LiBr-[BMIM]Cl/H2O新型三元工質對的密度、黏度、比熱容及比焓

羅春歡; 王亞楠; 韓旭; 李藝群; 蘇慶泉

doi:10.13374/j.issn2095-9389.2019.06.004

LiBr-[BMIM]Cl/H₂O新型三元工質對的密度、黏度、比熱容及比焓

doi: 10.13374/j.issn2095-9389.2019.06.004

羅春歡^{1, 2},
王亞楠¹,
韓旭¹,
李藝群¹,
蘇慶泉^{1, 2, ,}

1.
北京科技大學能源與環境工程學院, 北京 100083
2.
北京科技大學北京市高校節能與環保工程研究中心, 北京 100083

基金項目:

國家自然科學基金資助項目 51506005

中央高校基本科研業務費資助項目 FRF-TP-18-010A3

詳細信息

通訊作者:
蘇慶泉, E-mail: suqingquan@ustb.edu.cn

中圖分類號: TK01⁺9
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出版歷程
- 收稿日期: 2018-05-30
- 刊出日期: 2019-06-01

Density, viscosity, specific heat capacity, and specific enthalpy of a novel ternary working pair: LiBr-[BMIM]Cl/H₂O

LUO Chun-huan^{1, 2},
WANG Ya-nan¹,
HAN Xu¹,
LI Yi-qun¹,
SU Qing-quan^{1, 2
, ,}

1.
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Beijing Engineering Research Center for Energy Saving and Environmental Protection, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: SU Qing-quan, E-mail: suqingquan@ustb.edu.cn

摘要

摘要: 在前期研究的基礎上, 對LiBr-[BMIM]Cl/H₂O三元工質對的其他重要熱力學數據進行了系統地測定, 包括密度、黏度、比熱容和比焓.采用最小二乘法對測定的熱力學數據進行回歸, 得到了物性方程; 實驗值與物性方程計算值的平均絕對相對偏差(average absolute relative deviation, AARD)分別為0.03%、1.10%、0.29%和0.01%.除了結晶溫度和腐蝕性, 黏度是影響工質對實際應用的另外一個重要因素, LiBr-[BMIM]Cl/H₂O三元工質對的運動黏度小于25 mm²·s^-1, 滿足實際應用要求, 且很好地改善了離子液體的高黏度問題.
- 離子液體 /
- 溴化鋰 /
- 工質對 /
- 熱物性 /
- 吸收式熱泵
Abstract: Absorption heat pump (AHP) system is an energy-saving technology that utilizes renewable energy or industrial waste heat for refrigeration and heating. Therefore, it has attracted much attention for use in residential and industrial buildings. The thermodynamic performance of the AHP system greatly depends on the thermodynamic properties of its working pairs. In commercial applications, LiBr/H₂O is usually used as a traditional working pair. However, its shortcomings of easy crystallization and severe corrosion have significant impacts on the practical application of high-temperature AHP systems. To overcome the shortcomings of LiBr/H₂O, various ionic liquids (ILs)/H₂O mixtures have been recently investigated as alternative working pairs. Though ILs/H₂O has a wider operating temperature range and less corrosiveness, ILs/H₂O working pairs generally have very high viscosity, which restricts its practical applications. To further solve the above shortcomings of LiBr/H₂O and ILs/H₂O, a new ternary working pairs LiBr-[BMIM]Cl/H₂O was proposed in the previous study. Compared to the traditional LiBr/H₂O binary working pair, the LiBr-[BMIM]Cl/H₂O ternary working pair has advantages in terms of crystallization temperature and corrosiveness. LiBr-[BMIM]Cl/H₂O shows a great potential in the practical application of an AHP and refrigeration systems, especially at a high temperature. Based on the previous study, in this work, several important thermodynamic properties, including densities, viscosities, specific heat capacities, and specific enthalpies were systematically measured and correlated using the least-squares method, and the average absolute relative deviation (AARD) between the measured data and the calculated data is 0.03%, 1.10%, 0.29%, and 0.01%, respectively. In addition to the crystallization temperature and corrosiveness, viscosity is another key thermodynamic property affecting the practical application of working pairs in AHP system. The viscosity of LiBr-[BMIM]Cl/H₂O is less than 25 mm²·s^-1, which is well compatible with the application requirement. Moreover, the addition of LiBr in[BMIM]Cl/H₂O is beneficial for improving the high viscosity of ionic liquids.
- ionic liquid /
- lithium bromide /
- working pair /
- thermophysical properties /
- absorption heat pump

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圖 1 密度和黏度測量原理圖

Figure 1. Schematic of measurement apparatus for density and viscosity

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圖 2 質量分數為50%的LiBr/H₂O溶液的密度實驗值與文獻值比較

