CN107573901A - A kind of low melting point heat transfer accumulation of heat fused salt, preparation method and applications - Google Patents
A kind of low melting point heat transfer accumulation of heat fused salt, preparation method and applications Download PDFInfo
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Abstract
The present invention " a kind of low melting point heat transfer accumulation of heat fused salt and its preparation method and application ", it is characterised in that be made using following preparation process, (1) is by four kinds of monomer fused salt Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3It is put into corundum crucible, mixes；(2) mixed fused salt is placed in baking oven, incrementally heated 24 36 hours from 50 DEG C of start temperatures, finally heated and stirred until composite fused salt turns into uniform solution system at 150 DEG C；(3) composite fused salt is placed in 200 250 DEG C of Muffle furnaces, is incubated 8 12 hours, remove Ca (NO3)2·4H2The crystallization water in O；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains the homogeneous system composite fused salt of solid.Obtained low melting point fused salt stable operation in 150 550 degree Celsius temperature ranges, and viscosity not more than 5.5cp, viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage risk reduces, and the security and stability of whole system improves, life-span increase.
Description
Technical field
The present invention relates to a kind of low melting point heat transfer accumulation of heat fused salt, more particularly to a kind of low melting point heat transfer accumulation of heat fused salt, preparation
Method and its application.
Background technology
At present, in industrial accumulation of energy and solar energy high temperature heat utilization field, the nitrate molten salt body for the heat storage medium that conducts heat
Owner will include the Solar Salt fused salts (60wt%NaNO of binary3+ 40wt%KNO3) and ternary Hitec molten salt systems 7wt%
NaNO3+ 53wt%KNO3+ 40wt%NaNO2.In both melting salt systems, binary nitric acid salt system thermostabilization is good, cost
It is cheap, but higher up to 220 DEG C of its fusing point, it is higher to the safety and stability requirement of system, and operating temperature range is narrow,
Unit cold start process is complicated, and heat consumption is big, and system maintenance is costly.And although ternary nitric acid salt system fusing point is relatively low
140 DEG C or so, but upper limit temperature in use is relatively low, has heat endurance below 450 DEG C, can be run at 538 DEG C with the short time,
Heat endurance is poor, and needs to carry out inert gas such as nitrogen protection in use, prevents system oxidation deterioration.
People attempt to add other compositions into nitric acid molten salt system to solve the above problems, still in existing technology
While the ceiling temperature of nitric acid molten salt system after improvement improves, its lower working temperature is also enhanced, and causes to protect during obnubilation
Warm maintenance cost increase, test of the same aggravation to the safety and stability of system.For example, fourth waits quietly having invented a kind of quaternary and melted
Salt, i.e., add LiNO on the basis of ternary molten salt system3Obtain LiNO3-KNO3-NaNO3-NaNO2, its optimal use temperature range
For 250-550 DEG C.The upper limit working temperature of this system increases compared with ternary nitric acid molten salt system, reaches 550 DEG C, but
Its lower working temperature is also enhanced, and allows people to need to protect stable system using inert gas, prevents oxidation deterioration.Cause
This quaternary system is used as heat transfer heat storage medium, improvement of still needing as solar energy thermal-power-generating.
The present invention is proposed accordingly.
The content of the invention
The problems such as in order to overcome the high-melting-point of traditional fused salt, high working service cost, low specific heat capacity, low thermal conductivity, this
Invention provides a kind of new low melting point composite fused salt, and technical scheme is as follows：
A kind of low melting point heat transfer accumulation of heat fused salt, it is characterised in that：With Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3For original
Material is made, including following preparation process：
(1) by four kinds of raw materials of Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3It is put into corundum crucible, mixes；
(2) mixed fused salt is placed in baking oven, incrementally heats 24-36 hours from 50 DEG C of start temperatures, finally exist
150 DEG C are heated and stirred until composite fused salt turns into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt；
Ca (NO in manufactured fused salt3)2、KNO3、NaNO3、LiNO3The percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 10-16%, potassium nitrate 38-50%, sodium nitrate 23.5-35%, lithium nitrate 3-9%；
Calcium nitrate 15-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%；
Calcium nitrate 15-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 9%；Or
Calcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 15-30%, lithium nitrate 3-18%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 29-40%, potassium nitrate 40-52%, sodium nitrate 6-12%, lithium nitrate 3-14%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 29-40%, potassium nitrate 40-49.5%, sodium nitrate 6-12%, lithium nitrate 3-14%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 29-40%, potassium nitrate 38-50%, sodium nitrate 6-30%, lithium nitrate 3-9%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 22-30%, potassium nitrate 38-55%, sodium nitrate 6-30%, lithium nitrate 3-9%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 22-30%, potassium nitrate 38-49%, sodium nitrate 8-30%, lithium nitrate 3-9%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 22-28%, potassium nitrate 38-50%, sodium nitrate 6-30%, lithium nitrate 3-9%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 17-20%, potassium nitrate 36-54%, sodium nitrate 15-30%, lithium nitrate 1-14%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 15-28%, potassium nitrate 35-55%, sodium nitrate 21-30%, lithium nitrate 3-9%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as follows：
Calcium nitrate 15-35%, potassium nitrate 35-55.5%, sodium nitrate 15-30%, lithium nitrate 14.5-18%.
