CN107473201A - A kind of anti-corrosion fused salt material and its preparation method and application - Google Patents
A kind of anti-corrosion fused salt material and its preparation method and application Download PDFInfo
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- CN107473201A CN107473201A CN201710721921.0A CN201710721921A CN107473201A CN 107473201 A CN107473201 A CN 107473201A CN 201710721921 A CN201710721921 A CN 201710721921A CN 107473201 A CN107473201 A CN 107473201A
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- fused salt
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- temperature cabonization
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Abstract
The present invention relates to a kind of synthetic technology of the anti-corrosion fused salt material containing carbon.By can the organic matter of high temperature cabonization be completely dissolved in polar solvent, gained mixture is dispersed in the powder of raw material salt, stirred simultaneously still aging.This mixture is placed in drying box, drying is subject to material.Material after drying is put into nickel crucible and is placed in inert atmosphere high temperature furnace, 350 650 DEG C of 2 3h of insulation is warming up to, is continuously heating to 600 800 DEG C under vacuum condition, after being incubated 2 3h, naturally cools to room temperature, obtain grey black fused salt containing carbon.The present invention is readily synthesized out the homogeneous anti-corrosion fused salt material containing carbon using homogeneous scattered and high temperature cabonization technology.Preparation this method of the present invention has the characteristics that manufacturing cost is cheap, production is convenient, safe and reliable, production technology is easily-controllable, is adapted to large-scale promotion to be used for industrialized production.
Description
Technical field
Present invention relates particularly to a kind of anti-corrosion fused salt new material containing carbon reducing agent.Specifically using homogeneous scattered and
The technology of high temperature cabonization technology, under the high temperature conditions control synthesis anti-corrosion fused salt material.
Background technology
Because fuse salt has, temperature in use is high, temperature range is big, heat exchange property is good, cheap etc. a series of excellent
Point, very extensive application, the particularly rise recently as oil price and the world are obtained in fields such as chemical industry, the energy
Surge of the various countries to energy demand, and the utilization to renewable resource is extremely urgent, solar energy thermal-power-generating technology is as a kind of clear
Clean energy technology has caused the concern of world many countries.
Heat reservoir in solar energy thermal-power-generating technology can get off the storage of solar energy that daytime enriches to meet 24h not
Interval generation, and the fuse salt used in it is paid attention to as heat transfer heat-storage medium by research institution of various countries.Applied at present
For fused salt mainly based on nitrate, but because its high high-temp stability is poor, its maximum operation (service) temperature is 600 DEG C, is unfavorable for improving
The efficiency of utilization of solar heat power generation system.Under this application background, many scholars are proposed to new mixing chlorine
The fused salt research of other high specific surface areas such as salt dissolving, fluoride salt, to applied to solar heat power generation system.
However, the etching problem of fuse salt is one of operating key issue in solar energy thermal-power-generating power station.Research shows,
The main reason for causing metal material to corrode in fused salt is the impurity in fused salt, wherein, water is most critical and most normal in fused salt
With chlorion hydrolysis, i.e. Cl can occur for the impurity seen, water-+H2O=HCl+OH-, the HCl of generation has strong to metal material
Corrosivity, and oxygen is another usual impurities for aggravating fused salt corrosion.But the water and oxygen in air are in solar heat
Inevitably infiltrate into the metal tubes of Molten Salt Heat Transfer in the operation of generating power station, therefore, either contain in initial salt
There are water and oxygen, or water and oxygen in the running of photo-thermal power station in infiltration system, all can be to the gold in metal tubes
Category material causes to corrode.Because carbon can react under higher than certain temperature conditionss with water and oxygen, i.e. C+H2O=H2+
CO, C+O2=CO2, therefore, " preservative " of fused salt can be used as by the use of carbon.
However, being found in practical study, presently commercially available block or different-grain diameter powdery carbon is easily layered with fused salt
Phenomenon, it is difficult to be homogeneously dispersed in fused salt, the presence of which part high content carbon is easily to solar energy thermal-power-generating power station high temperature
Metal material used in fused salt loop causes to corrode.