Figure 2. Comparison of the density of 50%mass fraction of LiBr/H₂O between the data measured in this work and literature data

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圖 3 質量分數為50%的LiBr/H₂O溶液的黏度實驗值與文獻值比較

Figure 3. Comparison of the viscosity of 50%mass fraction of LiBr/H₂O between the data measured in this work and literature data

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圖 4 μRC微量熱儀測定比熱容原理圖

Figure 4. Schematic of measurement apparatus for specific heat capacity usingμRC

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圖 5 質量分數為50%的LiBr/H₂O溶液的比熱容實驗值與文獻值比較

Figure 5. Comparison of specific heat capacity of 50%mass fraction of LiBr/H₂O between the data measured in this work and literature data

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圖 6 溶解焓測定原理圖. (a) 注入組件; (b) 組件裝配圖; (c) 裝置圖

Figure 6. Schematic of apparatus for dissolution enthalpy: (a) plunger parts; (b) integration diagram; (c) set-up diagram

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圖 7 質量分數為50%和60%的LiBr/H₂O溶液的比焓實驗值與文獻值比較

Figure 7. Comparison of the specific heat capacity of 50%and 60% LiBr/H₂O between the data measured in this work and literature data

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圖 8 LiBr-[BMIM]Cl/H₂O三元工質對的密度

Figure 8. Densities ρ of LiBr-[BMIM]Cl/H₂O ternary working pair

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圖 9 LiBr-[BMIM]Cl/H₂O三元工質對的黏度

Figure 9. Viscosities v of LiBr-[BMIM]Cl/H₂O ternary working pair

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圖 10 LiBr-[BMIM]Cl/H₂O三元工質對的比熱容

Figure 10. Specific heat capacities C_p of the LiBr-[BMIM]Cl/H₂O ternary working pair

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圖 11 LiBr-[BMIM]Cl/H₂O三元工質對的比焓

Figure 11. Specific enthalpies h of the LiBr-[BMIM]Cl/H₂O ternary working pair

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表 1 實驗用試劑材料詳細數據

Table 1. Detailed information of chemical samples

試劑	純度/%	含水質量分數/%	分析方法
[BMIM] Cl	＞99. 0	＜0. 3	凱氏定氮法
LiBr	＞99. 5	—	—
KCl	＞99. 0	—	—

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表 2 溫度為298. 15 K和p = 0. 1 MPa時KCl在水中的積分溶解焓Δh_mix

Table 2. Integral dissolution enthalpy Δh_mix for KCl in water at 298. 15 K and p = 0. 1 MPa ? g·cm^-3

KCl質量分數/%	KCl /H₂O摩爾比	Δh_mix/(kJ·mol^-1)		相對偏差/%
KCl質量分數/%	KCl /H₂O摩爾比	實驗值	文獻值^[23]	相對偏差/%
7. 64	1∶ 50	16. 845	17. 083	1. 39
3. 97	1∶ 100	17. 122	17. 427	1. 75
2. 03	1∶ 200	17. 277	17. 556	1. 59

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表 3 p=0.1 MPa時LiBr-[BMIM]Cl/H₂O體系的密度

Table 3. Density of the system LiBr-[BMIM]Cl/H₂O at p=0.1 MPa ? g·cm^-3

T/K	ρ
T/K	w = 0.55	w = 0.60	w = 0.65	w = 0.70	w = 0.75
303.15	1.384	1.434	1.49	1.549	―
313.15	1.378	1.428	1.483	1.542	―
323.15	1.372	1.422	1.477	1.535	―
333.15	1.367	1.416	1.470	1.528	1.590
343.15	1.361	1.411	1.464	1.521	1.582
353.15	1.355	1.405	1.458	1.515	1.575
363.15	1.349	1.399	1.452	1.508	1.568
373.15	1.343	1.393	1.446	1.502	1.561

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表 4 密度方程擬合系數

Table 4. Values of A_i, B_i, and C_i for least-squares representation by Eq. (10)

i	A_i	B_i/10^-3	C_i/10^-5
0	0. 384514	6. 128884	-1.221983
1	2. 024635	-16.63302	3. 272392
2	8.490245×10^-2	8.778485	- 2. 017801

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表 5 p=0.1 MPa時LiBr-[BMIM]Cl/H₂O體系的運動黏度