Preferably, the percentage by weight of four kinds of monomer fused salts is as shown in any formula of following table：
Preferably, any of the above-described fused salt, 0.5-2%wt CsNO can also be included3And/or Sr (NO3)2。
In any of the above-described fused salt, it is preferable that it is described from 50 DEG C of start temperatures incrementally heat 24-36 hours refer at 50 DEG C plus
Heat and stir 8-12 hours, 80 DEG C heat and stir 8-12 hours, 120 DEG C heat and stir 8-12 hours.
Preferably, the Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3Four kinds of monomer fused salt raw materials are by recrystallization
The monomer fused salt of purification processes.Experimental data shows, obtained by the monomer nitric acid fused salt by recrystallizing purification processes is compound this
Invention fused salt, compared to the compound fused salt of the monomer nitric acid fused salt of technical pure level is directly used, its heat endurance significantly improves.
Any described low melting point conducts heat accumulation of heat fused salt in solar light-heat power-generation, energy storage peak shaving, clean energy resource station system
And the purposes in other heat transfer accumulation of heat fields.
The present invention also provides the preparation technology of any of the above-described low melting point heat transfer accumulation of heat fused salt：
(1) by four kinds of monomers fused salt raw materials of Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3It is put into corundum crucible,
Mix；
(2) mixed fused salt is placed in baking oven, incrementally heats 24-36 hours from 50 DEG C of start temperatures, finally exist
150 DEG C are heated and stirred until composite fused salt turns into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt.
After the present invention forms eutectic composite fused salt by various of monomer fused salt, its fusing point is reduced, increases specific heat capacity and heat conduction
Coefficient, by reducing LiNO in composite fused salt to greatest extent3Content and introduce multicomponent and reduce cost, it is low to obtain a kind of price
It is honest and clean, viscosity is still relatively low, temperature in use is wide, the low melting point of excellent performance heat transfer accumulation of heat composite fused salt.
Specifically：By adjusting the respective proportion and preparation technology of calcium nitrate, potassium nitrate, sodium nitrate and lithium nitrate, obtain
A series of as little as 80 DEG C of fusing points are obtained, decomposition temperature temperature may be up to 670 DEG C, and thermal conductivity factor is up to 0.57W (mK), specific heat capacity
Up to 1.75~1.9KJ/ (kgK).The fused salt is in preparation and in use, having many advantages：
On the one hand, relative to current photo-thermal power plant construction and the high cost consumption of operation, using fused salt provided by the invention,
Because the content of wherein lithium nitrate is low, cost of material is than relatively low；And the fused salt of the present invention is used and is incremented by since 50 degrees Celsius
Prepared by the mode of heating, not only can thoroughly remove hydrone, does not occur substantially more important is calcium nitrate in preparation process
Decomposition will not produce calcium nitrite and oxygen so that and system Nitrite Ion Content is extremely low, almost in nothing, and gained
The low melting point quaternary nitric acid composite fused salt heat endurance of the present invention is more preferable, and being not easy to produce during use has corrosive Asia
Nitrate, therefore, nitrogen need not be all added to prevent its oxidation deterioration during preparation and use, it is small to system corrosion；In addition, chlorine
Ion concentration is low, also further ensures the advantages of it is small to system corrosion；Above feature makes the fused salt of invention, either makes
Standby or use, can be greatly lowered using operating cost.
Second aspect, find that the saturated vapor of the fused salt of the present invention forces down after tested, not higher than 2 atmospheric pressure so that too
The security reliability of positive energy heat generating system is improved.