The content of the invention
It is an object of the invention to provide a kind of anti-corrosion fused salt new material containing carbon reducing agent, wherein carbon can be dispersed
In fused salt, so as to effectively slow down in current solar light-heat power-generation fuse salt to the etching problem of metal material.
The technical solution adopted in the present invention is as follows.
A kind of anti-corrosion fused salt material, using can the organic matter of high temperature cabonization, raw material salt be made as raw material, and the anti-corrosion fused salt
Phosphorus content is controlled in 2000 below ppm, preferably below 700ppm in material.
It is described can high temperature cabonization organic matter be selected under anaerobic, the carbon containing of generation is dehydrated after high-temperature process to be had
Machine thing；Preferably containing-OH ,-CHO ,-COOH ,-NO2、-NO、-SO3H、-NH2, it is RCO-, a kind of in-CH (O) CH- or-COO-
Or a variety of functional groups can high temperature cabonization organic matter, R is referred specifically to for alkane in wherein RCO-；Further preferred phenolic resin,
One or more mixtures in DEXTROSE ANHYDROUS, urea, sucrose or fructose.
The raw material salt is selected from nonoxidizing inorganic salts in the range of 700-800 DEG C of high temperature；It is preferred that halogen, fluoberyllate,
One or more mixtures in silicate, carbonate, phosphate, beryllate；Further preferred KCl, LiCl, NaCl, RuCl,
LiF, NaF, KF, RuF etc. (divalence, trivalent halogen), non-oxidative oxysalt (such as Na2CO3、SrCO3、LiPO3、NaPO3Deng)
And one or more mixtures in other salt.
The present invention a kind of preparation method of anti-corrosion fused salt material is also provided, specifically with can high temperature cabonization organic matter, raw material
Salt is raw material, is made through homogeneous dispersion technology and high temperature cabonization technology.
It is described can high temperature cabonization organic matter and the raw material salt mass ratio be less than 1:500.
The homogeneous dispersion technology refers to：By can the organic matter of high temperature cabonization be completely dissolved in polar solvent, mixed
Compound A, then mixture A is dispersed in the powder of raw material salt, stir and still aging, obtain mixture B.Wherein, it is described
The still aging time is 2-48h.
In the homogeneous dispersion technology, the polar solvent may be selected from polar solvent commonly used in the art, specifically chosen
It can be determined according to the general knowledge that those skilled in the art are grasped.
The high temperature cabonization technology refers to：First by solvent volatilization in mixture B totally, then by material the under noble gas atmosphere
The dehydration carburizing temperature of organic matter is once warming up to, is incubated for the first time；Continuation is warming up to material melts for the second time, vacuumizes, the
Secondary insulation；Room temperature is finally cooled down to, that is, obtains anti-corrosion fused salt material.Wherein, solvent volatilization can use drying or freezing dry
Dry mode.
In the high temperature cabonization technology, the first time programming rate is 1-10 DEG C/min；The first time insulation
Time is 0.5-5h；Second of programming rate is 1-10 DEG C/min；The time of second of insulation is 0.5-5h；Second
The vacuum of secondary insulation is 1 × 10-2-1×105Pa。
Another object of the present invention is to provide the anti-corrosion fused salt material as made from the above method, wherein, the anti-corrosion fused salt material
Phosphorus content is controlled in 2000 below ppm, preferably below 700ppm in material.
Another object of the present invention is to provide above-mentioned anti-corrosion fused salt material in the operating application in solar energy thermal-power-generating power station.
