制冷剂R1336mzz（E）液相黏度理论与实验研究

doi:10.11949/0438-1157.20201597

化工学报 ›› 2021, Vol. 72 ›› Issue (6): 3261-3269.DOI: 10.11949/0438-1157.20201597

制冷剂R1336mzz（E）液相黏度理论与实验研究

许晨怡¹(),叶恭然¹,郭豪文¹,庄园¹,郭智恺²,韩晓红¹(),陈光明¹

^1.浙江省制冷与低温重点实验室，浙江大学制冷与低温研究所，浙江杭州 310027
^2.含氟温室气体替代及控制处理国家重点实验室，浙江省化工研究院有限公司，浙江杭州 310023

收稿日期:2020-11-03 修回日期:2020-12-22 出版日期:2021-06-05 发布日期:2021-06-05
通讯作者: 韩晓红
作者简介:许晨怡（1995—），女，硕士研究生，21860013@zju.edu.cn
基金资助:
国家自然科学基金项目(51936007);浙江省自然科学基金项目(LZ19E060001)

Experimental and theoretical study on liquid viscosity of R1336mzz(E)

XU Chenyi¹(),YE Gongran¹,GUO Haowen¹,ZHUANG Yuan¹,GUO Zhikai²,HAN Xiaohong¹(),CHEN Guangming¹

^1.Key Laboratory of Refrigeration and Cryogenic Technology of Zhejiang Province, Institute of Refrigeration and Cryogenics, Zhejiang University, Hangzhou 310027, Zhejiang，China
^2.State Key Laboratory of Fluorinated Greenhouse Gases Replacement and Control Treatment, Zhejiang Research Institute of Chemical Industry Co. , Ltd. , Hangzhou 310023, Zhejiang，China

Received:2020-11-03 Revised:2020-12-22 Online:2021-06-05 Published:2021-06-05
Contact: HAN Xiaohong

摘要/Abstract

摘要：

研究新型制冷剂的热物理性质是制冷剂替代工作的基础。在新型环保HFO类制冷剂中，R1336mzz（E）因其与R245fa相似的热力学性质，在高温热泵和有机朗肯循环中有希望成为R245fa的替代制冷剂。采用旋转式毛细管黏度计，测量了278 ~ 333 K温度范围内R1336mzz（E）的液相黏度，并根据四种形式的液体黏度方程对实验数据进行拟合，得到R1336mzz（E）黏度与温度的关联式。结果表明，采用修正后的非线性Andrade关联式所关联的精度最高，其关联结果与实验结果之间平均绝对偏差（AAD）和最大绝对偏差（MAD）分别为0.170 %和0.311 %。基于R1336mzz（E）于高温热泵的应用前景，通过拟合所得的四种黏度关联式对实验数据进行至临界温度（403.37 K）的外推，根据误差分析，采用修正后的非线性Andrade关联式外推得到的数据最可靠，可作为R1336mzz（E）临界温度附近的黏度数据。研究工作可以为R1336mzz（E）的替代应用研究提供基础数据。

关键词: 黏度, 热力学性质, 制冷剂, R1336mzz（E）, 流体动力学

Abstract:

Studying the thermophysical properties of new refrigerants is the basis of refrigerant substitution. Among the new environment-friendly HFO refrigerants, R1336mzz(E) has similar thermal properties to R245fa and is a promising alternative to R245fa in high temperature heat pumps and organic Rankine cycles. The liquid viscosity of R1336mzz(E) in the range of 278—333 K was measured by rotating capillary viscometer. Besides, we correlated the experimental data according to four liquid viscosity equations, and obtained the correlation equation between the viscosity of R1336mzz(E) and temperature. As a result, it illustrated that the modified nonlinear Andrade correlation equation had the highest correlation accuracy. Besides, its average absolute deviation (AAD) and maximum absolute deviation (MAD) were 0.170% and 0.311%, respectively. Based on the application prospect of R1336mzz(E) in high temperature heat pump, through the fitting of four viscosity correlations, the experimental data were extrapolated to the critical temperature (403.37 K). What's more, the modified nonlinear Andrade correlation extrapolation obtained the most reliable data according to the error analysis. Of course, it could be used as the viscosity data near the critical temperature of R1336mzz(E). We intended to provide basic data for the alternative application research of R1336mzz(E).

Key words: viscosity, thermodynamic properties, refrigerant, R1336mzz(E), hydrodynamics

中图分类号:

TQ 028.8

许晨怡, 叶恭然, 郭豪文, 庄园, 郭智恺, 韩晓红, 陈光明. 制冷剂R1336mzz（E）液相黏度理论与实验研究[J]. 化工学报, 2021, 72(6): 3261-3269.

XU Chenyi, YE Gongran, GUO Haowen, ZHUANG Yuan, GUO Zhikai, HAN Xiaohong, CHEN Guangming. Experimental and theoretical study on liquid viscosity of R1336mzz(E)[J]. CIESC Journal, 2021, 72(6): 3261-3269.