The third aspect, fused salt stable operation in 150-550 degree Celsius temperature ranges of the present invention is found, and viscosity is most
Height is no more than 5.5cp, and viscosity is low, it can be ensured that has good heat transfer efficiency, generating efficiency, pipeline blockage risk reduces, whole
The security and stability of individual system improves, life-span increase.
Therefore, the invention provides a kind of significantly improved inexpensive clean energy resource medium of combination property, it is particularly suitable for making
For the heat transfer in clean energy resource boiler and heat storage medium, it can also be used to solar light-heat power-generation and other heat transfer accumulation of heat fields.
Brief description of the drawings
Fig. 1 is the mixed nitrate DTA curve of numbering 15 of the present invention；
Fig. 2 is the mixed nitrate TG curves of numbering 15 of the present invention.
Embodiment
Raw material：
Ca(NO3)2·4H2O、KNO3、NaNO3、LiNO3Technical pure level, general chemical article company are commercially available.
Recrystallize the Ca (NO of purification3)2·4H2O、KNO3、NaNO3、LiNO3Monomer salt：Preparation technology is as follows：
The monomer salt of various technical pure levels is set through low temperature (50-100 degrees Celsius) slow mechanism dissolved list product salting liquid by adsorbing
Fat is adsorbed, then by filter press press filtration, then is recrystallized after single product salting liquid is cooled down, with pure water to recrystallization after
Single salt of savoring washed, then single salt of savoring after washing is put into electric heating reacting kettle, heated after adding pure water, by electricity plus
Single product salting liquid in thermal response kettle is placed in crystallisation by cooling in cooler, by single salt of savoring after crystallization by centrifuge dewatering, then
Single salt of savoring after dehydration is washed with pure water, after washing then single salt of savoring is dried, obtained again by centrifuge dewatering
The single of high-purity savors salt.
1. first groups of composite fused salts of embodiment
Step 1. prepares this composite fused salt：
(1) KNO is weighed according to the composition of table 1-1 composite fused salt3、NaNO3、LiNO3, and according to Ca (NO3)2Ratio claim
Take required Ca (NO3)2·4H2O is put into corundum crucible, is mixed；
(2) mixed fused salt is placed in baking oven, 50 DEG C are heated and stirred and heat within 12 hours, 80 DEG C and to stir 10 small
When, 120 DEG C heat and stir 8 hours, 150 DEG C heat and stir until composite fused salt turn into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt.
Table 1-1 low-temperature molten salts 1-5 composition
Note：Wherein calcium nitrate %wt represents Ca (NO in the finally low-temperature molten salt of gained3)2Ratio, the raw material of fused salt is Ca
(NO3)2·4H2O, according to Ca (NO3)2Proportion calculate and it weighs Ca (NO3)2·4H2In O dosage, such as No. 1 fused salt,
Contain 11g Ca (NO in per 100g low-temperature molten salts3)2, due to Ca (NO3)2In Ca (NO3)2·4H2Content in O is about 70%,
Therefore, Ca (NO3)2·4H2O dosage is 11/0.7=15.7g.Meet obtained from anhydrous in the composite fused salt listed by 1
The weight percent of calcium nitrate.
Step 2. surveys thermal conductivity factor
Method：(being tested in a nitrogen atmosphere) is carried out using liquid thermal conductivity factor tester, every kind of fused salt takes three parts
Tested, test result takes the average value at 300 DEG C, and test result is shown in Table 1-3：
Step 3. surveys specific heat capacity
Method：(being scanned at ambient pressure) is carried out using general differential heating scan instrument DSC, every kind of fused salt takes three parts
Tested, test result takes the average value at 300 DEG C and/or 400 DEG C, and test result is shown in Table 1-3：
Step 4. determines fusing point
Method：(being scanned at ambient pressure) is carried out using general differential heating scan instrument DSC, every kind of fused salt takes three parts
Tested, test result is averaged, and test result is shown in Table 1-3：
Step 5. determines decomposition temperature
Method：(being scanned at ambient pressure) is carried out using general thermogravimetric analyzer TGA, every kind of fused salt takes three parts of progress
Test, test result are averaged, and test result is shown in Table 1-3：
Step 6 saturated vapor pressure
Tester：Using saturated vapor pressure analyzer, every kind of fused salt takes three parts to be tested, and test result is averaged
Value, test result are shown in Table 1-2.
