WO2017008371A1 - 一种热力循环混合工质可燃范围的预测方法 - Google Patents

一种热力循环混合工质可燃范围的预测方法 Download PDF

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WO2017008371A1
WO2017008371A1 PCT/CN2015/087986 CN2015087986W WO2017008371A1 WO 2017008371 A1 WO2017008371 A1 WO 2017008371A1 CN 2015087986 W CN2015087986 W CN 2015087986W WO 2017008371 A1 WO2017008371 A1 WO 2017008371A1
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李家俊
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Tianjin University
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  • the invention belongs to the technical field of thermodynamic cycles, and particularly relates to a method for predicting the combustible range of a thermodynamic circulating mixed working fluid.
  • the safety and environmental protection flame retardant CO 2 is added to the hydrocarbon working fluid to form a mixed working medium, and the properties thereof can be adjusted according to the composition ratio of the components, thereby fully suppressing the aforementioned flammability and improving the cycle performance.
  • both HCs and CO 2 are natural working fluids, ODP values are equal to zero, GWP values are small, in line with the development of environmentally friendly working fluids, and have the potential to become a long-term alternative working medium in the field of medium and high temperature waste heat utilization.
  • the flammability range of this type of mixed working fluid is very important for the safety assessment of its practical application under different mixing ratios.
  • the flammable range refers to the upper and lower limits of combustion that can be produced by the working fluid.
  • the Le Chatelier empirical formula and the critical flame temperature method are the most common methods for predicting the flammability limit of mixtures.
  • the Le Chatelier empirical formula mainly predicts the flammability limit of combustible working fluids composed of a mixture of multiple combustible components.
  • the flammability limit prediction accuracy of a mixture containing non-combustible substances similar to HCs/CO 2 is low.
  • the method of critical flame temperature theory is used to predict the high flammability limit of HCs/CO 2 mixture, but how to determine its relatively accurate critical temperature is very difficult. If the problem is solved then the method can be applied to mixtures of different ratios and compositions.
  • thermodynamic circulating working fluid composed of HCs/CO 2 .
  • the method establishes the HCS/CO 2 flammability limit prediction model for mixed working fluids.
  • the prediction model is obtained. Undetermined coefficient. This coefficient is verified by a large amount of experimental data, so that the accuracy of the flammability limit prediction of the HCs/CO 2 mixture is greatly improved.
  • the technical solution of the present invention is as follows:
  • the method for predicting the combustible range of the thermodynamic circulating mixed medium predicts the upper flammable upper limit and the lower flammable lower limit of the binary mixed working medium composed of HCs/CO 2 .
  • the prediction methods for the HCs/CO 2 flammable upper limit include:
  • U m is the upper limit of flammability of the HCs/CO 2 mixture
  • U 0 is the upper limit of flammability of the corresponding hydrocarbon substance
  • y is the volume fraction of CO 2 in the HCs/CO 2 mixture
  • K U is the undetermined coefficient of the flammable upper limit prediction model, This coefficient is related to the selected critical flame temperature.
  • step 1.2 The flammable upper limit obtained in step 1.2 and the corresponding CO 2 volume fraction are fitted according to the prediction model A, and the undetermined coefficient K U in the prediction model A is obtained;
  • L m is the lower flammable lower limit of the HCs/CO 2 mixture
  • L 0 is the lower flammable lower limit of the corresponding hydrocarbon substance
  • y is the volume fraction of CO 2 in the HCs/CO 2 mixture
  • K L is the undeterminable coefficient of the flammable lower limit prediction model, This coefficient is also related to the selected critical flame temperature.
  • the flammable lower limit value of the HCs/CO 2 mixed working fluid containing any CO 2 volume fraction is predicted based on the undetermined coefficient K L .
  • the advantages and benefits of the method of the present invention are: based on the critical flame temperature theory, the two prediction models of the upper and lower flammability limits are established, and the flammability limit can be predicted for any volume fraction mixture composed of HCs/CO 2 .
  • the undetermined coefficients in the prediction model obtained by fitting are verified by experimental data, which overcomes the defects that the theoretical prediction model needs to rely on selecting the appropriate critical flame temperature, which greatly improves the prediction accuracy.
  • the prediction accuracy can be controlled within 5%, which ensures the accuracy of the HCs/CO 2 mixed working fluid flammability limit prediction data, and provides an accurate reference for the safety assessment of the thermal circulation system using this type of mixed working fluid.
  • a method for predicting the upper and lower flammability limits of a binary mixed working fluid consisting of HCs/CO 2 includes the following steps:
  • the prediction methods for the HCs/CO 2 flammable upper limit include:
  • U m is the upper limit of flammability of the HCs/CO 2 mixture
  • U 0 is the upper limit of flammability of the corresponding hydrocarbon substance
  • y is the volume fraction of CO 2 in the HCs/CO 2 mixture
  • K U is the undetermined coefficient of the flammable upper limit prediction model, This coefficient is related to the selected critical flame temperature.
  • step 1.2 The flammable upper limit obtained in step 1.2 and the corresponding CO 2 volume fraction are fitted according to the prediction model A to obtain the undetermined coefficient K U in the prediction model A.
  • Lm and Um are in a one-to-one relationship with y, that is, as long as the volume fraction of CO 2 is known, the combustible range of the mixed working medium can be predicted.
  • Table 1 gives the prediction effect of the prediction method on the practical application of the upper limit of flammability.
  • L m is the lower flammable lower limit of the HCs/CO 2 mixture
  • L 0 is the lower flammable lower limit of the corresponding hydrocarbon substance
  • y is the volume fraction of CO 2 in the HCs/CO 2 mixture
  • K L is the undeterminable coefficient of the flammable lower limit prediction model, The coefficient is also related to the selected critical flame temperature
  • the flammable lower limit value of the HCs/CO 2 mixed working fluid containing any CO 2 volume fraction is predicted based on the undetermined coefficient K L .
  • Table 2 gives the prediction effect of the prediction method on the practical application of the lower flammable limit.
  • the flammability limit data in steps 1.2 and 2.2 is the actual data obtained from the actual test.
  • the HCs/CO 2 mixed working flammability limit of any CO 2 volume fraction can be predicted.
  • the error of the combustible range of the mixed working fluid calculated by the prediction model is within 5%.

