WO2020168605A1 - Modified chloride molten salt, preparation method and application thereof - Google Patents
Modified chloride molten salt, preparation method and application thereof Download PDFInfo
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- WO2020168605A1 WO2020168605A1 PCT/CN2019/078265 CN2019078265W WO2020168605A1 WO 2020168605 A1 WO2020168605 A1 WO 2020168605A1 CN 2019078265 W CN2019078265 W CN 2019078265W WO 2020168605 A1 WO2020168605 A1 WO 2020168605A1
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- the invention belongs to the field of energy storage materials, and relates to a molten salt, in particular to a modified chloride molten salt, and a preparation method and application thereof.
- Solar thermal power generation (Concentrating Solar Power, CSP for short) is a very promising renewable resource.
- Heat transfer and storage technology is one of the key technologies in the solar thermal power generation system.
- the heat transfer and storage media used for solar thermal power generation mainly include steam and water, heat transfer oil, liquid metal, hot air, molten salt, etc.
- molten salt As a high-temperature heat transfer and storage fluid, molten salt has good thermal conductivity, low vapor pressure, wide operating temperature range, and low price, making it a candidate medium with great potential for development. Its heat absorption efficiency has a great impact on the power generation efficiency of the entire CSP system. influences.
- the use of molten salt as a medium to directly absorb solar energy has been used as early as the 1990s.
- molten salt As an inorganic compound, molten salt has low viscosity, good thermal conductivity, weak corrosiveness, low vapor pressure, wide operating temperature range, and low price, making it the first choice for medium and high temperature heat transfer and heat storage materials. Studies have shown that, compared with high-temperature heat transfer oil, the use of molten salt (nitrate molten salt) can increase the maximum operating temperature of solar power stations to about 500°C and increase the power generation efficiency of steam turbines to 40%.
- the most used molten salt for solar thermal power generation is nitrate molten salt as a heat transfer and storage material, such as Solar Salt (60% KNO 3 -40wt% NaNO 3 ) and Hitec molten salt (53% KNO 3 -7%NaNO) 3 -40wt% NaNO 2 ).
- the upper limit of the mixed nitrate molten salt system is generally 550°C. As the working temperature rises, the molten nitrate will degrade and decompose, and the stability of the molten salt is poor; and the thermal conductivity of molten nitrate is very low.
- the minimum eutectic temperature of mixed molten salt of 56.6mol% Na 2 CO 3 +43.4mol% K 2 CO 3 is 710°C, which is stable below 830°C, but the melting point of carbonate is higher and the viscosity of liquid carbonate is higher. And the corrosiveness is relatively large, and some carbonates are easy to decompose, which largely limits their large-scale application.
- CN 104109508 A discloses a nitrate system molten salt heat storage material consisting of potassium nitrate and sodium nitrate, the mass ratio of sodium nitrate and potassium nitrate is 30-70:30-70, and the potassium nitrate and sodium nitrate are the Ca 2+, Mg 2+, Cl - , SO 4 2- ion content of impurities each less than 100ppm, 100ppm, 200ppm and 300ppm.
- the invention is based on Solar Salt molten salt, and improves the thermal stability of Solar Salt molten salt through purification process and impurity ion control, and extends the service life and operating cost of heat storage materials.
- the molten salt provided by the invention has a low thermal conductivity and a relatively high melting point.
- the present invention provides a modified chloride molten salt.
- the molten salt reduces the melting point, increases the upper limit temperature of the work, and improves the power generation efficiency of solar thermal power generation.
- the thermal conductivity is better, the heat transfer and heat storage performance is better, it can avoid the local overheating problem of the device, it can also reduce the amount of heat transfer and storage medium, reduce the volume of related transportation and storage equipment, and reduce the operating cost.
- the present invention provides a modified chloride molten salt.
- the raw materials of the molten salt include chloride and metal powder.
- the metal chloride includes sodium chloride and potassium chloride.
- the metal powder includes metal aluminum powder and/or metal zinc powder.
- the raw materials of the molten salt include sodium chloride, potassium chloride, metal aluminum powder and metal zinc powder.
- the present invention forms a modified mixed chloride molten salt by adding components such as metal aluminum powder and metal zinc powder with higher thermal conductivity on the basis of sodium chloride and potassium chloride. Since the melting point of metallic zinc is 419.5°C and that of metallic aluminum powder is 660°C, the melting point of the mixed chloride molten salt formed after modification is lower than that of single salts such as sodium chloride and potassium chloride. Since the thermal conductivity of metallic aluminum powder is 270W/(m ⁇ K) and that of metallic zinc powder is 176W/(m ⁇ K), a small amount of addition can significantly improve the thermal conductivity of the mixed chloride molten salt.