Step 7. viscosimetric
Tester：Carry out using rotational rheometer and (be passed through protective gas), every kind of fused salt takes three parts to be tested, test
As a result average value at 300 DEG C and/or 400 DEG C is taken, the results are shown in Table 1-3
Table 1-2 commonly uses fused salt test result in the prior art
Table 1-3 low-temperature molten salts 1-5 physical property measurement result
The fused salt fusing point of the group of formula is can be seen that substantially all below 100 degrees centigrades from table 1-3 and table 1-2, and
Decomposition temperature is all higher than 580 degrees Celsius, has preferable use temperature range, and this can correspondingly improve the generating effect of fused salt
Rate；Specific heat capacity, thermal conductivity factor and viscosity are all significantly better than commonly uses fused salt in the prior art.
In addition, use before to fused salt test, as a result show, be substantially free of in low-temperature molten salt provided by the invention nitrous acid from
Son, illustrate in preparation process, calcium nitrate is not decomposed substantially, reduces gained finished product low-temperature molten salt most possibly to system
The corrosivity of container.
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat-transfer capability improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 1：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 1.Test result data with
Table 1-3 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
2. second groups of composite fused salts of embodiment
Step 1. prepares this composite fused salt：
(1) KNO is weighed according to the composition of table 2-1 purpose composite fused salt3、NaNO3、LiNO3, and according to Ca (NO3)2Ratio
Example weighs required Ca (NO3)2·4H2O is put into corundum crucible, is mixed；
(2) mixed fused salt is placed in baking oven, 50 DEG C are heated and stirred and heat within 12 hours, 80 DEG C and to stir 12 small
When, 120 DEG C heat and stir 12 hours, 150 DEG C heat and stir until composite fused salt turn into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt.
Table 2-1 low-temperature molten salts 6-10 formula
Note：Wherein calcium nitrate %wt represents Ca (NO in the finally low-temperature molten salt of gained3)2Ratio, the raw material of fused salt is Ca
(NO3)2·4H2O, according to Ca (NO3)2Proportion calculate and it weighs Ca (NO3)2·4H2In O dosage, such as No. 1 fused salt,
Contain 11g Ca (NO in per 100g low-temperature molten salts3)2, due to Ca (NO3)2In Ca (NO3)2·4H2Content in O is about 70%,
Therefore, Ca (NO3)2·4H2O dosage is 11/0.7=15.7g.
For step 2-7. with embodiment 1, test result is shown in 2-2
Table 2-2 low-temperature molten salts 6-10 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.It is significantly higher than in combination property existing
The parallel embodiment of embodiment 2：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 2.Test result data with
Table 2-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 3rd group of composite fused salt of embodiment 3
Step 1. prepares this composite fused salt：
(1) KNO is weighed according to the composition of table 3-1 composite fused salt3、NaNO3、LiNO3, and according to Ca (NO3)2Ratio claim
Take required Ca (NO3)2·4H2O is put into corundum crucible, is mixed；
(2) mixed fused salt is placed in baking oven, 50 DEG C heat and stir 10 hours, 80 DEG C heat and stir 8 hours,
120 DEG C heat and stir 12 hours, 150 DEG C heat and stir until composite fused salt turn into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt.
Table 3-1 low-temperature molten salts 11-15 formula
For step 2-7. with embodiment 1, test result is shown in 2-2
Table 3-2 low-temperature molten salts 11-15 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 3：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 3.Test result data with
Table 3-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 4th group of composite fused salt of embodiment 4
Step 1. prepares this composite fused salt：
(1) KNO is weighed according to the composition of table 4-1 composite fused salt3、NaNO3、LiNO3, and according to Ca (NO3)2Ratio claim
Take required Ca (NO3)2·4H2O is put into corundum crucible, is mixed；
(2) mixed fused salt is placed in baking oven, 50 DEG C are heated and stirred and heat within 12 hours, 80 DEG C and to stir 10 small
When, 120 DEG C heat and stir 8 hours, 150 DEG C heat and stir until composite fused salt turn into uniform solution system；
(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Knot in O
Brilliant water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid
Homogeneous system composite fused salt.
Table 4-1 low-temperature molten salts 16-20 formula
For step 2-7. with embodiment 1, test result is shown in 4-2
Table 4-2 low-temperature molten salts 16-20 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 4：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 4.Test result data with
Table 4-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 5th group of composite fused salt of embodiment 5.
Step 1. molten salt preparation method is the same as embodiment 1.