The positive effect of the present invention is：
It is contemplated that a kind of anti-corrosion fused salt new material containing reproducibility carbon of synthesis, it can be avoided because in existing fused salt
Mixed water and oxygen impurities and cause the corrosion of fused salt loop metal material.Carbon in gained anti-corrosion fused salt new material of the invention
It is dispersed in fused salt, no precipitation or lamination, quality is homogeneous, and its condition of storage is not limited strictly, it is only necessary to dry
Dry storage.Gained anti-corrosion fused salt material of the invention when in use, can directly by cold conditions anti-corrosion fused salt be filled into it is existing too
In the fused salt storage tank of positive energy photo-thermal power station high-temperature circuit, heating melting can be used.
The present invention is readily synthesized out the homogeneous anti-corrosion fused salt material containing carbon using homogeneous scattered and high temperature cabonization technology.
Preparation this method of the present invention has the characteristics that manufacturing cost is cheap, production is convenient, safe and reliable, production technology is easily-controllable, fits
Close large-scale promotion and be used for industrialized production.
Brief description of the drawings
Fig. 1 is the outside drawing of anti-corrosion fused salt material prepared by embodiment 1
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
Agents useful for same and raw material of the present invention are commercially available.
In following embodiments, the detecting instrument and detection method of data are as described below：
High frequency infrared ray carbon sulphur analyser, Wuxi City high speed analysis Instrument Ltd., model：HIR-944；Testing standard is joined
Examine：Infrared absorption method (conventional method) after the measure Efco-Northrup furnace burning of the total carbon and sulphur contents of GB-T 20123-2006 steels.
Embodiment 1
740g KCl powders are taken, are put into 1L beakers, then take 0.5g phenolic resin to be dissolved in 100ml absolute ethyl alcohols, and
This solution is added in the beaker equipped with KCl powders, after still aging 24h, beaker is placed in vacuum drying oven, design temperature
For 60 DEG C, material is dried, the material after drying, which is put into nickel crucible, to be placed in noble gas atmosphere high temperature furnace, with 5 DEG C/
Min speed is warming up to 500 DEG C, is incubated 2h, is evacuated to vacuum as 1 × 10-2Pa, being continuously heating to 800 DEG C, (heating is specific
Speed is 5 DEG C/min), after being incubated 3h, naturally cool to room temperature, obtain grey black KCl containing carbon fused salts (be computed containing about
There is 464ppm carbon).
Embodiment 2
After taking 170g LiCl and 447g KCl powders well mixed, it is put into 1L beakers, then take 0.9g DEXTROSE ANHYDROUSs molten
Solution is added in the beaker equipped with LiCl and KCl mixed powders in 500ml deionized waters, and by this solution, and powder is complete
After dissolving, beaker is placed in freeze-drying instrument after 48h, the sample after freeze-drying is put into corundum crucible be placed in it is lazy
Property atmosphere high temperature furnace in, be warming up to 400 DEG C with 1 DEG C/min speed, be incubated 3h, be evacuated to vacuum 1 × 10-1Pa, continue
It is warming up to 600 DEG C (heating rate is 5 DEG C/min), after being incubated 2h, naturally cools to room temperature, obtains grey black containing carbon
ClLiK fused salts (are computed the about carbon containing 583ppm).
Embodiment 3
Take 212g Na2CO3With 444g SrCO3After powder is well mixed, it is put into 1L beakers, then take 2g urea to be dissolved in
In 350ml propanol solutions, and this solution is added to equipped with Na2CO3With SrCO3In the beaker of mixed powder, still aging 18h
Afterwards, beaker is placed in vacuum drying oven, design temperature is 100 DEG C, material is dried, the material after drying is put into graphite earthenware
It is placed in crucible in noble gas atmosphere high temperature furnace, is warming up to 650 DEG C with 10 DEG C/min speed, is incubated 3h, vacuumizes rear vacuum
For 1 × 10-2Pa, continue to be warming up to 800 DEG C with 10 DEG C/min speed, after being incubated 2h, naturally cool to room temperature, obtain ash
Carbonate fused salt (be computed about carbon containing 609ppm) of the black containing carbon.