- the raw materials of the molten salt in terms of mass fraction include:
- the mass fraction of sodium chloride can be 42%, 43%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, etc.
- potassium chloride The mass fraction of aluminum powder can be 30%, 31%, 32%, 35%, 38%, 40%, 42% or 45%, etc.
- the mass fraction of metal aluminum powder can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%, etc.
- the mass fraction of metal zinc powder can be 2%, 3%, 4%, 5%, 6%, 7%, 8 %, 9% or 10%, etc., but are not limited to the listed values, and other unlisted values within the above numerical ranges are also applicable.
- the mass fraction of metallic aluminum powder and metallic zinc powder in the molten salt is too small to improve the thermal conductivity of the mixed molten salt, and has little effect on its thermal conductivity; if the mass fraction is too large, the molten salt causes Mixed molten salt cannot form a eutectic mixture.
- the raw materials of the molten salt in terms of mass fraction include:
- the second aspect of the present invention is to provide a method for preparing the above-mentioned modified chloride molten salt.
- the method includes the following steps:
- the metal aluminum powder and metal zinc powder are prepared into metal aluminum and zinc mixed particles by ball milling.
- the metal aluminum and zinc mixed particles are mixed with the chloride; the mixture is heated to a molten state, the heating temperature is 780-830°C, and the holding time is 12-24 hours. .
- the cooled mixed molten salt is removed from the crucible, crushed into particles by mechanical methods, and sealed and stored in a sealed bag for use.
- the heating and heat preservation temperature is 780 ⁇ 830°C, such as 780°C, 785°C, 790°C, 795°C, 800°C, 805°C, 810°C, 815°C, 820°C, 825°C Or 830°C, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.
- the calcination temperature is higher than 850°C, which will cause the molten salt to deteriorate and decompose, and the thermal stability will be poor; the calcination temperature below 780°C will result in low power generation temperature and low power generation efficiency.
- the heat preservation time is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc., but it is not limited to For the listed values, other unlisted values within the range of values also apply.
- the metal powder In the preparation method of the present invention, if the particles of the metal powder are too large, the metal powder needs to be ball-milled and refined.
- the molten salt obtained after calcination and cooling has a relatively large particle size and needs to be crushed and ground into smaller particles for storage and transportation.
- the third object of the present invention is to provide an application of the above-mentioned chlorinated modified molten salt, which is used in the fields of solar thermal power generation, solar hydrogen production reaction, and industrial waste heat recovery.
- the present invention has at least the following beneficial effects:
- the mixed chloride molten salt of the present invention can lower the melting point and increase the upper limit operating temperature, improve the power generation efficiency of solar thermal power generation, etc.
- the lowering of the melting point can also save the insulation cost; at the same time, it also expands the use temperature range of the molten salt and can be applied In the related fields of solar thermal power generation, solar hydrogen production reaction and industrial waste heat recovery;
- the modified mixed chloride molten salt of the present invention has increased thermal conductivity, better heat transfer and heat storage performance, can avoid local overheating problems in the device, and can also reduce the amount of heat transfer and storage media, and reduce related transportation, The volume of storage equipment reduces operating costs.
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state at 780° C. and kept for 24 hours, and the molten salt is obtained after cooling.
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state and kept at 830° C. for 12 hours, and the molten salt is obtained after cooling.
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state and kept at 800° C. for 20 hours, and the molten salt is obtained after cooling.
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
- This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- This comparative example provides a modified chloride molten salt.
- the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the metal zinc powder is ball-milled and mixed with sodium chloride and potassium chloride to obtain a mixture; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
- This comparative example provides a modified chloride molten salt.
- the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the metal aluminum powder is ball-milled and mixed with sodium chloride and potassium chloride to obtain a mixture; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
- This comparative example provides a chloride molten salt.
- the raw materials of the molten salt in terms of mass fraction include:
- the preparation method of the molten salt is:
- the sodium chloride and potassium chloride are mixed according to the above-mentioned mass fraction; the mixture is heated to a molten state and kept at 790° C. for 18 hours, and the molten salt is obtained after cooling.
- This comparative example provides a chloride molten salt.
- the molten salt has the same conditions as in Example 3 except that the heating and holding temperature in the preparation method is 780°C.
- This comparative example provides a chloride molten salt.