Table 5-1 low-temperature molten salts 21-26 formula
For step 2-7. with embodiment 1, test result is shown in 5-2
Table 5-2 low-temperature molten salts 21-26 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 5：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 5.Test result data with
Table 2-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 6th group of composite fused salt of embodiment 6.
Step 1. molten salt preparation method is the same as embodiment 1.
Table 6-1 low-temperature molten salts 27-31 formula
For step 2-7. with embodiment 1, test result is shown in 6-2
Table 6-2 low-temperature molten salts 27-31 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 6：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 6.Test result data with
Table 6-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 7th group of composite fused salt of embodiment 7.
Step 1. molten salt preparation method is the same as embodiment 1.
Table 7-1 low-temperature molten salts 32-36 formula
For step 2-7. with embodiment 1, test result is shown in 7-2
Table 7-2 low-temperature molten salts 32-36 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 7：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 7.Test result data with
Table 7-2 shows close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 8th group of composite fused salt of embodiment 8.
Step 1. molten salt preparation method is the same as embodiment 1.
Table 8-1 low-temperature molten salts 37-41 formula
For step 2-7. with embodiment 1, test result is shown in 8-2
Table 8-2 low-temperature molten salts 32-31 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 8：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 8.Test result data with
Table 8-2 shows close.But upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
The 9th group of composite fused salt of embodiment 9
Step 1. molten salt preparation method is the same as embodiment 1.
Table 9-1 low-temperature molten salts 42-49 formula
For step 2-7. with embodiment 1, test result is shown in 9-2 and 9-3
Table 9-2 low-temperature molten salts 42-46 physical property measurement result
9-3 low-temperature molten salts 47-49 physical property measurement result
Saturated vapour pressure measurement result is average in 1.5-1.8 atmospheric pressure, and this pipeline pressure to system is small, therefore more pacifies
It is complete reliable.
Viscosity is low, and heat transfer efficiency is high, and generating efficiency is high, and pipeline blockage reduces, and the security and stability of whole system improves, the longevity
Life increase.
The more conventional fused salt increase of thermal conductivity factor, heat storage capacity improve, and specific heat capacity and the more conventional fused salt of use temperature range are good,
The more conventional fused salt increase of heat storage capacity, the heat accumulation fused salt of isodose, the quantity of heat storage using the fused salt of the present invention are significantly higher than routine
Hitec fused salts, and then reduce the cost for building heat reservoir.
The parallel embodiment of embodiment 9：
With differing only in using four kinds of molten salt monomers after recrystallization purification for embodiment 9.Test result data with
Table 9-2 and 9-3 show close.Upper limit temperature in use all averagely improves about 3-5 degrees Celsius.
Claims (18)
- The accumulation of heat fused salt 1. a kind of low melting point is conducted heat, it is characterised in that：With Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3For raw material It is made, is made up of following preparation process：(1) by four kinds of raw materials of Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3It is put into corundum crucible, mixes；(2) mixed fused salt is placed in baking oven, 24-36 hours is incrementally heated from 50 DEG C of start temperatures, finally at 150 DEG C Heat and stir until composite fused salt turns into uniform solution system；(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Crystallization in O Water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid Homogeneous system composite fused salt；Ca (NO in manufactured fused salt3)2、KNO3、NaNO3、LiNO3The percentage by weight of four kinds of monomer fused salts is as follows：Calcium nitrate 10-16%, potassium nitrate 38-50%, sodium nitrate 23.5-35%, lithium nitrate 3-9%；Calcium nitrate 15-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%；Calcium nitrate 15-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 9%；OrCalcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%.
- The accumulation of heat fused salt 2. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 6-30%, lithium nitrate 3-18%.
- The accumulation of heat fused salt 3. low melting point according to claim 2 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 29-40%, potassium nitrate 35-60%, sodium nitrate 15-30%, lithium nitrate 3-18%.
- The accumulation of heat fused salt 4. low melting point according to claim 2 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 29-40%, potassium nitrate 40-52%, sodium nitrate 6-12%, lithium nitrate 3-14%.
- The accumulation of heat fused salt 5. low melting point according to claim 2 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 29-40%, potassium nitrate 40-49.5%, sodium nitrate 6-12%, lithium nitrate 3-14%.
- The accumulation of heat fused salt 6. low melting point according to claim 2 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 29-40%, potassium nitrate 38-50%, sodium nitrate 6-30%, lithium nitrate 3-9%.
- The accumulation of heat fused salt 7. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 22-30%, potassium nitrate 38-55%, sodium nitrate 6-30%, lithium nitrate 3-9%.