Embodiment 4
After taking 121g LiF, 48.3g NaF and 244g KF powders well mixed, it is put into 1L beakers, then take 0.5g sugarcanes
Sugar is dissolved in 450ml absolute methanol solutions, and this solution is added in the beaker equipped with mixed powder, still aging 24h
Afterwards, beaker is placed in vacuum drying oven, design temperature is 50 DEG C, material is dried, the material after drying is put into corundum earthenware
It is placed in crucible in noble gas atmosphere high temperature furnace, is warming up to 450 DEG C with 6 DEG C/min speed, is incubated 3h, vacuumizing rear vacuum is
1×104Pa, continue to be warming up to 600 DEG C with 6 DEG C/min speed, after being incubated 2h, naturally cool to room temperature, obtain greyish black
FLiNaK fused salt (be computed about carbon containing 509ppm) of the color containing carbon.
Embodiment 5
Take 215g LiPO3With 255g NaPO3After powder is well mixed, it is put into 1L beakers, then take 1g fructose to be dissolved in
In 300ml diethyl ether solutions, and this solution is added in the beaker equipped with mixed powder, after still aging 12h, beaker be placed in
In vacuum drying oven, design temperature is 80 DEG C, material is dried, the material after drying, which is put into graphite crucible, is placed in noble gas
In atmosphere high temperature furnace, 450 DEG C are warming up to 3 DEG C/min speed, is incubated 3h, vacuumize rear vacuum as 1 × 105Pa, continue
650 DEG C are warming up to 3 DEG C/min speed, after being incubated 2h, room temperature is naturally cooled to, obtains inclined phosphorus of the grey black containing carbon
Hydrochlorate fused salt (is computed the about carbon containing 851ppm).
Compliance test result
At present, metal material used in solar energy thermal-power-generating power station high-temperature molten salt loop is high-temperature alloy steel, is commonly used
Be 316 and 304 stainless steels, their phosphorus content is respectively<0.12% He<0.07%.
And phosphorus content obtained by 1-5 of the embodiment of the present invention in the anti-corrosion fused salt new material containing carbon reducing agent is controllable is formed on
700ppm is (i.e.<0.07%) below.Due to alloy carbon content of steel (with<0.12% He<Based on 0.07%) with anti-corrosion fused salt in
The carbon potential difference very little of phosphorus content, thus, present invention gained new material not only will not be because of the presence of carbon in fused salt and to metal material
Have undesirable effect, " preservative " can be used as effectively to prevent from corroding now in the high-temperature molten salt loop of solar energy thermal-power-generating power station on the contrary
The generation of elephant, achieve significant technological progress.
Claims (10)
- A kind of 1. anti-corrosion fused salt material, it is characterised in that using can the organic matter of high temperature cabonization, raw material salt be made as raw material, and institute State phosphorus content in anti-corrosion fused salt material and be controlled in below 2000ppm, preferably below 700ppm.
- 2. anti-corrosion fused salt material according to claim 1, it is characterised in that it is described can high temperature cabonization organic matter be selected from Under oxygen free condition, the carbonaceous organic material of generation is dehydrated after high-temperature process；Preferably containing-OH ,-CHO ,-COOH ,-NO2 ,- In NO ,-SO3H ,-NH2, RCO- ,-CH (O) CH- or-COO- one or more functional groups can high temperature cabonization organic matter, its In, R is alkyl；One or more mixtures in further preferred phenolic resin, DEXTROSE ANHYDROUS, urea, sucrose or fructose.
- 3. anti-corrosion fused salt material according to claim 1 or 2, it is characterised in that the raw material salt is selected from high temperature 700-800 Nonoxidizing inorganic salts in the range of DEG C；It is preferred that one in halogen, fluoberyllate, silicate, carbonate, phosphate, beryllate Kind or a variety of mixtures；In further preferred KCl, LiCl, NaCl, RuCl, LiF, NaF, KF, RuF, non-oxidative oxysalt One or more mixtures.
- A kind of 4. preparation method of anti-corrosion fused salt material, it is characterised in that using can the organic matter of high temperature cabonization, raw material salt as original Material, is made through homogeneous dispersion technology, high temperature cabonization technology.