图/表 13

表1 制冷剂发展历程

Table 1 Development history of refrigerants

阶段	原则	主要制冷剂
第一阶段（1830—1930年）	能用即可	自然制冷剂
第二阶段（1931—1990年）	提高制冷效率、安全性和耐久性	氯氟烃（CFCs）、氢氯氟烃（HCFCs）、氢氟烃（HFCs）
第三阶段（1991—2010年）	对臭氧层无破坏作用	烃类（HCs）、氢氯氟烃（HCFCs）、氢氟烃（HFCs）
第四阶段（2011年至今）	零臭氧层消耗潜值（ODP）、低全球变暖潜值（GWP）、较高的制冷效率	低GWP的氢氟烃（HFCs）、不饱和氢氟烃类（HFOs）、烃类（HCs）、自然制冷剂

表2 黏度测量仪器比较

Table 2 Comparison of viscometers

黏度测量仪器	基本原理	优缺点分析
毛细管黏度计	测量已知体积的液体在重力或外力作用下流过毛细管上下刻度线的时间	结构简单、操作简便、精度较高。需要采用已知黏度的液体进行校准；易挥发流体在密闭环境下测量，需要考虑承压问题；抽吸法会改变易挥发混合流体的组分
旋转式黏度计	测量固体在黏性流体中以一定的角速度旋转所需要的已知力或扭矩的旋转速率	测量范围广，可对同一试样在不同剪切速率下进行多次测量，对性能随温度变化的材料进行连续测量。但对牛顿流体的测量精度较低
落球黏度计	固体在重力作用下通过黏性流体下落，测量固体的终端速度	落体的Re会影响测量精度，获得高精度数据耗时较长
振动式黏度计	测量沉浸在黏性流体中的振动机电谐振器的阻尼	所需的样品量少，灵敏度高，操作简便，可连续读数，范围广，测试液的流通性强，易于清理
孔隙黏度计	测量固定体积的液体流过孔口的时间	简便易用。无法进行绝对测量，无法确定非牛顿流体的黏度
超声波黏度计	测量球体在黏性液体中的振荡运动产生的电动势	流体不经过仪器内部，测量方便；可以进行瞬时和连续的黏度测量

图1 旋转式毛细管黏度计

Fig.1 The rotatable capillary viscometer

图2 黏度测量系统示意图

Fig.2 The schematic layout of viscosity measurement system

表3 黏度测量系统主要仪器设备

Table 3 Main instruments and equipment

设备	型号	量程	精度
铂电阻温度计	WZPB-I	—	0.001 K
压力传感器	PMP4010	0 ~ 3.5 MPa	0.04 % F.S.
机械秒表	M504	0 ~ 15 min	0.1 s
一次恒温槽	RTS-40T	-40 ~ 95℃	0.01℃
气相色谱仪	GC1690T	—	0.3 %
电子天平	BL-5000S	0 ~ 5000 g	0.01 g

表4 R1336mzz(E)的基本热物性[7]

Table 4 Fundamental characteristic properties of R1336mzz(E) [7]

临界温度T_C/K	临界密度ρ_C/(kg/m³)	临界压力p_C/kPa	常压沸点T_b/K	摩尔质量M/(g/mol)	偏心因子ω
403.37	515.3	2766.4	280.58	164.05	0.4053

表5 R1336mzz(E)的液相黏度测量结果

Table 5 Experimental data of the liquid viscosity of R1336mzz(E)

T/K	$ρ L$ /(kg/m³)	$ρ V$ /(kg/m³)	k	t/s	ν/(mm²/s)	η_exp/(μPa·s)
279.238	1363.40	7.078	0.9946	441.7	0.283	389
283.214	1351.34	8.232	0.9938	425.2	0.272	370
288.184	1336.04	9.879	0.9927	405.1	0.258	348
293.183	1320.37	11.789	0.9914	387.5	0.246	328
298.138	1304.54	13.961	0.9898	369.0	0.234	307
303.250	1287.88	16.529	0.9880	350.8	0.221	287
308.106	1271.72	19.308	0.9859	336.3	0.211	270
313.077	1254.79	22.535	0.9833	321.0	0.200	253
323.091	1219.36	30.397	0.9769	295.1	0.182	223
333.166	1181.60	40.535	0.9678	274.4	0.167	198

表5 R1336mzz(E)的液相黏度测量结果

Table 5 Experimental data of the liquid viscosity of R1336mzz(E)

