CN119242273A - A low-viscosity liquid sulfur working fluid and its preparation method and application - Google Patents
A low-viscosity liquid sulfur working fluid and its preparation method and application Download PDFInfo
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- CN119242273A CN119242273A CN202411358312.XA CN202411358312A CN119242273A CN 119242273 A CN119242273 A CN 119242273A CN 202411358312 A CN202411358312 A CN 202411358312A CN 119242273 A CN119242273 A CN 119242273A
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Abstract
The invention discloses a low-viscosity liquid sulfur working medium and a preparation method and application thereof, wherein the low-viscosity liquid sulfur working medium comprises liquid sulfur and at least one doping substance, the doping substance contains sodium sulfide or cupric chloride, the doping substance is preferably sodium sulfide nonahydrate or cupric chloride dihydrate, and the weight percentage of the sodium sulfide or cupric chloride to the liquid sulfur is preferably 2-10%. According to the invention, by doping metal salts such as sodium sulfide or copper chloride and the like into liquid sulfur, free hydrogen atoms or chlorine atoms can occupy the tail end position of chain sulfur, and the chain segment of the long-chain sulfur is broken, so that the viscosity of the liquid sulfur working medium is reduced. Compared with dopants with strong volatility such as hydrogen sulfide, halogen, organic substances and the like, the modified sulfur obtained by doping the metal salts has more stable viscosity change and better high-temperature tolerance after heat storage and release circulation for many times, does not decompose the dopants due to high temperature, has simple doping process and low cost, and is favorable for realizing the large-scale application of the liquid sulfur working medium.
Description
Technical Field
The invention belongs to the technical field of high-temperature heat storage, and particularly relates to a low-viscosity liquid sulfur working medium, and a preparation method and application thereof.
Background
Compared with sensible heat materials such as molten salt or phase change heat storage materials, the simple substance sulfur has the advantages that firstly, the simple substance sulfur has abundant reserves in the global scope and extremely low production cost (about 1/5 of commercial molten salt), secondly, the simple substance sulfur has excellent heat stability and can be used as heat storage fluid at high temperature 600 ℃, meanwhile, the low melting point (114 ℃) of the simple substance sulfur is also favorable for keeping the simple substance sulfur to store heat in liquid state at relatively low temperature so as to provide a wider working temperature area, and in addition, experimental and numerical simulation results show that the simple substance sulfur has good heat transfer performance, and the heat charging and discharging rate of a heat storage system is 3-14 times higher than that of a phase change heat storage system (PCM-TES). Therefore, the liquid sulfur heat storage technology with moderate energy density, high thermal stability and low cost is expected to be applied in the future novel energy system in large scale.
However, the viscosity of liquid elemental sulfur is an important factor affecting its heat transfer properties, and the maximum viscosity at 160 ℃ in the lambda transition zone occurs at about 186-188 ℃, a particular viscosity-temperature relationship that may be caused by the polymerization behavior of sulfur. In liquid sulfur, there is a balance between cyclic sulfur (S 8) and chain sulfur (S x, x > 8), and as the temperature increases, the S 8 ring breaks to form longer chain sulfur, and the entanglement and interlacing of these long chains results in an increase in viscosity. After the critical temperature of 188 ℃ is exceeded, chain sulfur starts to break, at this time, the viscosity of the liquid sulfur gradually decreases with increasing temperature, and thus the drastic viscosity change can significantly affect the flow and heat transfer characteristics of the liquid sulfur.
Several doping substances capable of reducing the viscosity of elemental sulfur are screened from the prior research literature, wherein the doping substances comprise hydrogen sulfide, halogen and organic substances, different doping substances have different degrees of influence on the viscosity of sulfur, the temperature zone where the viscosity peak value of sulfur is positioned can be changed, and the mechanism for reducing the viscosity is to break chain segments of long-chain sulfur by occupying the tail end position of chain sulfur through impurity atoms, so that the viscosity is reduced. However, halogen and hydrogen sulfide have high-temperature volatility and toxicity, and hydrogen sulfide needs to be doped in a high-pressure environment, which increases the technical difficulty in industrial application, so that large-scale implementation of such doped modified sulfur is difficult.
Disclosure of Invention
The invention aims to provide a low-viscosity liquid sulfur working medium, a preparation method and application thereof, so as to solve the problem that the existing doped modified sulfur is difficult to realize industrial application due to factors such as safety, manufacturing difficulty, production cost and the like, and provide a new way with simple process, low cost, safety and stability for modifying the liquid sulfur.
In order to achieve the aim, the invention provides a low-viscosity liquid sulfur working medium, which comprises liquid sulfur and at least one doping substance, wherein the doping substance contains sodium sulfide or copper chloride.