- the molten salt has the same conditions as in Example 3 except that the heating and holding temperature in the preparation method is 900°C.
- Example 1 765.8 950°C 3.788
- Example 2 755.6 960°C 4.215
- Example 3 761.2 980°C 4.873
- Example 4 762.9 980°C 4.576
- Example 5 764.5 970°C 4.019
- Example 6 764.8 980°C 4.158 Comparative example 1 771.6 900°C 3.134 Comparative example 2 773.5 900°C 3.381 Comparative example 3 786.4 900°C 2.689 Comparative example 4 756.2 950°C 2.672 Comparative example 5 786.8 950°C 2.679
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Abstract
The invention relates to a modified chloride molten salt, a preparation method and an application thereof. The raw material of the molten salt comprises chloride and metal powder. The molten salt lowers the melting point, increases the upper operating temperature limit, and increases the power generation efficiency of solar thermal power generation. In addition, the molten salt has a larger thermal conductivity, better heat transfer and heat storage performance, and can help prevent local overheating of a device. The use of a heat transfer and a heat storage medium can also be reduced, thereby reducing the volume of transportation and storage equipment and lowering operating costs.
Description
本发明属于储能材料领域，涉及一种熔盐，尤其涉及一种改性氯化物熔盐及其制备方法和应用。The invention belongs to the field of energy storage materials, and relates to a molten salt, in particular to a modified chloride molten salt, and a preparation method and application thereof.
太阳能热发电(Concentrating Solar Power，简称CSP)是一种非常有发展前途的可再生资源。传热蓄热技术是太阳能热发电系统中的关键技术之一，用于太阳能热发电的传热蓄热介质主要有蒸汽和水、导热油、液态金属、热空气、熔盐等。熔盐作为一种高温传蓄热流体，导热性能好、蒸汽压低、使用温度范围广、价格便宜，使其成为非常有发展潜力的候选介质，其吸热效率对整个CSP系统发电效率有很大影响。使用熔盐作为直接吸收太阳能的介质，早在上世纪九十年代就已经得到应用。Solar thermal power generation (Concentrating Solar Power, CSP for short) is a very promising renewable resource. Heat transfer and storage technology is one of the key technologies in the solar thermal power generation system. The heat transfer and storage media used for solar thermal power generation mainly include steam and water, heat transfer oil, liquid metal, hot air, molten salt, etc. As a high-temperature heat transfer and storage fluid, molten salt has good thermal conductivity, low vapor pressure, wide operating temperature range, and low price, making it a candidate medium with great potential for development. Its heat absorption efficiency has a great impact on the power generation efficiency of the entire CSP system. influences. The use of molten salt as a medium to directly absorb solar energy has been used as early as the 1990s.
熔融盐作为一种无机化合物，粘度小、导热性能好、腐蚀性弱、蒸汽压低、使用温度范围广、价格便宜，成为中高温传热蓄热材料的首选。研究表明，与高温导热油相比，运用熔融盐(硝酸熔盐)可以使太阳能电站最高工作温度提高到500℃左右，使得蒸汽轮机发电效率提高到40％。As an inorganic compound, molten salt has low viscosity, good thermal conductivity, weak corrosiveness, low vapor pressure, wide operating temperature range, and low price, making it the first choice for medium and high temperature heat transfer and heat storage materials. Studies have shown that, compared with high-temperature heat transfer oil, the use of molten salt (nitrate molten salt) can increase the maximum operating temperature of solar power stations to about 500°C and increase the power generation efficiency of steam turbines to 40%.
