离子液体型热泵新工质的性质研究
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摘要
吸收式热泵可用于低品位热能的回收利用,对于能源的综合利用,回收工业废热,保护环境具有重要的意义。热泵工质对热泵的操作性能和操作费用有重要的影响。传统的热泵工质存在腐蚀性、结晶及工作压力高和毒性等问题,因此,热泵新工质一直是人们关注的热点。
离子液体又称低温熔融盐,是一类完全由离子组成的物质,具有很多独特的性质,如:良好的热稳定性和化学稳定性,很宽的液态范围,蒸汽压极低等。因此,有可能作为热泵新工质的吸收剂。本文提出以含离子液体的二元溶液作为新型的热泵工质对,其中离子液体硫酸二乙酯1-甲基-3-乙基咪唑(EMISE)、1-乙基-3-甲基咪唑磷酸二乙酯([EMIM]DEP)为吸收剂,以水为制冷剂,本文制备了离子液体,并对其结构进行表征,测定了其分别与水组成的二元溶液的热力学性质及物理性质,为热力学模型的研究提供基础数据,为计算吸收式热泵的性能奠定基础。
吸收式热泵工质要求体系在汽液相平衡特性上表现为对Roualt定律的负偏差,因此,本文测量了两个含离子液体的二元溶液在不同温度、不同离子液体浓度下的饱和蒸汽压数据,并采用非电解质溶液活度系数模型进行关联,预测了两体系在323.15K下的蒸汽压数据,结果表明NRTL模型可以很好的预测含离子液体溶液的汽液平衡数据,两体系均对Roualt定律呈负偏差,具有成为热泵新工质的潜力。
本文测定了离子液体EMISE/[EMIM]DEP与水在298.15K时的混合热数据,并测定了含离子液体的二元溶液在不同温度下不同浓度下的比热数据。结果表明,离子液体EMISE/[EMIM]DEP与水混合均放热,而且随着离子浓度的增加,放热量先增加后减小,[EMIM]DEP与水体系混合放出的热量比EMISE+水体系放出的热量大得多。两个二元溶液的比热均与温度呈线性关系,随着离子浓度的增加,比热逐渐减小,并用经验式对比热关联,结果显示计算值和实验值符合较好。
本文采用品氏粘度计和比重天平分别测定了不同温度下、不同离子浓度下EMISE/[EMIM]DEP与水的二元溶液的粘度和密度。研究结果表明,水的加入使离子液体EMISE/[EMIM]DEP的粘度减小,随着离子液体浓度的减小,粘度逐渐减小,最后趋向于一个极限值。二元溶液的密度与温度也呈线性关系,随着水的加入,其密度逐渐减小,对于相同浓度的溶液,温度升高,溶液密度减小。本文采用含温度和浓度的经验式对粘度和浓度进行关联,结果表明,实验值和计算值符合较好。
Absorption heat pump can recover and utilize waster heat with lower temperature,it has important significance for energy comprehensive utilization,recovering industrial waste heat and environment protection.The working pair has important influence in the operational performance and operating costs.The conventional working pairs have the problems of corrosion,crystallization,high working pressure,toxicity.So many people have pay attention on the study of the working pairs of the heat pump.
Ionic liquid(IL) were known as low temperature molten salts,which are solely composed of ions and have many unique attributes,e.g.good thermal and chemical stabilities,wide liquid-state range,negligible vapor pressure et al.Due to these features,it's possible that ionic liquids could be used as the novel working fluids in the absorption heat pump.In this paper, the binary solution containing ionic liquid were chosen as novel working fluids,the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate(EMISE),1-ehtyl-3-methylimidazolium diethylphosphate([EMIM]DEP)act as absorbent and water acts as refrigerant,we have prepared the ionic liquids,characterized the structure and measured the thermodynamic and physical properties,providing the basic information for the research of the thermodynamic model and establishing the foundation for calculating the performance of an absorption heat pump.
The working fluid of the absorption heat pump should have a considerable negative deviation from Raoult's law in the aspect of the vapor-liquid equilibrium.Therefore,the saturated vapor pressure of the two binary solutions at the different temperature and the different IL-containing were measured,correlated by the nonelectrolyte activity coefficient model and predicted the vapor pressure of the two systems at the temperature of 323.15K. The results showed that the NRTL model could suitably predict the vapor-liquid equilibrium of the solution containing ionic liquid,the two systems had a considerable negative deviation from Raoult's law,so they could be chosen as potential working fluid.
In this paper,the mixing enthalpy of the ionic liquid EMISE/[EMIM]DEP with water at the temperature of 298.15K and the heat capacity of the binary solution containing ionic liquid at the different temperatures and the different IL-containing were measured.The results showed that the ionic liquid EMISE/[EMIM]DEP has exothermic heat when they mixed with water and the releasing heat first increased and then decreased with the increasing of the IL molar fraction.The mixing heat of the[EMIM]DEP with water was much larger than that of the EMISE with water.The heat capacity of the two binary solutions showed a linear relationship with the temperature,and decreased with the increasing of the molar fraction of the ionic liquid EMISE/[EMIM]DEP.The heat capacities were correlated by the empirical formula,the results showed the calculated data had good agreement with the experimental data.
The viscosity and the density of the binary solution EMISE/[EMIM]DEP with water at the different temperatures and the different IL-containing were respectively measured by the viscometer and specific gravity balance.The results showed that the viscosity of the ionic liquid EMISE/[EMIM]DEP were decreased with the addition of water.The viscosity were decreased with the molar fraction of the ionic liquid and tended to a limiting value.The densities also showed a linear relationship with the temperature,the values were decreased with the addition of water and the increasing of the temperature.The viscosity and the density were respectively correlated by the empirical formula which containing the temperature and the molar fraction of the IL,the experimental data showed good agreement with the caculated data.