- The accumulation of heat fused salt 8. low melting point according to claim 7 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 22-30%, potassium nitrate 38-49%, sodium nitrate 8-30%, lithium nitrate 3-9%.
- The accumulation of heat fused salt 9. low melting point according to claim 7 is conducted heat, it is characterised in that：The weight percent of four kinds of monomer fused salts Than as follows：Calcium nitrate 22-28%, potassium nitrate 38-50%, sodium nitrate 6-30%, lithium nitrate 3-9%.
- The accumulation of heat fused salt 10. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight hundred of four kinds of monomer fused salts Divide ratio as follows：Calcium nitrate 17-20%, potassium nitrate 36-54%, sodium nitrate 15-30%, lithium nitrate 1-14%.
- The accumulation of heat fused salt 11. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight hundred of four kinds of monomer fused salts Divide ratio as follows：Calcium nitrate 15-28%, potassium nitrate 35-55%, sodium nitrate 21-30%, lithium nitrate 3-9%.
- The accumulation of heat fused salt 12. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight hundred of four kinds of monomer fused salts Divide ratio as follows：Calcium nitrate 15-35%, potassium nitrate 35-55.5%, sodium nitrate 15-30%, lithium nitrate 14.5-18%.
- The accumulation of heat fused salt 13. low melting point according to claim 1 is conducted heat, it is characterised in that：The weight hundred of four kinds of monomer fused salts Divide than shown in following any formula：
- 14. according to any described low melting point heat transfer accumulation of heat fused salts of claim 1-13,0.5-2%wt CsNO may also include3 And/or Sr (NO3)2。
- 15. conducted heat accumulation of heat fused salt according to any described low melting points of claim 1-14, it is described from 50 DEG C of start temperatures incrementally Heating 24-36 hours refer to heat and stir at 50 DEG C 8-12 hours, 80 DEG C heat and stir 8-12 hours, 120 DEG C heat and stir Mix 8-12 hours.
- 16. according to any described low melting point heat transfer accumulation of heat fused salts of claim 1-15, the Ca (NO3)2·4H2O、KNO3、 NaNO3、LiNO3Four kinds of monomer fused salts are by recrystallizing monomer fused salt obtained by purification processes.
- 17. any described low melting points of claim 1-16 conduct heat accumulation of heat fused salt in solar light-heat power-generation, energy storage peak shaving, cleaning Energy source station system and the purposes in other heat transfer accumulation of heat fields.
- 18. the preparation technology of any described low melting point heat transfer accumulation of heat fused salts of claim 1-16：(1) by four kinds of monomers fused salt raw materials of Ca (NO3)2·4H2O、KNO3、NaNO3、LiNO3It is put into corundum crucible, mixes Stirring；(2) mixed fused salt is placed in baking oven, 24-36 hours is incrementally heated from 50 DEG C of start temperatures, finally at 150 DEG C Heat and stir until composite fused salt turns into uniform solution system；(3) composite fused salt is placed in 200-250 DEG C of Muffle furnace, is incubated 8-12 hours, remove Ca (NO3)2·4H2Crystallization in O Water；After water evaporation to be crystallized removes, 350 DEG C are continuously heating to, the moisture in fused salt is thoroughly removed, after cooling, obtains solid Homogeneous system composite fused salt.
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Cited By (4)
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| CN109054773A (en) * | 2018-06-08 | 2018-12-21 | 全球能源互联网研究院有限公司 | A kind of nitric acid Molten Salt Heat Transfer heat storage medium and preparation method thereof |
| CN109097001A (en) * | 2018-09-25 | 2018-12-28 | 中国科学院上海应用物理研究所 | A kind of preparation method of multicomponent chloride eutectics fused salt |
| CN110671517A (en) * | 2019-09-30 | 2020-01-10 | 中国科学院上海应用物理研究所 | Molten salt cut-off device, and use method and application thereof |
| CN111995990A (en) * | 2020-07-31 | 2020-11-27 | 华北电力大学 | Multi-element molten salt with melting point close to room temperature and preparation method thereof |
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| CN113408904B (en) * | 2021-06-21 | 2023-05-30 | 西安热工研究院有限公司 | Fused salt reserve calculation method for fused salt heat storage assisted deep peak shaving of thermal power generating unit |
| CN114699992B (en) * | 2022-02-17 | 2023-01-06 | 四川马边龙泰磷电有限责任公司 | Calcium nitrate pyrolysis device |
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