莰烯+(+)-3-蒈烯体系汽液平衡数据的测定与关联

doi:10.11949/0438-1157.20190028

摘要/Abstract

摘要：

改进了Ellis平衡釜的保温、搅拌与压力控制系统，建立了一套可视窗口的实验装置。测定了莰烯+(+)-3-蒈烯体系在313.15、373.15和433.15 K下的汽液平衡数据；采用面积法和Van Ness检验法对实验数据进行热力学一致性检验，所有数据均符合Gibbs-Duhenm的热力学一致性；选用Aspen plus软件中NRTL、Wilson和UNIQUAC模型，由最大似然法对目标函数进行优化，实现对实验数据的关联。结果表明，气相组成和平衡压力的估算值与实验值的最大平均相对偏差为0.0128和0.0009，最大均方根偏差为0.0003和0.0012 kPa，相对挥发度的估算值与实验值的绝对平均偏差分别为0.09%、0.03%和0.04%。

关键词: 莰烯, (+)-3-蒈烯, Ellis平衡釜, 等温汽液平衡, 测定, 关联

Abstract:

The insulation, stirring and pressure control system of Ellis equilibrium still with double circulator for the vapor and liquid phases was improved, and a set of phase equilibrium experimental device with visual window was established. The vapor-liquid equilibrium data of terpene+(+)-3-decene system at 313.15, 373.15 and 433.15 K were determined. The thermodynamic consistency test was performed on the experimental data by area method and Van Ness test. All data were consistent with Gibbs-Duhenm. Furthermore, the VLE data were correlated by the nonrandom two-liquid (NRTL), Wilson and universal quasichemical (UNIQUAC) activity coefficient models in Aspen plus. The objective function was optimized by the maximum likelihood method and the corresponding binary interaction parameters were returned. The results show that the maximum average relative deviation between calculated values and experimental data of the vapor phase molar composition and equilibrium pressure was 0.0128 and 0.0009, the maximum root mean square deviations are 0.0003 and 0.0012 kPa, and the absolute average deviations of relative volatility are 0.09%, 0.03% and 0.04%, respectively.

Key words: camphene, (+)-3-carene, Ellis equilibrium still, isothermal vapor-liquid equilibrium, determination, correlation

中图分类号:

TQ 013.1

吴金芝, 王琳琳, 陈小鹏, 童张法, 范孝雄, 梁保芳. 莰烯+(+)-3-蒈烯体系汽液平衡数据的测定与关联[J]. 化工学报, 2019, 70(6): 2092-2101.

Jinzhi WU, Linlin WANG, Xiaopeng CHEN, Zhangfa TONG, Xiaoxiong FAN, Baofang LIANG. Determination and correlation of vapor-liquid equilibrium data for camphene+(+)-3-carene system[J]. CIESC Journal, 2019, 70(6): 2092-2101.

图/表 18

图1 试剂的化学结构

Fig.1 Chemical structures of reagents

图2 汽液平衡测定实验装置

Fig. 2 Apparatus diagram for VLE experimental measurement

图3 53.3 kPa下α-蒎烯+对伞花烃的汽液平衡相图

Fig.3 VLE phase diagram for system of α-pinene + p-cymene at 53.3 kPa

图4 莰烯+(+)-3-蒈烯体系在313.15 K条件下的P-x-y相图

Fig.4 P-x-y diagram of camphene+(+)-3-carene system at 313.15 K

图5 莰烯+(+)-3-蒈烯体系在373.15 K条件下的P-x-y相图

Fig.5 P-x-y diagram of camphene+(+)-3-carene system at 373.15 K

图6 莰烯+(+)-3-蒈烯体系在433.15 K条件下的P-x-y相图

Fig.6 P-x-y diagram of camphene+(+)-3-carene system at 433.15 K

表1 莰烯+(+)-3-蒈烯在313.15 K下的汽液平衡实验数据①及相对挥发度

Table 1 VLE data and relative volatility for camphene+(+)-3-carene at 313.15 K

No.	P/kPa	x ₁	y ₁	α ₁₂
1	1.09	0.0000	0.0000	—
2	1.10	0.0499	0.0585	1.1825
3	1.11	0.1248	0.1447	1.1863
4	1.12	0.1748	0.2012	1.1885
5	1.13	0.2247	0.2566	1.1906
6	1.14	0.2747	0.3111	1.1923
7	1.15	0.3247	0.3646	1.1937
8	1.16	0.3746	0.4171	1.1949
9	1.17	0.3996	0.4431	1.1953
10	1.18	0.4496	0.4942	1.1960
11	1.19	0.4994	0.5441	1.1962
12	1.20	0.5494	0.5932	1.1961
13	1.21	0.5998	0.6418	1.1955
14	1.22	0.6495	0.6888	1.1944
15	1.24	0.7246	0.7582	1.1918
16	1.25	0.7747	0.8035	1.1893
17	1.26	0.8248	0.8482	1.1862
18	1.7	0.8749	0.8921	1.1824
19	1.28	0.9249	0.9355	1.1780
20	1.29	0.9750	0.9786	1.1724
21	1.29	1.0000	1.0000	—