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Abstract

一种热力循环混合工质可燃范围的预测方法，该方法是对混合介质的可燃上限和下限分别进行预测，基于临界火焰温度理论建立可燃极限预测模型，然后通过对试验获取的HCs/CO2混合工质的可燃极限值和对应的CO2体积分数按照预测模型进行线性拟合，得出预测模型中的待定系数，以获得最佳可燃极限预测模型。该方法克服了理论预测模型需要依赖选取合适的临界火焰温度确定的缺陷，极大提高了预测精度，保证了HCs/CO2混合工质可燃极限预测数据的准确性，为热力循环系统应用该类型混合工质的安全评估提供准确的参考依据。

Description

一种热力循环混合工质可燃范围的预测方法 技术领域
本发明属于热力循环技术领域，具体涉及到对一种热力循环混合工质可燃烧范围的预测方法。
背景技术
近年来，能源短缺和环境污染的问题越来越严重，开展节能减排是缓解这两大问题的有效途径。余热(如内燃机排气余热和工业余热等)发电技术的研究，对于减少化石能源消耗和CO2等温室气体的排放具有重要意义。采用有机朗肯循环进行余热发电是一种有效的节能减排方式，但如果余热温度过高超过有机工质的分解温度，就会导致工质的热物性发生改变，进而影响整个循环系统的性能。所以对于内燃机等具有高温排气特征的中高温余热利用，尚缺乏适合的循环工质。循环性能较好的中高温混合工质主要集中在烃类HCs和硅氧烷类，但是它们属于易燃易爆的危险物质，一旦发生泄漏，后果不堪设想，限制了进一步的推广和实际应用。
在烃类工质中加入安全环保的阻燃剂CO2形成混合工质，其性质可以随着组元配比的不同得到调和，既可以充分抑制前述的可燃性，也可以改善其循环性能等。此外，HCs和CO2都是自然工质，ODP值都等于零，GWP值都较小，符合环保工质发展的方向，在中高温余热利用领域具有成为长远替代工质的潜力。但不同混合比例下，该类型混合工质的可燃范围对其实际应用的安全性评估十分重要。
可燃范围系指工质可以产生燃烧的上限与下限。目前，Le Chatelier经验公式和临界火焰温度方法是最常见的混合物可燃极限预测方法，Le Chatelier经验公式主要是对由多种可燃组元混合所构成可燃工质的可燃极限进行预测。但是对类似于HCs/CO2这种含有不可燃物质的混合物可燃极限预测精度较低。采用临界火焰温度理论的方法预测HCs/CO2混合物的可燃极限精度较高，但是如何确定其相对准确的临界温度，则是非常困难的。如果该问题得到解决那么该方法就可以适用于不同比例及成分的混合物。
发明内容
为了解决上述问题，本发明的目的是，提供一种由HCs/CO2组成的热力循环混合工质可燃范围进行预测的方法。
该方法基于临界火焰温度的理论，建立混合工质HCs/CO2可燃极限预测模型，通过对五组以上混合工质可燃极限值和对应的CO2体积分数进行线性拟合，得到预测模型中的待定系数。该系数通过大量的试验数据验证，使得对HCs/CO2混合物的可燃极限预测的精度得到大幅提高。
为了实现上述目的，本发明的技术方案如下：该热力循环混合工质可燃范围的预测方法，预测由HCs/CO2组成的二元混合工质的可燃上限和可燃下限。
(1)对于HCs/CO2可燃上限的预测方法包括：
1.1建立HCs/CO2混合工质可燃上限预测模型：
Figure PCTCN2015087986-appb-000001
其中，Um是HCs/CO2混合物的可燃上限；U0是相应烃类物质的可燃上限；y为CO2在HCs/CO2混合物中的体积分数；KU是可燃上限预测模型待定系数，该系数与选取的临界火焰温度相关。
1.2对含有不同体积分数CO2的HCs/CO2混合物的可燃上限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃上限值；
1.3将步骤1.2取得的可燃上限值与对应的CO2体积分数按照预测模型A进行拟合，得到预测模型A中的待定系数KU；
1.4根据待定系数KU预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃上限值。
(2)对于HCs/CO2可燃下限的预测方法包括：
2.1建立HCs/CO2混合工质可燃下限预测模型：
Figure PCTCN2015087986-appb-000002