T/K	$ρ L$ /(kg/m³)	$ρ V$ /(kg/m³)	k	t/s	ν/(mm²/s)	η_exp/(μPa·s)
279.238	1363.40	7.078	0.9946	441.7	0.283	389
283.214	1351.34	8.232	0.9938	425.2	0.272	370
288.184	1336.04	9.879	0.9927	405.1	0.258	348
293.183	1320.37	11.789	0.9914	387.5	0.246	328
298.138	1304.54	13.961	0.9898	369.0	0.234	307
303.250	1287.88	16.529	0.9880	350.8	0.221	287
308.106	1271.72	19.308	0.9859	336.3	0.211	270
313.077	1254.79	22.535	0.9833	321.0	0.200	253
323.091	1219.36	30.397	0.9769	295.1	0.182	223
333.166	1181.60	40.535	0.9678	274.4	0.167	198

图3 R1336mzz(E)黏度随温度变化散点图

Fig.3 Scatter plots of the temperature dependence of viscosity of R1336mzz(E)

表6 四种模型的拟合参数和拟合偏差

Table 6 The correlation parameters, AAD and MAD of four viscosity models

参数	式(9)	式(10)	式(11)	式(12)
A	1.811	-1.778	4.282	-0.1488
B	1164	3347	-8.997	-1252
C	—	-3.31×10⁵	-0.00626	-177.4
D	—	—	1.1350×10^-6	—
AAD/%	0.930	0.170	0.181	0.597
MAD/%	1.693	0.311	0.390	1.492

表7 四种模型的拟合结果与实验数据对比

Table 7 The experimental data and correlation results of four viscosity models

T/K	η_exp/(μPa·s)	式(9)		式(10)		式(11)		式(12)
T/K	η_exp/(μPa·s)	η_cal/(μPa·s)	Δη/%	η_cal/(μPa·s)	Δη/%	η_cal/(μPa·s)	Δη/%	η_cal/(μPa·s)	Δη/%
279.24	388.66	395.24	1.69	389.34	0.17	389.27	0.16	391.72	0.79
283.21	370.05	372.77	0.74	370.37	0.09	370.13	0.02	370.95	0.24
288.18	347.55	347.26	-0.08	347.85	0.09	347.54	0.00	346.97	-0.17
293.18	327.53	324.15	-1.03	326.51	-0.31	326.25	-0.39	324.89	-0.81
298.14	306.97	303.46	-1.14	306.62	-0.11	306.45	-0.17	304.80	-0.71
303.25	286.85	284.13	-0.95	287.38	0.18	287.32	0.16	285.76	-0.38
308.11	270.32	267.45	-1.06	270.26	-0.02	270.27	-0.02	269.12	-0.44
313.08	253.19	251.88	-0.52	253.85	0.26	253.89	0.28	253.41	0.09
323.09	223.36	224.46	0.49	223.95	0.26	223.92	0.25	225.29	0.86
333.17	198.13	201.29	1.59	197.74	-0.20	197.41	-0.36	201.09	1.49

图4 四种模型关联方程与实验数据的偏差

Fig.4 Deviations for R1336mzz(E) of the correlation of four viscosity models from the experimental viscosity

表8 R1336mzz(E)黏度的四种模型关联方程外推结果

Table 8 The extrapolation results of the four models of R1336mzz(E) viscosity

T/K	η_cal/(μPa·s)
T/K	式（9）	式（10）	式（11）	式（12）
273.15	433.7	420.0	420.6	426.6
278.15	401.7	394.7	394.7	397.7
283.15	373.1	370.7	370.4	371.3
288.15	347.4	348.0	347.7	347.1
293.15	324.3	326.6	326.4	325.0
298.15	303.4	306.6	306.4	304.7
303.15	284.5	287.7	287.7	286.1
308.15	267.3	270.1	270.1	269.0
313.15	251.7	253.6	253.7	253.2
318.15	237.4	238.2	238.2	238.6
323.15	224.3	223.8	223.7	225.1
328.15	212.3	210.3	210.2	212.7
333.15	201.3	197.8	197.4	201.1
338.15	191.2	186.1	185.5	190.4
343.15	181.8	175.1	174.3	180.4
348.15	173.2	165.0	163.8	171.2
353.15	165.2	155.4	153.9	162.6
358.15	157.8	146.6	144.7	154.5
363.15	150.9	138.3	136.0	147.0
368.15	144.4	130.6	127.9	140.0
373.15	138.4	123.4	120.2	133.4
378.15	132.8	116.6	113.1	127.3
383.15	127.6	110.3	106.3	121.5
388.15	122.7	104.4	100.0	116.1
393.15	118.1	98.9	94.1	111.1
398.15	113.8	93.8	88.5	106.3
403.15	109.8	89.0	83.3	101.8
403.37	109.6	88.8	83.0	101.6

图5 R1336mzz(E)黏度的四种模型关联方程外推结果

Fig.5 The extrapolation results of the four models of R1336mzz(E) viscosity

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制冷剂R1336mzz（E）液相黏度理论与实验研究

Experimental and theoretical study on liquid viscosity of R1336mzz(E)

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