基于吸收式制冷循环的CaCl2-LiCl/H2O工质对研究

doi:10.11949/0438-1157.20190169

摘要/Abstract

摘要：

利用低品位的太阳能热、地热或者工业领域低温余热废热进行吸收式制冷是实现节能减排的一个有效途径。对具有良好制冷吸收特性的工质对CaCl₂-LiCl/H₂O进行了实验研究，通过测定不同质量比的CaCl₂-LiCl/H₂O溶液的饱和蒸气压，得出了CaCl₂与LiCl的质量比为2∶1的工质对即CaCl₂-LiCl(2∶1)/H₂O的制冷吸收特性最佳。CaCl₂-LiCl(2∶1)/H₂O与常规的工质对LiBr/H₂O相比，在大幅降低工质对成本的同时，在同一制冷工况下所需驱动热源温度即发生温度降低了5.8℃，而制冷COP提高0.041，?效率提高0.052。还系统测定了CaCl₂-LiCl(2∶1)/H₂O的结晶温度、密度、黏度、比热容、比焓以及腐蚀性。结果表明，相较于其他几种以CaCl₂为主要成分的工质对，CaCl₂-LiCl(2∶1)/H₂O具有较低的黏性，且对碳钢和紫铜的腐蚀性也较小，可满足实际工程应用的要求。

关键词: 吸收式制冷, 制冷吸收特性, 工质对, 结晶, 黏度, 腐蚀

Abstract:

Absorption refrigeration using low-grade solar heat, geothermal heat or industrial waste heat as driving heat source is an effective way to achieve energy saving and emission reduction. A new working pair of CaCl₂-LiCl/H₂O, which has an excellent refrigeration absorption characteristic, was studied by measuring its crystallization temperature and vapor pressure with different mass ratios of CaCl₂∶LiCl. The results showed that CaCl₂-LiCl(2∶1)/H₂O with a mass ratio of 2∶1 was the most suitable working pair for an absorption refrigeration system. Compared with LiBr/H₂O, under the same refrigeration conditions, the required driving heat source temperature, that is, the required generation temperature for CaCl₂-LiCl(2∶1)/H₂O was 5.8℃ lower, COP and exergy efficiency for CaCl₂-LiCl(2∶1)/H₂O were 0.041 and 0.052 higher, respectively. Furthermore, the cost of working pair was greatly reduced. In addition, the crystallization temperature, saturated vapor pressure, density, viscosity, specific heat capacity, specific enthalpy, and corrosivity of CaCl₂-LiCl(2∶1)/H₂O were measured systematically. Compared with other working pairs using CaCl₂ as the main component, CaCl₂-LiCl(2∶1)/H₂O had a relatively low viscosity and low corrosion rates for carbon steel and copper, so it could meet the requirements of practical engineering application.

Key words: absorption refrigeration, absorption characteristic of refrigeration, working pair, crystallization, viscosity, corrosion

中图分类号:

TB 61.6

李艺群, 罗春欢, 李娜, 苏庆泉. 基于吸收式制冷循环的CaCl₂-LiCl/H₂O工质对研究[J]. 化工学报, 2019, 70(9): 3483-3494.

Yiqun LI, Chunhuan LUO, Na LI, Qingquan SU. Study on CaCl₂-LiCl/H₂O as working pair of absorption refrigeration cycle[J]. CIESC Journal, 2019, 70(9): 3483-3494.

图/表 28

参考文献 31

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成分	碳钢	紫铜
C	0.16	—
Mn	0.53	—
Si	0.3	0.006
P	0.035	—
S	0.04	0.01
Zn	—	0.005
Pb	—	0.05
Sn	—	0.05
Fe	余量	0.05
Cu	—	余量

成分	碳钢	紫铜
C	0.16	—
Mn	0.53	—
Si	0.3	0.006
P	0.035	—
S	0.04	0.01
Zn	—	0.005
Pb	—	0.05
Sn	—	0.05
Fe	余量	0.05
Cu	—	余量