目前，太阳能热发电使用最多的熔盐是硝酸熔盐作为传热蓄热材料，例如Solar Salt熔盐(60％KNO
3-40wt％NaNO
3)和Hitec熔盐(53％KNO
3-7％NaNO
3-40wt％NaNO
2)。混合硝酸熔盐体系存在上限使用温度一般在550℃，随着工作温度的升高，硝酸熔盐会产生劣化分解，熔盐的稳定性较差；且硝酸熔盐存在导热系数很低，一般在0.4～0.6W/(m·K)之间，再同一热功率下，需要更多传热蓄热材料，增大了储热系统尺寸，增加了电站的运行难度，提高 了成本。56.6mol％Na
2CO
3+43.4mol％K
2CO
3混合熔盐最低共熔温度为710℃，在低于830℃时性质稳定，但是碳酸盐的熔点较高且液态碳酸盐的粘度和腐蚀性均比较大，有些碳酸盐容易分解，很大程度上限制了其规模化应用。
At present, the most used molten salt for solar thermal power generation is nitrate molten salt as a heat transfer and storage material, such as Solar Salt (60% KNO 3 -40wt% NaNO 3 ) and Hitec molten salt (53% KNO 3 -7％NaNO) 3 -40wt% NaNO 2 ). The upper limit of the mixed nitrate molten salt system is generally 550℃. As the working temperature rises, the molten nitrate will degrade and decompose, and the stability of the molten salt is poor; and the thermal conductivity of molten nitrate is very low. Between 0.4 and 0.6W/(m·K), under the same thermal power, more heat transfer and heat storage materials are needed, which increases the size of the heat storage system, increases the difficulty of power station operation, and increases the cost. The minimum eutectic temperature of mixed molten salt of 56.6mol% Na 2 CO 3 +43.4mol% K 2 CO 3 is 710℃, which is stable below 830℃, but the melting point of carbonate is higher and the viscosity of liquid carbonate is higher. And the corrosiveness is relatively large, and some carbonates are easy to decompose, which largely limits their large-scale application.
CN 104109508 A公开了一种硝酸盐体系熔盐储热材料由硝酸钾和硝酸钠组成，所述硝酸钠和硝酸钾的质量比为30～70∶30～70，所述硝酸钾和硝酸钠中的Ca
2+、Mg
2+、Cl
-、SO
4
2-杂质离子含量分别小于100ppm、100ppm、200ppm以及300ppm。该发明已Solar Salt熔盐为基础，通过提纯工艺和杂质离子控制提高了Solar Salt熔盐的热稳定性，延长储热材质的使用寿命和运行成本。但是该发明提供的熔盐的导热系数较低，熔点也相对偏高。
CN 104109508 A discloses a nitrate system molten salt heat storage material consisting of potassium nitrate and sodium nitrate, the mass ratio of sodium nitrate and potassium nitrate is 30-70:30-70, and the potassium nitrate and sodium nitrate are the Ca 2+, Mg 2+, Cl - , SO 4 2- ion content of impurities each less than 100ppm, 100ppm, 200ppm and 300ppm. The invention is based on Solar Salt molten salt, and improves the thermal stability of Solar Salt molten salt through purification process and impurity ion control, and extends the service life and operating cost of heat storage materials. However, the molten salt provided by the invention has a low thermal conductivity and a relatively high melting point.
目前，随着太阳能热发电和太阳能制氢的工作温度更高，提出了对传热蓄热介质性能更高的要求。迫切需要工作温度上限高、熔点低、导热系数高等优点的传热蓄热熔盐介质，从而提高太阳能热发电的发电效率、工业余热回收效率、节约成本等。At present, with the higher working temperature of solar thermal power generation and solar hydrogen production, higher requirements for the performance of heat transfer and storage media have been put forward. There is an urgent need for a heat transfer and storage molten salt medium with the advantages of high working temperature upper limit, low melting point, and high thermal conductivity, so as to improve the power generation efficiency of solar thermal power generation, industrial waste heat recovery efficiency, and cost savings.
发明内容Summary of the invention
为解决上述技术问题，本发明提供一种改性氯化物熔盐，所述熔盐降低了熔点，提高了工作上限温度，提高了太阳能热发电的发电效率，同时所述熔盐就有较大的导热系数，传热蓄热性能更好，能避免装置局部出现过热问题，也可以减少传热蓄热介质用量，减少有关运输、储存设备的体积，降低运行成本。In order to solve the above technical problems, the present invention provides a modified chloride molten salt. The molten salt reduces the melting point, increases the upper limit temperature of the work, and improves the power generation efficiency of solar thermal power generation. The thermal conductivity is better, the heat transfer and heat storage performance is better, it can avoid the local overheating problem of the device, it can also reduce the amount of heat transfer and storage medium, reduce the volume of related transportation and storage equipment, and reduce the operating cost.
本发明提供一种改性氯化物熔盐，所述熔盐的原料包括氯化物以及金属粉。The present invention provides a modified chloride molten salt. The raw materials of the molten salt include chloride and metal powder.
作为本发明的技术方案，所述金属氯化物包括氯化钠和氯化钾。As a technical solution of the present invention, the metal chloride includes sodium chloride and potassium chloride.
作为本发明优选的技术方案，所述金属粉包括金属铝粉和/或金属锌粉。As a preferred technical solution of the present invention, the metal powder includes metal aluminum powder and/or metal zinc powder.