Table 5. Viscosity of the system LiBr-[BMIM]Cl/H₂O at p=0.1 MPa ? mm²·s^-1

T/K	V
T/K	w =0.55	w= 0.60	w = 0.65	w = 0.70	w = 0.75
303.15	3.81	6.21	10.31	23.01	—
313.15	3.01	4.88	7.82	16.13	—
323.15	2.44	3.87	6.02	11.61	—
333.15	1.99	3.06	4.66	8.39	21.29
343.15	1.68	2.49	3.71	6.35	14.14
353.15	1.46	2.11	3.05	4.94	10.00
363.15	1.30	1.83	2.60	4.03	7.46
373.15	1.18	1.63	2.22	3.34	5.81

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表 6 運動黏度方程(11) 擬合系數

Table 6. Values of A_i, B_i, and C_i for least-squares representation by Eq. (11) ?

i	A_i/10²	B_i/10⁴	C_i/10⁶
0	1. 217521	- 5. 828088	3. 460217
1	-3. 896274	13. 818580	8. 897532
2	3. 291964	- 1. 092322	- 51. 704210
3	- 0. 295650	- 9. 908650	46. 722780

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表 7 p=0.1 MPa時LiBr-[BMIM]Cl/H₂O體系的比熱容

Table 7. Specific heat capacity of the system LiBr-[BMIM]Cl/H₂O at J·g^-1·K^-1p=0.1 MPa ? J·g^-1·K^-1

T/K	C_p
T/K	w = 0. 55	w = 0. 60	w = 0. 65	w = 0. 70	w = 0. 75
303. 15	2. 30	2.20	2.05	1. 94	—
313. 15	2. 32	2. 21	2. 07	1. 96	—
323. 15	2. 33	2. 22	2. 08	1. 96	—
333. 15	2. 34	2. 22	2. 10	1. 97	1. 85
343. 15	2. 35	2. 23	2. 11	1. 98	1. 86
353. 15	2. 38	2. 24	2. 12	2. 01	1. 88
363. 15	2. 40	2. 27	2. 16	2. 03	1. 91
373. 15	2. 45	2. 30	2. 19	2. 07	1. 93

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表 8 比熱容方程(12) 擬合系數

Table 8. Values of A_i, B_i, C_i for least-squares representation by Eq. (12)

i	A_i	B_i/10^-2	C_i/10^-5
0	4. 656718	- 1. 447759	3. 392384
1	3. 182206	- 1. 114172	-1.471251
2	- 6. 925005	2. 383878	-1. 126738

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表 9 p=0.1 MPa時不同溫度下離子液體[BMIM]Cl的比熱容

Table 9. Specific heat capacities of ionic liquid[BMIM]Cl at p=0.1 MPa and different temperatures

溫度/K	283.15	293.15	303. 15	313. 15	323.15	333. 15	343.15	353. 15	363. 15	373. 15
比熱容/(J.g^-1·K^-1)	1. 55	1.62	1.73	1.94	2. 55	6. 31	1. 98	1. 98	2. 025	2. 05

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表 10 溫度為313.15 K和p=0.1 MPa時不同質量分數LiBr-[BMIM]Cl/H₂O體系的溶解焓

Table 10. Dissolution enthalpies at various mass fractions of LiBr-[BMIM]Cl/H₂O at 313.15 K and p=0.1 MPa

質量分數	0. 55	0. 60	0. 65	0. 70
溶解焓/(kJ·kg^-1)	－ 160. 66	－ 173. 93	－ 189. 89	－ 168. 04

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表 11 p=0.1 MPa時LiBr-[BMIM]Cl/H₂O體系的比焓

Table 11. Specific enthalpies of the system LiBr-[BMIM]Cl/H₂O at p=0.1 MPa ? J·g^-1

T /K	h
T /K	w =0. 55	w = 0. 60	w = 0. 65	w = 0. 70
303. 15	331. 04	312.51	291.33	307. 99
313. 15	354. 18	334. 45	312. 04	327. 44
323.15	377. 38	356. 45	332. 82	346. 97
333. 15	400. 70	378. 56	353. 70	366. 60
343. 15	424. 17	400. 81	374. 72	386. 39
353. 15	447. 84	423. 24	395. 92	406. 35
363. 15	471.75	445. 91	417. 34	426. 54
373. 15	495. 96	468. 84	439. 01	446. 98

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表 12 比焓方程(13) 擬合系數

Table 12. Values of A_i, B_i, C_i for least-squares representation by Eq. (13)

i	A_i	B_i	C_i	D_i
0	-1. 184934 x10⁴	5.791208 x10⁴	-9. 675233 x10⁴	5.399248 x10⁴
1	7. 876601 x10^-1	4.862318	-5.643877	2.016601 x10^-3
2	4. 233235 x10^-3	-1.054922x10^-2	8. 114677 x10^-3	-2. 862036 x10^-6

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