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa
25.1	1.255	25.0	0.898	25.0	0.667	25.2	0.388
30.0	1.980	29.7	1.313	29.8	0.914	30.1	0.491
34.8	2.801	35.2	1.827	35.1	1.248	35.0	0.691
40.2	3.835	40.0	2.440	40.1	1.711	40.2	0.990
45.3	5.172	45.0	3.222	45.5	2.240	44.8	1.342
50.0	6.735	49.9	4.191	49.7	2.895	49.6	1.915
55.2	8.418	54.8	5.379	55.1	3.755	55.3	2.602
60.5	10.736	59.6	6.855	60.0	4.804	60.1	3.351
65.0	13.016	65.1	8.746	65.3	6.060	65.0	4.392
69.9	16.262	70.0	10.840	69.7	7.640	70.4	5.525	70.1	4.529
74.6	19.902	75.3	13.457	74.8	9.578	74.9	7.008	75.0	5.660
80.0	24.473	80.2	16.629	79.9	11.942	79.6	8.794	80.3	7.173
85.1	29.233	84.8	20.408	85.1	14.799	85.0	10.985	85.3	8.735
89.7	35.130	89.9	24.920	90.1	18.241	90.1	13.647	89.9	10.847
95.0	42.020	95.0	30.250	95.2	22.364	95.3	16.832	95.2	13.227
100.2	49.987	100.0	36.798	100.3	27.363	99.9	20.640	100.1	16.154

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa	T/℃	p/kPa
25.1	1.255	25.0	0.898	25.0	0.667	25.2	0.388
30.0	1.980	29.7	1.313	29.8	0.914	30.1	0.491
34.8	2.801	35.2	1.827	35.1	1.248	35.0	0.691
40.2	3.835	40.0	2.440	40.1	1.711	40.2	0.990
45.3	5.172	45.0	3.222	45.5	2.240	44.8	1.342
50.0	6.735	49.9	4.191	49.7	2.895	49.6	1.915
55.2	8.418	54.8	5.379	55.1	3.755	55.3	2.602
60.5	10.736	59.6	6.855	60.0	4.804	60.1	3.351
65.0	13.016	65.1	8.746	65.3	6.060	65.0	4.392
69.9	16.262	70.0	10.840	69.7	7.640	70.4	5.525	70.1	4.529
74.6	19.902	75.3	13.457	74.8	9.578	74.9	7.008	75.0	5.660
80.0	24.473	80.2	16.629	79.9	11.942	79.6	8.794	80.3	7.173
85.1	29.233	84.8	20.408	85.1	14.799	85.0	10.985	85.3	8.735
89.7	35.130	89.9	24.920	90.1	18.241	90.1	13.647	89.9	10.847
95.0	42.020	95.0	30.250	95.2	22.364	95.3	16.832	95.2	13.227
100.2	49.987	100.0	36.798	100.3	27.363	99.9	20.640	100.1	16.154

i	A_i	B_i	C_i	AARD
0	-1.596×10²	-1.484×10⁵	5.184×10²	0.74%
1	1.143×10³	2.559×10⁶	7.668×10²
2	1.362×10⁴	2.625×10³	4.173×10²
3	1.536×10³	-9.150×10⁶	-1.481×10²
4	8.118	2.110×10⁶	8.453×10

基于吸收式制冷循环的CaCl₂-LiCl/H₂O工质对研究

Study on CaCl₂-LiCl/H₂O as working pair of absorption refrigeration cycle

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参考文献 31

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w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	ρ/(g·cm^-3)	T/℃	ρ/(g·cm^-3)	T/℃	ρ/(g·cm^-3)	T/℃	ρ/(g·cm^-3)	T/℃	ρ/(g·cm^-3)
30.0	1.8957	30.0	1.9434	30.1	1.9927	30.9	2.0393	—	—
39.8	1.8896	39.8	1.9374	39.9	1.9856	40.1	2.0331	—	—
50.0	1.8829	50.1	1.9309	50.0	1.9789	50.0	2.0267	—	—
60.0	1.8770	60.3	1.9241	60.0	1.9789	60.1	2.0203	60.0	2.0449
69.8	1.8708	69.9	1.9181	69.6	1.9672	69.9	2.0143	70.1	2.0371
79.9	1.8647	79.7	1.9125	79.6	1.9612	80.0	2.0085	80.0	2.0299
89.8	1.8590	89.7	1.9069	89.8	1.9550	89.9	2.0029	90.1	2.0248
99.9	1.8535	99.6	1.9012	99.6	1.9500	99.8	1.9978	99.9	2.0195