Specifically, the doping substance is preferably sodium sulfide nonahydrate, wherein the weight percentage of sodium sulfide to liquid sulfur is preferably 2-10%.
The modified sulfur obtained by doping sodium sulfide nonahydrate can be stably subjected to heat storage and release circulation, the sodium sulfide nonahydrate is low in price and easy to obtain, the doping process is simple, complex equipment or process improvement is not needed, and the viscosity reduction effect is more remarkable than that of sodium sulfide. The reason for limiting the doping proportion is that if the proportion of sodium sulfide is too low, the viscosity reduction effect is difficult to ensure, and if the proportion is too high, the heat storage and release efficiency of the liquid sulfur working medium can be affected.
Specifically, the doping substance is preferably cupric chloride dihydrate, wherein the weight percentage of cupric chloride to liquid sulfur is preferably 2-10%.
The modified sulfur obtained by doping the copper chloride dihydrate can also be subjected to heat storage and release circulation stably, the copper chloride dihydrate is stable in property at room temperature, toxic gases such as hydrogen sulfide and the like can not be released in the heating process, the doping process is simple, complex equipment or process improvement is not needed, and the viscosity reduction effect is more remarkable than that of the copper chloride. The reason for limiting the doping proportion is that if the proportion of the copper chloride is too low, the viscosity reduction effect is difficult to ensure, and if the proportion is too high, the heat storage and release efficiency of the liquid sulfur working medium can be affected.
Further, the invention also discloses a preparation method of the low-viscosity liquid sulfur working medium, which comprises the following steps:
And dissolving the doping substance in liquid sulfur to form a low-viscosity liquid sulfur working medium.
In particular, it is preferable that the dopant is dissolved in liquid sulfur after being ground.
In addition, the invention also comprises application of the low-viscosity liquid sulfur working medium, and the low-viscosity liquid sulfur working medium can be used for reversible energy storage.
The beneficial effects are that:
According to the invention, by doping metal salts such as sodium sulfide or copper chloride and the like into liquid sulfur, free hydrogen atoms or chlorine atoms can occupy the tail end position of chain sulfur, and the chain segment of the long-chain sulfur is broken, so that the viscosity of the liquid sulfur working medium is reduced. Compared with dopants with strong volatility such as hydrogen sulfide, halogen, organic substances and the like, the modified sulfur obtained by doping the metal salts has more stable viscosity change after heat storage and release circulation for a plurality of times, has better high-temperature tolerance, does not decompose the dopants due to high temperature, has simple doping process and low cost, and is favorable for realizing the large-scale application of the liquid sulfur working medium.
Drawings
FIG. 1 is a schematic diagram of the composition of the liquid sulfur working medium in the invention;
FIG. 2 is a graph showing the viscosity change of three liquid sulfur working fluids at high temperature in example 1 of the present invention;
Fig. 3 is a graph showing the viscosity change of three liquid sulfur working fluids at high temperature in example 2 of the present invention.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 shows a low-viscosity liquid sulfur working medium provided by the invention, which comprises liquid sulfur and at least one doping substance, wherein the doping substance contains sodium sulfide or copper chloride. The low-viscosity liquid sulfur working medium can be applied to reversible energy storage, and particularly can be applied to the technical field of high-temperature heat storage.
Example 1:
sodium sulfide nonahydrate was selected as a doping substance, and 2%, 5% and 10% by weight of sodium sulfide were doped into liquid sulfur, respectively, whereby a viscosity test at high temperature was performed. As can be seen from fig. 2, these three modified sulfur compounds achieve a significant viscosity reduction effect, and the viscosity peak of the liquid sulfur working fluid can be reduced from 90000mpa·s to 1700mpa·s, 740mpa·s and 250mpa·s.
Example 2:
Copper chloride dihydrate is selected as the doping substance, which is subjected to a grinding pretreatment in order to react more fully with the liquid sulfur. The viscosity test at high temperature was performed by incorporating 2%, 5% and 10% by weight of copper chloride in liquid sulfur, respectively. As can be seen from fig. 3, these three modified sulfur compounds can also achieve a significant viscosity reduction effect, and the viscosity peak of the liquid sulfur working fluid can be reduced from 90000mpa·s to 350mpa·s, 230mpa·s, and 140mpa·s.
The high-temperature viscosimeter in the experiment adopts a rotary method to test the viscosity of the high-temperature melt, and mainly determines the viscosity of the fluid by measuring the viscous moment of the fluid acting on the rotor, and performs effective calibration before testing so as to ensure the accuracy of a test result. Meanwhile, in order to verify the stability of the modified sulfur, each liquid sulfur working medium is subjected to heat storage and release cycles for more than 3 times, and for the same liquid sulfur working medium, the obtained viscosity test curves are basically the same, which shows that the dopant is not decomposed due to high temperature, and the high temperature tolerance is better than that of the dopant with volatility.