作为本发明的技术方案，所述熔盐的原料包括氯化钠、氯化钾、金属铝粉和金属锌粉。As a technical solution of the present invention, the raw materials of the molten salt include sodium chloride, potassium chloride, metal aluminum powder and metal zinc powder.
本发明通过在氯化钠、氯化钾的基础上添加导热系数更高的金属铝粉、金属锌粉等成分，形成改性的混合氯化物熔盐。由于金属锌熔点为419.5℃，金属铝粉的熔点为660℃，改性后形成的混合氯化物熔盐的熔点低于氯化钠、氯化钾等单盐的熔点。由于金属铝粉的导热系数为270W/(m·K)和金属锌粉的导热系数为176W/(m·K)，微量的添加就能显著提高混合氯化物熔盐的导热性能。The present invention forms a modified mixed chloride molten salt by adding components such as metal aluminum powder and metal zinc powder with higher thermal conductivity on the basis of sodium chloride and potassium chloride. Since the melting point of metallic zinc is 419.5°C and that of metallic aluminum powder is 660°C, the melting point of the mixed chloride molten salt formed after modification is lower than that of single salts such as sodium chloride and potassium chloride. Since the thermal conductivity of metallic aluminum powder is 270W/(m·K) and that of metallic zinc powder is 176W/(m·K), a small amount of addition can significantly improve the thermal conductivity of the mixed chloride molten salt.
作为本发明的技术方案，按照质量分数计所述熔盐的原料包括：As a technical solution of the present invention, the raw materials of the molten salt in terms of mass fraction include:
其中，氯化钠的质量分数可以是42％、43％、45％、48％、50％、52％、55％、58％、60％、62％、65％或68％等，氯化钾的质量分数可以是30％、31％、32％、35％、38％、40％、42％或45％等，金属铝粉的质量分数可以是2％、3％、4％、5％、6％、7％、8％、9％、10％、11％或12％等，金属锌粉的质量的分数可以是2％、3％、4％、5％、6％、7％、8％、9％或10％等，但并不仅限于所列举的数值，上述各数值范围内其他未列举的数值同样适用。Among them, the mass fraction of sodium chloride can be 42%, 43%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, etc., potassium chloride The mass fraction of aluminum powder can be 30%, 31%, 32%, 35%, 38%, 40%, 42% or 45%, etc. The mass fraction of metal aluminum powder can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%, etc., the mass fraction of metal zinc powder can be 2%, 3%, 4%, 5%, 6%, 7%, 8 %, 9% or 10%, etc., but are not limited to the listed values, and other unlisted values within the above numerical ranges are also applicable.
本发明中，所述熔盐中金属铝粉和金属锌粉的质量分数过小，起不到提高混合熔盐的导热系数作用，对其导热性能影响不大；质量分数过大，熔盐造成混合熔盐无法形成共融的混合物。In the present invention, the mass fraction of metallic aluminum powder and metallic zinc powder in the molten salt is too small to improve the thermal conductivity of the mixed molten salt, and has little effect on its thermal conductivity; if the mass fraction is too large, the molten salt causes Mixed molten salt cannot form a eutectic mixture.
作为本发明更佳的技术方案，按照质量分数计所述熔盐的原料包括：As a better technical solution of the present invention, the raw materials of the molten salt in terms of mass fraction include:
本发明之二在于提供一种上述改性氯化物熔盐的制备方法，所述方法包括扩以下步骤：The second aspect of the present invention is to provide a method for preparing the above-mentioned modified chloride molten salt. The method includes the following steps:
用球磨法将金属铝粉和金属锌粉制备成金属铝、锌混合颗粒。The metal aluminum powder and metal zinc powder are prepared into metal aluminum and zinc mixed particles by ball milling.
将金属铝、锌混合颗粒与氯化物混合；将所述混合物加热至熔融状态，加热温度为780-830℃，保温时间为12～24小时。。The metal aluminum and zinc mixed particles are mixed with the chloride; the mixture is heated to a molten state, the heating temperature is 780-830°C, and the holding time is 12-24 hours. .
将混合熔盐从马弗炉中取出，放入干燥皿中冷却到室温。Take the mixed molten salt out of the muffle furnace and place it in a drying dish to cool to room temperature.
将冷却后的混合熔盐从坩埚中取去，利用机械方法粉碎成颗粒，并用密封袋对其密封保存，以备使用。The cooled mixed molten salt is removed from the crucible, crushed into particles by mechanical methods, and sealed and stored in a sealed bag for use.