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	η/(mPa·s)	T/℃	η/(mPa·s)	T/℃	η/(mPa·s)	T/℃	η/(mPa·s)	T/℃	η/(mPa·s)
30.0	6.4417	30.0	10.0894	30.1	18.4371	30.9	33.5353	—	—
39.8	5.0810	39.8	7.9360	39.9	13.5747	40.1	23.8138	—	—
50.0	4.1293	50.1	6.2727	50.0	10.1141	50.0	17.5305	—	—
60.0	3.4514	60.3	5.0874	60.0	8.3263	60.1	13.6596	60.0	18.4415
69.8	2.9182	69.9	4.2625	69.6	6.6501	69.9	10.7005	70.1	14.0103
79.9	2.5188	79.7	3.5989	79.6	5.5813	80.0	8.7180	80.0	11.0275
89.8	2.1855	89.7	3.0674	89.8	4.7153	89.9	7.1871	90.1	9.0751
99.9	1.9162	99.6	2.6789	99.6	3.9853	99.8	6.0610	99.9	7.5790

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	c_p /(kJ·kg^-1·℃^-1)	T/℃	c_p /(kJ·kg^-1·℃^-1)	T/℃	c_p /(kJ·kg^-1·℃^-1)	T/℃	c_p /(kJ·kg^-1·℃^-1)	T/℃	c_p /(kJ·kg^-1·℃^-1)
30.0	2.68	30.0	2.56	30.0	2.43	30.0	2.28	—	—
40.0	2.69	40.0	2.57	40.0	2.45	40.0	2.30	—	—
50.0	2.70	50.0	2.59	50.0	2.46	50.0	2.31	—	—
60.0	2.71	60.0	2.60	60.0	2.48	60.0	2.34	60.0	2.21
70.0	2.74	70.0	2.63	70.0	2.50	70.0	2.35	70.0	2.23
80.0	2.76	80.0	2.65	80.0	2.52	80.0	2.38	80.0	2.26
90.0	2.78	90.0	2.68	90.0	2.55	90.0	2.40	90.0	2.28
100.0	2.80	100.0	2.70	100.0	2.57	100.0	2.42	100.0	2..29

i	A_i	B_i	C_i	AARD
0	2.2760×10	2.9488×10^-2	1.8683×10^-4	0.19%
1	3.6877×10	-1.2945×10^-1	8.6798×10^-4
2	-6.9317×10²	1.4542×10^-1	-9.6057×10^-4

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	h/(kJ·kg^-1)	T/℃	h/(kJ·kg^-1)	T/℃	h/(kJ·kg^-1)	T/℃	h/(kJ·kg^-1)	T/℃	h/(kJ·kg^-1)
30.0	321.29	30.0	310.46	30.0	304.27	30.0	298.49	—	—
40.0	348.13	40.0	336.07	40.0	328.64	40.0	321.34	—	—
50.0	375.14	50.0	361.88	50.0	353.22	50.0	344.40	—	—
60.0	402.33	60.0	387.89	60.0	378.01	60.0	367.66	60.0	353.23
70.0	429.71	70.0	414.10	70.0	403.00	70.0	391.14	70.0	375.46
80.0	457.26	80.0	440.51	80.0	428.21	80.0	414.82	80.0	397.92
90.0	484.99	90.0	467.12	90.0	453.63	90.0	438.72	90.0	420.60
100.0	512.91	100.0	493.93	100.0	479.26	100.0	462.83	100.0	443.52

