is mixed with calcium chloride, solid is heated in inert gas shielding atmosphere and is all melt into liquid, be incubated, then cool down, crush, dry, obtain the metal chloride fused salt material of high heat conduction.The metal chloride fused salt material feedstock of the high heat conduction comes from caused tailing waste salt in Salt Lake Potash production process; salt lake tailing waste salt is set to obtain higher value application; realize salt lake resources comprehensive exploitation and environmental protection; and the system thermal conductivity factor is high; good thermal conduction, it is suitably applied regenerative resource scale and utilizes and industrial energy saving field.
Description
Technical field
The invention belongs to industrial energy saving and regenerative resource scale to utilize field, more particularly to a kind of gold of high heat conduction
Category-molten chloride material and preparation method and application.
Background technology
Industry is the maximum terminal in China energy consumer sector, accounts for 70% or so of national total energy consumption.It is wherein big
Scale raw and semifinished materials industries accounts for the 43% of national total industrial output value, but energy consumption accounts for the 72% of industrial total energy consumption, accounts for national energy total amount
52%.The average recovery utilization rate of waste heat is far below international most advanced level, is the main original for causing industrial energy utilization ratio low
Cause.By taking hot industry waste heat recovery as an example, according to incompletely statistics, China has gone into operation and in the 1000m built3It is more than level large-scale
Blast furnace there are about 169, estimate comprehensive pig iron production capacity at 3.2 hundred million tons or so, therefore annual Chinese large-sized blast furnace produces the quantity of slag close to 100,000,000
Ton, the tapping temperature of high temperature furnace slag carry equivalent 6,000,000 tons of the coal of mark of heat between 700~1600 DEG C.And actual pig iron yield
All it is higher than theoretical value with slag iron ratio, therefore the heat entrained by high temperature furnace slag is more huge.Realize high temperature furnace slag energy recovery profit
A kind of method is to be contacted or radiated with high temperature furnace slag using medium to carry out heat exchange, and high-temperature medium then is carried into huge energy
The energy that amount is converted into other forms is used.Therefore develop one kind in high temperature (≤800 DEG C) under good heat-transfer, property it is steady
Fixed heat transferring medium just turns into critical problem.The recycling of high temperature furnace slag heat energy is realized, country at this stage is not only conformed with and advocates
The energy-saving and emission-reduction policy and the strategy of sustainable development led, and enterprise's production cost can be saved, energy consumption is reduced, realizes that itself is imitated
The maximization of benefit.
On the other hand, solar energy high temperature heat utilization includes solar energy thermal-power-generating and solar heat chemical reaction accumulation of energy.Due to
Solar energy has the shortcomings that intermittent, energy density is low and stability is poor, it is difficult to meets continuous the needs of using energy, and sunshine gathers
It is defocused to produce very high temperature.Therefore the selection reliable high temperature heat transfer heat-storing material of performance will improve solar energy thermal-power-generating and too
One of key technology of positive energy thermal chemical reaction energy storage efficiency.
Fuse salt is as a kind of inorganic compound, and viscosity is small, good heat conductivity, corrosivity is weak, steam forces down, temperature in use
Scope is wide, cheap, turns into the first choice of high temperature heat transfer heat-storing material.Research shows, compared with high temperature heat conductive oil, with molten
Melting salt (nitric acid fused salt) can make solar power station maximum operating temperature bring up to 500 DEG C or so so that steam turbine, which generates electricity, imitates
Rate brings up to 40%.In addition, with fuse salt heat accumulation efficiency can also be made to improve 2.5 times, heat storage capacity is enhanced, reduces storage
Hot cost.
Heat transfer heat-storing material currently used for solar energy thermal-power-generating field comparative maturity is two end number mixing nitric acid fused salt (60%
KNO3- 40wt%NaNO3, Solar Salt) and ternary mixed nitrate fused salt (53%KNO3- 7%NaNO3- 40wt%NaNO2,
Hitec).Chinese patent 00111406.9,200710027954.1,201110287684.4 and 201110425668.7 and the U.S.