作为本发明的技术方案，所述加热及保温的温度为780～830℃，如780℃、785℃、790℃、795℃、800℃、805℃、810℃、815℃、820℃、825℃或830℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。As the technical solution of the present invention, the heating and heat preservation temperature is 780～830℃, such as 780℃, 785℃, 790℃, 795℃, 800℃, 805℃, 810℃, 815℃, 820℃, 825℃ Or 830°C, etc., but not limited to the listed values, and other unlisted values within this range are also applicable.
本发明中，煅烧温度大于850℃，会导致熔盐劣化与分解，热稳定性能较差；煅烧温度低于780℃会导致发电温度时不高，发电效率偏低。In the present invention, the calcination temperature is higher than 850°C, which will cause the molten salt to deteriorate and decompose, and the thermal stability will be poor; the calcination temperature below 780°C will result in low power generation temperature and low power generation efficiency.
作为本发明的技术方案，所述保温的时间为12～24h，如12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h或24h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。As a technical solution of the present invention, the heat preservation time is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc., but it is not limited to For the listed values, other unlisted values within the range of values also apply.
本发明所述制备方法中，如金属粉的颗粒度过大，则需要对金属粉进行球磨细化。煅烧冷却后得到的熔盐的颗粒度较大，需要经过粉碎以及研磨等处理成较小的颗粒以便储存和运输。In the preparation method of the present invention, if the particles of the metal powder are too large, the metal powder needs to be ball-milled and refined. The molten salt obtained after calcination and cooling has a relatively large particle size and needs to be crushed and ground into smaller particles for storage and transportation.
本发明目的之三在于提供一种上述氯化改性熔盐的应用，所述熔盐用于太阳能热发电、太阳能制氢反应及工业余热回收领域。The third object of the present invention is to provide an application of the above-mentioned chlorinated modified molten salt, which is used in the fields of solar thermal power generation, solar hydrogen production reaction, and industrial waste heat recovery.
与现有技术相比，本发明至少具有以下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:
(1)本发明混合氯化物熔盐能降低熔点和提高上限工作温度，提高太阳能热发电的发电效率等，熔点的降低也可以节省保温成本；同时也扩大了熔盐的使用温度范围，可以应用于太阳能热发电、太阳能制氢反应及工业余热回收等相关领域；(1) The mixed chloride molten salt of the present invention can lower the melting point and increase the upper limit operating temperature, improve the power generation efficiency of solar thermal power generation, etc. The lowering of the melting point can also save the insulation cost; at the same time, it also expands the use temperature range of the molten salt and can be applied In the related fields of solar thermal power generation, solar hydrogen production reaction and industrial waste heat recovery;
(2)本发明改性后的混合氯化物熔盐的导热系数增大，传热蓄热性能更好，能避免装置局部出现过热问题，也可以减少传热蓄热介质用量，减少有关运输、储存设备的体积，降低运行成本。(2) The modified mixed chloride molten salt of the present invention has increased thermal conductivity, better heat transfer and heat storage performance, can avoid local overheating problems in the device, and can also reduce the amount of heat transfer and storage media, and reduce related transportation, The volume of storage equipment reduces operating costs.
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。To facilitate the understanding of the present invention, examples of the present invention are listed below. Those skilled in the art should understand that the described embodiments are only to help understand the present invention and should not be regarded as specific limitations to the present invention.
实施例1Example 1
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在780℃下并保温24h，冷却后得到所述熔盐。The ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state at 780° C. and kept for 24 hours, and the molten salt is obtained after cooling.
实施例2Example 2
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在830℃下保温12h，冷却后得到所述熔盐。The ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state and kept at 830° C. for 12 hours, and the molten salt is obtained after cooling.
实施例3Example 3
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在800℃下保温20h，冷却后得到所述熔盐。The ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state and kept at 800° C. for 20 hours, and the molten salt is obtained after cooling.
实施例4Example 4
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在820℃下保温16h，冷却后得到所述熔盐。Mix the ball-milled metal aluminum and metal zinc particles with sodium chloride and potassium chloride according to the above-mentioned mass fraction; heat the mixture to a molten state at 820° C. for 16 hours, and obtain the molten salt after cooling.