- 5. the preparation method of anti-corrosion fused salt material according to claim 4, it is characterised in that it is described can high temperature cabonization have The mass ratio of phosphorus content and the raw material salt in machine thing is less than 1：500.
- 6. the preparation method of the anti-corrosion fused salt material according to claim 4 or 5, it is characterised in that the homogeneously scattered skill Art refers to：By can the organic matter of high temperature cabonization be completely dissolved in polar solvent, obtain mixture A, then mixture A is uniformly divided Dissipate in the powder of raw material salt, stir and still aging, obtain mixture B.
- 7. according to the preparation method of any described anti-corrosion fused salt materials of claim 4-6, it is characterised in that the high temperature cabonization Technology refers to：First by solvent volatilization in mixture B totally, then material is warming up to the de- of organic matter for the first time under noble gas atmosphere Water carburizing temperature, it is incubated for the first time；Continuation is warming up to material melts for the second time, vacuumizes, second of insulation；Finally cool down to Room temperature, that is, obtain anti-corrosion fused salt material.
- 8. the preparation method of anti-corrosion fused salt material according to claim 7, it is characterised in that in the high temperature cabonization technology In, the first time programming rate is 1-10 DEG C/min；The time of the first time insulation is 0.5-5h.
- 9. the preparation method of anti-corrosion fused salt material according to claim 7, it is characterised in that second of programming rate For 1-10 DEG C/min；The time of second of insulation is 0.5-5h；The vacuum condition of second of insulation is 1 × 10-2-1× 105Pa。
- 10. anti-corrosion fused salt material made from any preparation methods of claim 4-9.
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| JP2010132845A (en) * | 2008-12-08 | 2010-06-17 | Nitto Sangyo Kk | Hybrid heat storage agent, heat storage material using the same, and heat retention and storage system utilizing the same |
| CN102888209A (en) * | 2012-09-21 | 2013-01-23 | 中国科学院过程工程研究所 | Medium-high temperature composite structural heat storage material, preparation method and application thereof |
| WO2013045317A1 (en) * | 2011-09-29 | 2013-04-04 | Siemens Aktiengesellschaft | Salt blend as a heat transfer and/or storage medium for solar thermal power plants, process for production thereof |
| US20140202541A1 (en) * | 2013-01-24 | 2014-07-24 | Southwest Research Institute | Encapsulaton Of High Temperature Molten Salts |
| CN105502386A (en) * | 2015-12-17 | 2016-04-20 | 中北大学 | Preparation method of microporous carbon nanosheets |
| CN106517097A (en) * | 2015-09-09 | 2017-03-22 | 中国科学院上海应用物理研究所 | Deoxidation method for molten salt and deoxidated molten salt |
-
2017
- 2017-08-22 CN CN201710721921.0A patent/CN107473201A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010132845A (en) * | 2008-12-08 | 2010-06-17 | Nitto Sangyo Kk | Hybrid heat storage agent, heat storage material using the same, and heat retention and storage system utilizing the same |
| WO2013045317A1 (en) * | 2011-09-29 | 2013-04-04 | Siemens Aktiengesellschaft | Salt blend as a heat transfer and/or storage medium for solar thermal power plants, process for production thereof |
| CN102888209A (en) * | 2012-09-21 | 2013-01-23 | 中国科学院过程工程研究所 | Medium-high temperature composite structural heat storage material, preparation method and application thereof |
| US20140202541A1 (en) * | 2013-01-24 | 2014-07-24 | Southwest Research Institute | Encapsulaton Of High Temperature Molten Salts |
| CN106517097A (en) * | 2015-09-09 | 2017-03-22 | 中国科学院上海应用物理研究所 | Deoxidation method for molten salt and deoxidated molten salt |
| CN105502386A (en) * | 2015-12-17 | 2016-04-20 | 中北大学 | Preparation method of microporous carbon nanosheets |
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