Through a great deal of experimental researches, not all metal salts can effectively improve the viscosity of the liquid sulfur working medium, such as NaCl, znCl2 and the like, but doping substances containing sodium sulfide or cupric chloride can realize effective viscosity reduction effects, such as sodium sulfide or cupric chloride, but have weaker effects compared with metal salts containing hydrate. The two metal salts are modified by the principle that sodium sulfide has hygroscopicity in the doping process, partial hydrogen sulfide can be generated, so that hydrogen atoms occupy the tail end position of chain sulfur to break the chain segment of the chain sulfur, thereby effectively reducing the viscosity of the liquid sulfur working medium, and chlorine atoms in copper chloride can directly occupy the tail end position of the chain sulfur to break the chain segment of the chain sulfur, thereby effectively reducing the viscosity of the liquid sulfur working medium.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A low viscosity liquid sulfur working fluid comprising liquid sulfur and at least one dopant species comprising sodium sulfide or copper chloride.
2. The low viscosity liquid sulfur working medium of claim 1, wherein the doping substance is sodium sulfide nonahydrate, and the weight percentage of sodium sulfide to liquid sulfur is 2-10%.
3. The low viscosity liquid sulfur working medium of claim 1, wherein the doping substance is cupric chloride dihydrate, and the weight percentage of cupric chloride to liquid sulfur is 2-10%.
4. A method for preparing a low viscosity liquid sulfur working medium according to any one of claims 1 to 3, comprising:
And dissolving the doping substance in liquid sulfur to form a low-viscosity liquid sulfur working medium.
5. The method according to claim 4, wherein the dopant is ground and dissolved in liquid sulfur.
6. The use of a low viscosity liquid sulfur working medium as claimed in claim 1, wherein, the low-viscosity liquid sulfur working medium is used for reversible energy storage.
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| CN202411358312.XA CN119242273B (en) | 2024-09-27 | 2024-09-27 | Low-viscosity liquid sulfur working medium and preparation method and application thereof |
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| CN119242273B CN119242273B (en) | 2025-12-09 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008046071A1 (en) * | 2008-09-05 | 2010-03-11 | Sterzel, Christoph Henrik | Use of a heat transfer liquid comprising sulfur modified with inorganic components, to transport and storage of heat energy |
| CN102177216A (en) * | 2008-09-05 | 2011-09-07 | 弗拉格赛欧股份有限公司 | Application of Improved, Low Viscosity Sulfur as a Heat Conducting and Storage Fluid |
| CN102695671A (en) * | 2010-01-05 | 2012-09-26 | 巴斯夫欧洲公司 | Heat transfer and heat storage fluids for extremely high temperatures, based on polysulfides |
| CN102884154A (en) * | 2010-04-09 | 2013-01-16 | 巴斯夫欧洲公司 | Fluid sulfur with improved viscosity as heat transfer medium |
| US20130037741A1 (en) * | 2010-04-20 | 2013-02-14 | Juergen Birnbaum | Heat transfer medium based on sulphur and use of the heat transfer medium |
| CN104428241A (en) * | 2012-06-01 | 2015-03-18 | 阿克马法国公司 | Low-viscosity liquid sulphur |
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- 2024-09-27 CN CN202411358312.XA patent/CN119242273B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008046071A1 (en) * | 2008-09-05 | 2010-03-11 | Sterzel, Christoph Henrik | Use of a heat transfer liquid comprising sulfur modified with inorganic components, to transport and storage of heat energy |
| CN102177216A (en) * | 2008-09-05 | 2011-09-07 | 弗拉格赛欧股份有限公司 | Application of Improved, Low Viscosity Sulfur as a Heat Conducting and Storage Fluid |
| US20110259552A1 (en) * | 2008-09-05 | 2011-10-27 | Flagsol Gmbh | Use of modified, low-viscosity sulfur as heat transfer and heat storage fluid |
| CN102695671A (en) * | 2010-01-05 | 2012-09-26 | 巴斯夫欧洲公司 | Heat transfer and heat storage fluids for extremely high temperatures, based on polysulfides |
| CN102884154A (en) * | 2010-04-09 | 2013-01-16 | 巴斯夫欧洲公司 | Fluid sulfur with improved viscosity as heat transfer medium |
| US20130037741A1 (en) * | 2010-04-20 | 2013-02-14 | Juergen Birnbaum | Heat transfer medium based on sulphur and use of the heat transfer medium |
| CN104428241A (en) * | 2012-06-01 | 2015-03-18 | 阿克马法国公司 | Low-viscosity liquid sulphur |
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