离子液体又称低温熔融盐,是一类完全由离子组成的物质,具有很多独特的性质,如:良好的热稳定性和化学稳定性,很宽的液态范围,蒸汽压极低等。因此,有可能作为热泵新工质的吸收剂。本文提出以含离子液体的二元溶液作为新型的热泵工质对,其中离子液体硫酸二乙酯1-甲基-3-乙基咪唑(EMISE)、1-乙基-3-甲基咪唑磷酸二乙酯([EMIM]DEP)为吸收剂,以水为制冷剂,本文制备了离子液体,并对其结构进行表征,测定了其分别与水组成的二元溶液的热力学性质及物理性质,为热力学模型的研究提供基础数据,为计算吸收式热泵的性能奠定基础。
吸收式热泵工质要求体系在汽液相平衡特性上表现为对Roualt定律的负偏差,因此,本文测量了两个含离子液体的二元溶液在不同温度、不同离子液体浓度下的饱和蒸汽压数据,并采用非电解质溶液活度系数模型进行关联,预测了两体系在323.15K下的蒸汽压数据,结果表明NRTL模型可以很好的预测含离子液体溶液的汽液平衡数据,两体系均对Roualt定律呈负偏差,具有成为热泵新工质的潜力。
本文测定了离子液体EMISE/[EMIM]DEP与水在298.15K时的混合热数据,并测定了含离子液体的二元溶液在不同温度下不同浓度下的比热数据。结果表明,离子液体EMISE/[EMIM]DEP与水混合均放热,而且随着离子浓度的增加,放热量先增加后减小,[EMIM]DEP与水体系混合放出的热量比EMISE+水体系放出的热量大得多。两个二元溶液的比热均与温度呈线性关系,随着离子浓度的增加,比热逐渐减小,并用经验式对比热关联,结果显示计算值和实验值符合较好。
本文采用品氏粘度计和比重天平分别测定了不同温度下、不同离子浓度下EMISE/[EMIM]DEP与水的二元溶液的粘度和密度。研究结果表明,水的加入使离子液体EMISE/[EMIM]DEP的粘度减小,随着离子液体浓度的减小,粘度逐渐减小,最后趋向于一个极限值。二元溶液的密度与温度也呈线性关系,随着水的加入,其密度逐渐减小,对于相同浓度的溶液,温度升高,溶液密度减小。本文采用含温度和浓度的经验式对粘度和浓度进行关联,结果表明,实验值和计算值符合较好。
Absorption heat pump can recover and utilize waster heat with lower temperature,it has important significance for energy comprehensive utilization,recovering industrial waste heat and environment protection.The working pair has important influence in the operational performance and operating costs.The conventional working pairs have the problems of corrosion,crystallization,high working pressure,toxicity.So many people have pay attention on the study of the working pairs of the heat pump.
Ionic liquid(IL) were known as low temperature molten salts,which are solely composed of ions and have many unique attributes,e.g.good thermal and chemical stabilities,wide liquid-state range,negligible vapor pressure et al.Due to these features,it's possible that ionic liquids could be used as the novel working fluids in the absorption heat pump.In this paper, the binary solution containing ionic liquid were chosen as novel working fluids,the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate(EMISE),1-ehtyl-3-methylimidazolium diethylphosphate([EMIM]DEP)act as absorbent and water acts as refrigerant,we have prepared the ionic liquids,characterized the structure and measured the thermodynamic and physical properties,providing the basic information for the research of the thermodynamic model and establishing the foundation for calculating the performance of an absorption heat pump.
The working fluid of the absorption heat pump should have a considerable negative deviation from Raoult's law in the aspect of the vapor-liquid equilibrium.Therefore,the saturated vapor pressure of the two binary solutions at the different temperature and the different IL-containing were measured,correlated by the nonelectrolyte activity coefficient model and predicted the vapor pressure of the two systems at the temperature of 323.15K. The results showed that the NRTL model could suitably predict the vapor-liquid equilibrium of the solution containing ionic liquid,the two systems had a considerable negative deviation from Raoult's law,so they could be chosen as potential working fluid.
In this paper,the mixing enthalpy of the ionic liquid EMISE/[EMIM]DEP with water at the temperature of 298.15K and the heat capacity of the binary solution containing ionic liquid at the different temperatures and the different IL-containing were measured.The results showed that the ionic liquid EMISE/[EMIM]DEP has exothermic heat when they mixed with water and the releasing heat first increased and then decreased with the increasing of the IL molar fraction.The mixing heat of the[EMIM]DEP with water was much larger than that of the EMISE with water.The heat capacity of the two binary solutions showed a linear relationship with the temperature,and decreased with the increasing of the molar fraction of the ionic liquid EMISE/[EMIM]DEP.The heat capacities were correlated by the empirical formula,the results showed the calculated data had good agreement with the experimental data.
The viscosity and the density of the binary solution EMISE/[EMIM]DEP with water at the different temperatures and the different IL-containing were respectively measured by the viscometer and specific gravity balance.The results showed that the viscosity of the ionic liquid EMISE/[EMIM]DEP were decreased with the addition of water.The viscosity were decreased with the molar fraction of the ionic liquid and tended to a limiting value.The densities also showed a linear relationship with the temperature,the values were decreased with the addition of water and the increasing of the temperature.The viscosity and the density were respectively correlated by the empirical formula which containing the temperature and the molar fraction of the IL,the experimental data showed good agreement with the caculated data.
引文
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