Patent US007588694B1 also individually discloses five kinds of nitric acid molten salt systems.The upper limit temperature in use one of both nitric acid fused salts
As be no more than 600 DEG C, being run under the relatively low trough type solar power generation of temperature is possible, and in the higher tower of running temperature
The overcritical heat of formula solar energy generates electricity and light collection solar chemical utilization is such as pyrolyzed the problem of decomposition and failure occurs in hydrogen manufacturing.
It is right typically between 0.5~0.55W/ (mK) and the thermal conductivity factor of nitric acid fused salt (particularly polynary nitric acid fused salt) is very low
The power station run under these high temperature, it is desirable to which heat transfer medium has bigger heat conductivility, the height that optically focused can be obtained rapidly
Warm can transfer out, and prevent hot-spot situation from occurring.
The patent application of Application No. 201310733403.2,201310731924.4 and 201310731910.2 carries respectively
Waterglass, quartz sand and metal oxide (or nonmetal oxide) nano-particle and carbonic acid fused salt has been supplied to form compound system,
The carbonic acid fused salt of these three systems can use under 800 DEG C of high temperature, can meet wanting for solar energy high temperature heat generating well
Ask, but carbonate system still suffers from the problem of thermal conductivity factor (thermal conductivity factor particularly under high temperature) is not high, it is impossible to meet to pass
Thermal medium quickly stores/needs of heat release, and also the fusing point of these additives is high, is deposited in solid particulate form in liquid fused salt
Due to density variation, it is being difficult to be stabilized under longtime running environment, the problems such as layering, and is making solid particle
In the presence of cause whole system viscosity increase, the high temperature heat transfer heat-storing material being not suitable as under service condition steady in a long-term.
For China, China possesses the sufficient salt lake resources for being available for utilizing.Qinghai is the distribution of China salt lake
Main area, just there are 32 salt lakes in the only Caidamu Basin, contain the salts resources such as abundant potassium, magnesium, lithium, calcium, potential
Economic value is huge.So that Qinghai Salt Lake discards the utilization of bittern magnesium resource as an example, magnesium chloride reserves are 40.6 hundred million tons, sodium chloride reserves
For 555.4 hundred million tons, it would be highly desirable to which solution is mine tailing stacking-bischofite MgCl2·6H2(year discharges about 20,000,000 m to O3) and NaCl,
About 20,000,000 tons of abraum salt caused by high sodium salt ore deposit and production potassium chloride.If using salt lake during potash fertilizer is produced caused tail
The discarded salt of ore deposit prepares magnesium sodium calcium base molten chloride and is applied to industrial energy saving and renewable energy as heat storage and transition material
Source scale utilizes field, can not only make Making Use of Tailings, solves discarded bittern pollution, and can also realize its scale height
Value utilizes.Particular, it is important that the hold over system efficiency of solar energy high temperature heat utilization and industrial afterheat recovery can be improved, significantly
Degree reduces the accumulation of heat cost of high enterprise, all meaningful great to salt lake resources high-value-use and the sustainable development of potash fertilizer industry.Shen
Number it please develop for 200510110315.2 a patent application and a kind of use calcium chloride hexahydrate as heat-storage medium, magnesium chloride hexahydrate
Apply the heat collecting system in terms of low-temperature heat accumulating as nucleator, but molten chloride as high temperature heat transfer heat-storing material should
It is also fewer at present with studying.
The content of the invention
The shortcomings that in order to overcome existing fusion tray of thermal transmission and storage material to exist under long term high temperature environmental operating conditions with
Deficiency, the present invention promote it in industrial energy saving and regenerative resource scale to realize that Salt Lake Potash produces mine tailing high level recycling
It is target to change using the application in equal energy source technology.The primary and foremost purpose of the present invention is the metal-chlorination for providing a kind of high heat conduction
Thing fused salt material.
Another object of the present invention is to the preparation method for the metal-chloride fused salt material for providing the high heat conduction.
It is still another object of the present invention to provide the application of the metal-chloride fused salt material of the high heat conduction.
The purpose of the present invention is achieved through the following technical solutions：A kind of metal-chloride fused salt material of high heat conduction, by with
Under by mass percentage composition composition：Metal magnesium powder 0.05~2%, calcium chloride 98~99.95%.