实施例5Example 5
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在790℃下保温18h，冷却后得到所述熔盐。The ball-milled metal aluminum and metal zinc particles are mixed with sodium chloride and potassium chloride according to the above mass fraction; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
实施例6Example 6
本实施例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This embodiment provides a modified chloride molten salt, and the raw materials of the molten salt in terms of mass fraction include:
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将经过球磨的金属铝与金属锌颗粒与氯化钠和氯化钾混合；将所述混合物加热至熔融状态在810℃下保温15h，冷却后得到所述熔盐。Mix the ball-milled metal aluminum and metal zinc particles with sodium chloride and potassium chloride according to the above mass fraction; heat the mixture to a molten state at 810° C. for 15 hours, and obtain the molten salt after cooling.
对比例1Comparative example 1
本对比例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This comparative example provides a modified chloride molten salt. The raw materials of the molten salt in terms of mass fraction include:
氯化钠 66％；Sodium chloride 66%;
氯化钾 30％；Potassium chloride 30%;
金属锌粉 4％。Metal zinc powder 4%.
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将金属锌粉球磨细化后与氯化钠和氯化钾混合，得到混合料；将所述混合料加热至熔融状态在790℃下保温18h，冷却后得到所述熔盐。According to the above mass fraction, the metal zinc powder is ball-milled and mixed with sodium chloride and potassium chloride to obtain a mixture; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
对比例2Comparative example 2
本对比例提供一种改性氯化物熔盐，按照质量分数计所述熔盐的原料包括：This comparative example provides a modified chloride molten salt. The raw materials of the molten salt in terms of mass fraction include:
氯化钠 66％；Sodium chloride 66%;
氯化钾 30％；Potassium chloride 30%;
金属铝粉 4％。Metal aluminum powder 4%.
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将金属铝粉球磨细化后与氯化钠和氯化钾混合，得到混合料；将所述混合料加热至熔融状态在790℃下保温18h，冷却后得到所述熔盐。According to the above mass fraction, the metal aluminum powder is ball-milled and mixed with sodium chloride and potassium chloride to obtain a mixture; the mixture is heated to a molten state at 790° C. for 18 hours, and the molten salt is obtained after cooling.
对比例3Comparative example 3
本对比例提供一种氯化物熔盐，按照质量分数计所述熔盐的原料包括：This comparative example provides a chloride molten salt. The raw materials of the molten salt in terms of mass fraction include:
氯化钠 55％；Sodium chloride 55%;
氯化钾 45％；Potassium chloride 45%;
所述熔盐的制备方法为：The preparation method of the molten salt is:
按照上述质量分数将氯化钠和氯化钾混合；将所述混合物加热至熔融状态在790℃下保温18h，冷却后得到所述熔盐。The sodium chloride and potassium chloride are mixed according to the above-mentioned mass fraction; the mixture is heated to a molten state and kept at 790° C. for 18 hours, and the molten salt is obtained after cooling.
对比例4Comparative example 4
本对比例提供一种氯化物熔盐，所述熔盐除了制备方法中加热及保温温度为780℃外，其他条件均与实施例3相同。This comparative example provides a chloride molten salt. The molten salt has the same conditions as in Example 3 except that the heating and holding temperature in the preparation method is 780°C.
对比例5Comparative example 5
本对比例提供一种氯化物熔盐，所述熔盐除了制备方法中加热及保温温度 为900℃外，其他条件均与实施例3相同。This comparative example provides a chloride molten salt. The molten salt has the same conditions as in Example 3 except that the heating and holding temperature in the preparation method is 900°C.
对实施例1-6以及对比例1-5提供的熔盐的熔点、工作上限温度以及导热系数进行测试，结果如表1所示。The melting point, upper working temperature and thermal conductivity of the molten salt provided in Examples 1-6 and Comparative Examples 1-5 were tested, and the results are shown in Table 1.