其中，Lm是HCs/CO2混合物的可燃下限；L0是相应烃类物质的可燃下限；y为CO2在HCs/CO2混合物中的体积分数；KL为可燃下限预测模型待定系数，该系数也与选取的临界火焰温度相关。
2.2对含有不同体积分数CO2的HCs/CO2混合物的可燃下限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃下限值；
2.3将步骤2.2取得的可燃下限值与对应的CO2体积分数按照预测模型B进行拟合，得到预测模型B中的待定系数KL；
2.4根据待定系数KL预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃下限值。
本发明方法的优点及有益效果是：基于临界火焰温度理论，所建立的上、下可燃极限两个预测模型，对由HCs/CO2组成的任何体积分数的混合物都可进行可燃极限的预测。通过拟合得到的预测模型中的待定系数，均加以实验数据验证，克服了理论预测模型需要依赖选取合适的临界火焰温度确定的缺陷，极大提高了预测精度。可将预测精度控制在5％以内，保证了HCs/CO2混合工质可燃极限预测数据的准确性，为热力循环系统应用该类型混合工质的安全评估提供准确的参考依据。
具体实施方式
以下通过具体实施例对本发明方法及技术方案，进行详细的说明。需要说明的是，所描述的实施例仅用于本发明方法的详尽解释。基于该实施例的基本原理与过程，尚未涉及到的其他数据实施，都属于本发明保护的范围。
预测由HCs/CO2组成的二元混合工质可燃上限和可燃下限的预测方法，包括以下步骤：
(1)对于HCs/CO2可燃上限的预测方法包括：
1.1基于临界火焰温度理论，建立HCs/CO2混合工质可燃上限预测模型：
Figure PCTCN2015087986-appb-000003
其中，Um是HCs/CO2混合物的可燃上限；U0是相应烃类物质的可燃上限；y为CO2在HCs/CO2混合物中的体积分数；KU是可燃上限预测模型待定系数，该系数与选取的临界火焰温度相关。
1.2按照ASTM(美国材料与试验协会)E681:04标准，对含有不同体积分数CO2的HCs/CO2混合物的可燃上限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃上限值。
1.3将步骤1.2取得的可燃上限值与对应的CO2体积分数按照预测模型A进行拟合，得到预测模型A中的待定系数KU。
1.4根据待定系数KU预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃上限值。
待定系数确定后，Lm和Um与y是一对一的关系，即只要知道了CO2的体积分数，就可以预测混合工质的可燃范围。
以丙烷/CO2和异丁烷/CO2为例，表1给出了该预测方法对可燃上限的实际应用预测效果。
Figure PCTCN2015087986-appb-000004
(2)对于HCs/CO2可燃下限的预测方法包括：
2.1基于临界火焰温度理论建立HCs/CO2混合工质可燃下限预测模型：
Figure PCTCN2015087986-appb-000005
其中，Lm是HCs/CO2混合物的可燃下限；L0是相应烃类物质的可燃下限；y为CO2在HCs/CO2混合物中的体积分数；KL为可燃下限预测模型待定系数，该系数也与选取的临界火焰温度相关；
2.2按照ASTM(美国材料与试验协会)E681:04标准，对含有不同体积分数CO2的HCs/CO2混合物的可燃下限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃下限值；
2.3将步骤2.2取得的可燃下限值与对应的CO2体积分数按照预测模型B进行拟合，得到预测模型B中的待定系数KL；
2.4根据待定系数KL预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃下限值。
以丙烷/CO2和异丁烷/CO2为例，表2给出了该预测方法对可燃下限的实际应用预测效果。
Figure PCTCN2015087986-appb-000006
步骤1.2和2.2中的可燃极限数据为实际测试得到的真实数据。
当预测模型中的待定系数确定后，可以预测任何CO2体积分数下的HCs/CO2混合工质可燃极限。预测模型计算得到的混合工质可燃范围的误差在5％以内。