i	A_i	B_i	C_i	D_i	AARD
0	-1.4508×10³	5.7582×10³	-1.1136×10⁴	8.1644×10³	0.02%
1	1.4530×10¹	-7.3293×10¹	1.4604×10²	-1.0071×10^-2
2	-1.9842×10^-2	1.2769×10^-1	-2.6044×10^-1	1.7708×10^-1

w＝40.0%		w＝45.0%		w＝50.0%		w＝55.0%		w＝60.0%
T/℃	s/(kJ·kg^-1·℃^-1)	T/℃	s/(kJ·kg^-1·℃^-1)	T/℃	s/(kJ·kg^-1·℃^-1)	T/℃	s/(kJ·kg^-1·℃^-1)	T/℃	s/(kJ·kg^-1·℃^-1)
30.0	1.6839	30.0	1.6936	30.0	1.7027	30.0	1.7132	—	—
40.0	1.7710	40.0	1.7768	40.0	1.7819	40.0	1.7875	—	—
50.0	1.8558	50.0	1.8578	50.0	1.8595	50.0	1.8592	—	—
60.0	1.9387	60.0	1.9371	60.0	1.9353	60.0	1.9298	60.0	1.9398
70..0	2.0210	70..0	2.0152	70..0	2.0088	70..0	1.9995	70..0	2.0054
80.0	2.0991	80.0	2.0921	80.0	2.0813	80.0	2.0689	80.0	2.0701
90.0	2.1769	90.0	2.1667	90.0	2.1524	90.0	2.1358	90.0	2.1338
100.0	2.2531	100.0	2.2400	100.0	2.2221	100.0	2.2014	100.0	2.1949

i	A_i	B_i	C_i	D_i	AARD
0	1.5469×10²	-1.0106×10³	2.1465×10³	-1.5011×10³	0.98%
1	-1.2590×10⁰	8.1964×10⁰	-1.7371×10¹	1.2146×10¹
2	3.4252×10^-3	-2.2055×10^-2	4.6621×10^-2	-3.2573×10^-2
3	-3.0971×10^-6	1.9836×10^-5	-4.1854×10^-5	2.9198×10^-5

工质对	稀溶液	浓溶液
① CaCl₂-LiCl (2∶1)/H₂O	54.20%	57.20%
② LiBr/H₂O	56.40%	59.40%
③ CaCl₂-LiBr-LiNO₃-KNO₃(16.2∶2∶2∶1)/H₂O	58.50%	61.50%
④ CaCl₂-LiNO₃-LiBr (8.72∶1∶1)/H₂O	57.30%	60.30%
⑤ CaCl₂-LiBr (1.35∶1)/H₂O	55.80%	58.80%

点	物质	p/k Pa	T/℃	w/%	h/ (kJ·kg^-1)	s/ (kJ·kg^-1·℃^-1)	D/ (kg·s^-1)
1	冷凝水	0.872	5.0	0	439.6	1.6082	1
1′	水蒸气	0.872	5.0	0	2927.9	10.5598	1
2	稀溶液	0.872	37.0	54.2	314.7	1.7639	19.1
3	冷凝水	6.290	37.0	0	573.5	2.0639	1
4	浓溶液	6.290	75.2	57.2	397.1	2.0360	18.1
4′	水蒸气	6.290	75.2	0	3058.5	10.0539	1
5	稀溶液	6.290	72.2	54.2	398.5	2.0168	19.1
6	浓溶液	6.290	39.9	57.2	316.8	1.7908	18.1
7	稀溶液	—	64.8	54.2	380.8	1.9654	19.1
8	浓溶液	—	44.6	57.2	327.3	1.8274	18.1

过程	?损失/kW
过程	CaCl₂-LiCl(2∶1)/H₂O	LiBr/H₂O
蒸发过程	0.5	0.5
冷凝过程	0.3	0.8
吸收过程	49.2	55.3
发生过程	310.9	332.7
热交换过程	25.7	31.4

过程	?损失/kW
过程	CaCl₂-LiCl(2∶1)/H₂O	LiBr/H₂O
蒸发过程	0.5	0.5
冷凝过程	0.3	0.8
吸收过程	49.2	55.3
发生过程	310.9	332.7
热交换过程	25.7	31.4

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