In order to have higher thermal conductivity factor and bigger heat-transfer capability, it is ensured that fused salt can quickly by high temperature heat absorb and
Transmission, improves the storage efficiency of heat energy, the hot-spot of avoiding device, and the metal-chloride fused salt material of above-mentioned high heat conduction is excellent
Choosing is made up of following composition by mass percentage：Metal magnesium powder 0.1~0.5%, calcium chloride 99.5~99.9%.
The preparation method of the metal-chloride fused salt material of above-mentioned high heat conduction, comprises the following steps：By metal magnesium powder and chlorine
Change calcium mixing, stir, all solids are heated in inert gas shielding atmosphere and become liquid, be incubated, then cooling, powder
It is broken, dry, obtain the metal-chloride fused salt material of high heat conduction；
Wherein, metal magnesium powder and calcium chloride (0.05~2) in mass ratio：(98~99.95) match, preferably press (0.1~
0.5)：(99.5~99.9) match.
Described inert gas is preferably argon gas.
The temperature of described heating is preferably 800~900 DEG C.
The time of described insulation is preferably 6~8 hours.
The temperature of described cooling is preferably 20~40 DEG C, more preferably 25 DEG C.
The metal-chloride fused salt material of above-mentioned high heat conduction can be applied to hot industry waste heat recovery field and the high temperature sun
The hot power field of energy, particularly apply in the overcritical heat hair in the high temperature furnace slag energy recovery field of steel industry and tower type solar
Electrical domain.
The present invention is had the following advantages relative to prior art and effect：
(1) metal-chloride provided by the invention melts the fusing point of molten chloride in salt material hardly feed change
With upper limit temperature in use, and thermal conductivity factor is high, good thermal conduction, can apply to high-temperature residual heat recovery and tower type solar is super faces
The hot power field in boundary.
(2) metal-chloride provided by the invention melting salt material not only overcome for example empty gas and water of traditional heat transfer media,
Conduction oil etc. because under the upper limit temperature in use low and high temperature vapour pressure it is big can not be efficiently applied to high-temperature residual heat recovery and solar heat
The defects of power field, and compared with all-chloride fused salt, the heat conduction of system is significantly increased under the conditions of trace meter is added
Performance.
(3) metal-chloride melting salt material provided by the invention, makes the application of fuse salt be extended to renewable energy
Source and hot industry waste heat recovery field, and tailing waste salt of the raw material sources in Salt Lake Potash production process, are realized
The comprehensive development and utilization of salt lake resources.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of metal-chloride melts salt material, and preparation method is as follows：
By 0.05wt% magnesium powder, 99.95wt% calcium chloride, (the tailing waste salt in Salt Lake Potash production process refines
Obtain, specific steps are by " such as Zhang Shuxia utilizes feasibility analysis [J] the Yunnan of the old halogen extraction chloride dehydrate calcium in Huo Buxun salt pans
Chemical industry, 2008,35 (4):17-20 " is operated, and material is with embodiment 1 used in example below) it is mixed and stirred for uniformly, static state heating
All melted to 850 DEG C to solid, be then incubated 8 hours, then naturally cool to room temperature, mechanical crushing, obtain metal-chloride
Melt salt material.
The metal-chloride melting salt material that the present embodiment is prepared using differential scanning calorimeter carries out fusing point survey
Examination, test result are as shown in table 1.The present embodiment is prepared at normal temperatures using Hotdisk TPS2500 thermal constants analyzers
The metal-chloride melting salt material arrived carries out Determination of conductive coefficients, as a result as shown in table 2.
Embodiment 2
A kind of metal-chloride melts salt material, and preparation method is as follows：
The calcium chloride of 0.1wt% magnesium powder, 99.9wt% is mixed and stirred for uniformly, static state is heated to 850 DEG C and arrives solid
All meltings, 8 hours then are incubated, then naturally cool to room temperature, mechanical crushing, obtain metal-chloride melting salt material.
Method of testing is with embodiment 1, as a result as shown in table 1~2.