Claims (1)

  1. 一种热力循环混合工质可燃范围的预测方法，其特征在于，预测由HCs/CO2组成的二元混合工质可燃上限和可燃下限的预测方法，包括以下步骤：
    (1)对于HCs/CO2可燃上限的预测方法包括：
    1.1建立HCs/CO2混合工质可燃上限预测模型：
    Figure PCTCN2015087986-appb-100001
    其中，Um是HCs/CO2混合物的可燃上限；U0是相应烃类物质的可燃上限；y为CO2在HCs/CO2混合物中的体积分数；KU是可燃上限预测模型待定系数，该系数与选取的临界火焰温度相关；
    1.2对含有不同体积分数CO2的HCs/CO2混合物的可燃上限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃上限值；
    1.3将步骤1.2取得的可燃上限值与对应的CO2体积分数按照预测模型A进行拟合，得到预测模型A中的待定系数KU；
    1.4根据待定系数KU预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃上限值；
    (2)对于HCs/CO2可燃下限的预测方法包括：
    2.1建立HCs/CO2混合工质可燃下限预测模型；
    Figure PCTCN2015087986-appb-100002
    其中，Lm是HCs/CO2混合物的可燃下限；L0是相应烃类物质的可燃下限；y为CO2在HCs/CO2混合物中的体积分数；KL为可燃下限预测模型待定系数，该系数与选取的临界火焰温度相关；
    2.2对含有不同体积分数CO2的HCs/CO2混合物的可燃下限进行测试，得到5组以上不同CO2体积分数下的混合工质可燃下限值；
    2.3将步骤2.2取得的可燃下限值与对应的CO2体积分数按照预测模型B进行拟合，得到预测模型B中的待定系数KL；
    2.4根据待定系数KL预测出含有任何CO2体积分数的HCs/CO2混合工质的可燃下限值。
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CN102608284A (zh) * 2011-12-23 2012-07-25 南京工业大学 一种确定多元混合气体爆炸极限的方法
CN103939941A (zh) * 2014-04-25 2014-07-23 国家电网公司 一种融入了不可逆热力学的锅炉燃烧优化方法

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