表1Table 1
| To | 熔点/℃Melting point/℃ | 工作上限温度/℃Maximum working temperature/℃ | 导热系数/W/(m·K)Thermal conductivity/W/(m·K) |
| 实施例1Example 1 | 765.8765.8 | 950℃950°C | 3.7883.788 |
| 实施例2Example 2 | 755.6755.6 | 960℃960°C | 4.2154.215 |
| 实施例3Example 3 | 761.2761.2 | 980℃980°C | 4.8734.873 |
| 实施例4Example 4 | 762.9762.9 | 980℃980°C | 4.5764.576 |
| 实施例5Example 5 | 764.5764.5 | 970℃970°C | 4.0194.019 |
| 实施例6Example 6 | 764.8764.8 | 980℃980°C | 4.1584.158 |
| 对比例1Comparative example 1 | 771.6771.6 | 900℃900°C | 3.1343.134 |
| 对比例2Comparative example 2 | 773.5773.5 | 900℃900°C | 3.3813.381 |
| 对比例3Comparative example 3 | 786.4786.4 | 900℃900°C | 2.6892.689 |
| 对比例4Comparative example 4 | 756.2756.2 | 950℃950°C | 2.6722.672 |
| 对比例5Comparative example 5 | 786.8786.8 | 950℃950°C | 2.6792.679 |
从表1的测试结果可以看出，对比例1和对比例2与实施例1相比仅添加了锌粉和铝粉中的一种，导致对比例1和对比例2得到的氯化物熔盐的熔点上升，工作上限温度下降，导热系数下降。对比例3与实施例1相比未添加金属粉，导致对比例3得到的氯化物熔盐的熔点上升，工作上限温度下降，导热系数下降。对比例4相比于实施例3煅烧温度较低，而对比例5相比于实施例3煅烧温度较高，对比例4和对比例5制备得到的氯化物熔盐的各项性能均差于It can be seen from the test results in Table 1 that compared with Example 1, Comparative Example 1 and Comparative Example 2 only added one of zinc powder and aluminum powder, resulting in the chloride molten salt obtained in Comparative Example 1 and Comparative Example 2. The melting point rises, the upper working temperature drops, and the thermal conductivity drops. Compared with Example 1, in Comparative Example 3, no metal powder was added, resulting in an increase in the melting point of the chloride molten salt obtained in Comparative Example 3, a decrease in the operating upper limit temperature, and a decrease in thermal conductivity. The calcination temperature of Comparative Example 4 is lower than that of Example 3, and the calcination temperature of Comparative Example 5 is higher than that of Example 3. The performance of the chloride molten salt prepared in Comparative Example 4 and Comparative Example 5 is worse than
实施例3。Example 3.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention uses the above embodiments to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, which does not mean that the present invention must rely on the above detailed process equipment and process flow. The process can be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. fall within the scope of protection and disclosure of the present invention.
Claims (10)
- 一种改性氯化物熔盐，其特征在于，所述熔盐的原料包括氯化物以及金属粉。A modified chloride molten salt, characterized in that the raw materials of the molten salt include chloride and metal powder.
- 根据权利要求1所述的熔盐，其特征在于，所述氯化物包括氯化钠和氯化钾。The molten salt according to claim 1, wherein the chloride includes sodium chloride and potassium chloride.
- 根据权利要求1或2所述的熔盐，其特征在于，所述金属粉包括金属铝粉和金属锌粉。The molten salt according to claim 1 or 2, wherein the metal powder comprises metal aluminum powder and metal zinc powder.
- 根据权利要求2或3所述的熔盐，其特征在于，所述熔盐的原料包括氯化钠、氯化钾、金属铝粉和金属锌粉。The molten salt according to claim 2 or 3, wherein the raw materials of the molten salt include sodium chloride, potassium chloride, metal aluminum powder and metal zinc powder.
- 根据权利要求4所述的熔盐，其特征在于，按照质量分数计所述熔盐的原料包括：The molten salt according to claim 4, wherein the raw material of the molten salt in terms of mass fraction comprises:
- 根据权利要求5所述性能更佳的熔盐，其特征在于，按照质量分数计所述熔盐的原料包括：The molten salt with better performance according to claim 5, wherein the raw material of the molten salt in terms of mass fraction comprises:
- 一种权利要求1-6任一项所述的熔盐的制备方法，其特征在于，所述方法包括扩以下步骤：A method for preparing molten salt according to any one of claims 1 to 6, characterized in that the method comprises the following steps:将金属粉与金属氯化物混合，得到混合料；将所述混合料加热至熔融状态 进行煅烧，冷却后得到所述熔盐。The metal powder and the metal chloride are mixed to obtain a mixture; the mixture is heated to a molten state for calcination, and the molten salt is obtained after cooling.
- 根据权利要求7所述的制备方法，其特征在于，所述煅烧的温度为780～830℃。The preparation method according to claim 7, wherein the calcination temperature is 780-830°C.
- 根据权利要求7或8所述的制备方法，其特征在于，所述煅烧的时间为12～24h。The preparation method according to claim 7 or 8, wherein the calcination time is 12-24 hours.
- 一种权利要求1-6任一项所述的熔盐的应用，其特征在于，所述熔盐用于太阳能热发电、太阳能制氢反应及工业余热回收领域。An application of the molten salt according to any one of claims 1 to 6, wherein the molten salt is used in the fields of solar thermal power generation, solar hydrogen production reaction, and industrial waste heat recovery.
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