Embodiment 3
A kind of metal-chloride melts salt material, and preparation method is as follows：
The calcium chloride of 0.3wt% magnesium powder, 99.7wt% is mixed and stirred for uniformly, static state is heated to 850 DEG C and arrives solid
All meltings, 8 hours then are incubated, then naturally cool to room temperature, mechanical crushing, obtain metal-chloride melting salt material.
Method of testing is with embodiment 1, as a result as shown in table 1~2.
Embodiment 4
A kind of metal-chloride melts salt material, and preparation method is as follows：
The calcium chloride of 0.5wt% magnesium powder, 99.5wt% is mixed and stirred for uniformly, static state is heated to 850 DEG C and arrives solid
All meltings, 8 hours then are incubated, then naturally cool to room temperature, mechanical crushing, obtain metal-chloride melting salt material.
Method of testing is with embodiment 1, as a result as shown in table 1~2.
Comparative example 1
Directly carried out using the method for testing of embodiment 1 to analyzing pure calcium chloride (Chemical Reagent Co., Ltd., Sinopharm Group)
Test, as a result as shown in table 1~2.
Comparative example 2
The calcium chloride of 0.3wt% aluminium powder, 99.7wt% is mixed and stirred for uniformly, static state is heated to 850 DEG C and arrives solid
All meltings, 8 hours then are incubated, then naturally cool to room temperature, mechanical crushing, obtain metal-chloride melting salt material.
Method of testing is with embodiment 1, as a result as shown in table 1~2.
Table 1
| Sample number into spectrum | Tenor (wt%) in system | Fusing point (DEG C) |
| Embodiment 1 | 0.05 | 773.33 |
| Embodiment 2 | 0.1 | 774.6 |
| Embodiment 3 | 0.3 | 775.28 |
| Embodiment 4 | 0.5 | 772.16 |
| Comparative example 1 | 0 | 776.69 |
| Comparative example 2 | 0.3 | 774.32 |
Table 2
From the result of Tables 1 and 2, it is seen that a small amount of magnesium metal is added in calcium chloride, hardly changes system fusing point and upper
Temperature in use is limited, and the thermal conductivity factor of obtained chloride melting salt material is high, good thermal conduction.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
- A kind of 1. metal-chloride fused salt material of high heat conduction, it is characterised in that by it is following by mass percentage into packet Into：Metal magnesium powder 0.05~2%, calcium chloride 98~99.95%.
- 2. the metal-chloride fused salt material of high heat conduction according to claim 1, it is characterised in that by pressing quality hundred below Divide the composition composition than meter：Metal magnesium powder 0.1~0.5%, calcium chloride 99.5~99.9%.
- 3. the preparation method of the metal-chloride fused salt material of the high heat conduction described in claim 1 or 2, it is characterised in that including Following steps：Metal magnesium powder is mixed with calcium chloride, stirred, all solids change is heated in inert gas shielding atmosphere Into liquid, insulation, then cool down, crush, dry, obtain the metal-chloride fused salt material of high heat conduction；Described inert gas is argon gas；The temperature of described heating is 800~900 DEG C；The time of described insulation is 6~8 hours.
- 4. the preparation method of the metal-chloride fused salt material of high heat conduction according to claim 3, it is characterised in that：Institute The temperature for the cooling stated is 20~40 DEG C.
- 5. the preparation method of the metal-chloride fused salt material of high heat conduction according to claim 4, it is characterised in that：Institute The temperature for the cooling stated is 25 DEG C.
- 6. the application of the metal-chloride fused salt material of the high heat conduction described in claim 1 or 2, it is characterised in that：Described height The metal-chloride fused salt materials application of heat conduction is in hot industry waste heat recovery field and high-temperature solar power field.
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| CN107177348A (en) * | 2017-05-22 | 2017-09-19 | 华南理工大学 | A kind of metal carbonate fused salt material of high heat conduction and preparation method and application |
| 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 |
| CN109796940A (en) * | 2019-02-22 | 2019-05-24 | 广州特种承压设备检测研究院 | A kind of mixed chloride fused salt of high thermal conductivity and its preparation method and application |
| 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 |
| CN111909664A (en) * | 2020-07-14 | 2020-11-10 | 中盐金坛盐化有限责任公司 | Inorganic fiber composite chlorine system molten salt heat storage material and preparation method and application thereof |
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