表2 莰烯+(+)-3-蒈烯在373.15 K下的汽液平衡实验数据①及相对挥发度

Table 2 VLE data and relative volatility for camphene+(+)-3-carene at 373.15 K

No.	P/kPa	x ₁	y ₁	α ₁₂
1	13.05	0.0000	0.0000	—
2	13.26	0.0502	0.0653	1.3218
3	13.48	0.1003	0.1285	1.3226
4	13.69	0.1499	0.1891	1.3225
5	13.90	0.2001	0.2486	1.3226
6	14.11	0.2496	0.3056	1.3231
7	14.43	0.3253	0.3895	1.3233
8	14.64	0.3747	0.4423	1.3235
9	14.95	0.4502	0.5202	1.3241
10	15.16	0.4998	0.5695	1.3239
11	15.48	0.5752	0.6420	1.3244
12	15.69	0.6256	0.6888	1.3246
13	15.90	0.6747	0.7332	1.3250
14	16.22	0.7500	0.7991	1.3259
15	16.43	0.8004	0.8417	1.3260
16	16.75	0.8749	0.9027	1.3266
17	16.86	0.9003	0.9230	1.3275
18	16.96	0.9251	0.9425	1.3271
19	17.17	0.9752	0.9812	1.3273
20	17.28	1.0000	1.0000	—

表3 莰烯+(+)-3-蒈烯在433.15 K下的汽液平衡实验数据①及相对挥发度

Table 3 VLE data and relative volatility for camphene+(+)-3-carene at 433.15 K

No.	P/kPa	x ₁	y ₁	α ₁₂
1	78.73	0.0000	0.0000	—
2	79.29	0.0252	0.0321	1.2819
3	80.40	0.0753	0.0945	1.2821
4	81.52	0.1249	0.1547	1.2822
5	82.63	0.1751	0.2140	1.2824
6	84.31	0.2502	0.2997	1.2827
7	85.43	0.3006	0.3554	1.2828
8	87.10	0.3748	0.4348	1.2831
9	88.21	0.4252	0.4870	1.2832
10	89.32	0.4749	0.5372	1.2834
11	90.45	0.5254	0.5869	1.2836
12	92.12	0.5995	0.6578	1.2838
13	93.79	0.6755	0.7277	1.2841
14	94.91	0.7246	0.7716	1.2842
15	96.03	0.7753	0.8159	1.2844
16	98.26	0.8748	0.8998	1.2847
17	99.38	0.9254	0.9410	1.2849
18	100.49	0.9747	0.9802	1.2851
19	101.05	1.0000	1.0000	—

表4 汽液平衡实验数据的热力学一致性检验

Table 4 Thermodynamic consistency test of vapor-liquid equilibrium experimental data

T/K	AREA^①		Van Ness^②
	AREA^①		NRTL		Wilson		UNIQUAC		Result
	Value	Result	Δy	ΔP	Δy	ΔP	Δy	ΔP	Result
313.15	4.5287	passed	0.0012	0.0004	0.0092	0.0006	0.0027	0.0005	passed
373.15	8.6831	passed	0.0030	0.0013	0.0029	0.0020	0.0034	0.0010	passed
433.15	1.3367	passed	0.0039	0.0010	0.0039	0.0010	0.0037	0.0009	passed

表5 莰烯+3-蒈烯体系NRTL，Wilson和UNIQUAC活度系数模型的二元相互作用能量参数，以及莰烯组分的气相组成(y 1)和平衡压力(P)的均方根偏差(RMSD)和平均绝对偏差(AAD)

Table 5 Binary interaction energy parameters of NRTL, Wilson and UNIQUAC activity coefficient models for camphene +3-carene systeme, and root mean square deviation (RMSD) and average absolute deviations (AAD) for vapor phase mole fraction (y 1) and equilibrium pressure (P)

model	Binary interaction parameters							RMSD		AAD
model	$a i j$	$a j i$		$b i j / Κ$	$b j i / Κ$		$c i j$	y ₁	P/kPa	y ₁	P/kPa
NRTL	0.131792		-0.160414	118.289487		-87.54019	0.3	0.0000	0.0005	0.0000	0.0004
Wilson	0.124744		-0.090117	70.204871		-105.15032		0.0000	0.0005	0.0000	0.0004
UNIQUAC	0.033377		0.008403	36.4785569		-422.10712		0.0001	0.0004	0.0001	0.0003

model	Binary interaction parameters							RMSD		AAD
model	$a i j$	$a j i$		$b i j / Κ$	$b j i / Κ$		$c i j$	y ₁	P/kPa	y ₁	P/kPa
NRTL	0.131792		-0.160414	118.289487		-87.54019	0.3	0.0000	0.0005	0.0000	0.0004
Wilson	0.124744		-0.090117	70.204871		-105.15032		0.0000	0.0005	0.0000	0.0004
UNIQUAC	0.033377		0.008403	36.4785569		-422.10712		0.0001	0.0004	0.0001	0.0003

表6 UNIQUAC模型分子参数r(van der Waals分子体积)和q(van der Waals分子表面积)

Table 6 van der Waals volume (r) and surface area (q) of components for UNIQUAC equation

Component	r	q
camphene	6.0560	4.7600
(+)-3-carene	6.0541	4.7560

图7 莰烯+(+)-3-蒈烯体系在313.15 K条件下实验值与模型估算值的相对偏差

Fig.7 Relative deviations of experimental data, P exp, and y exp from calculated results of models, P cal and y cal, for camphene+(+)-3-carene system at 313.15 K

图8 莰烯+(+)-3-蒈烯体系在373.15 K条件下实验值与模型估算值的相对偏差

Fig.8 Relative deviations of experimental data, P exp, and y exp from calculated results of models, P cal and y cal, for camphene+(+)-3-carene system at 373.15 K

图9 莰烯+(+)-3-蒈烯体系在433.15 K条件下实验值与模型估算值的相对偏差

Fig.9 Relative deviations of experimental data, P exp, and y exp from calculated results of models, P cal and y cal, for camphene+(+)-3-carene system at 433.15 K

图10 莰烯+(+)-3-蒈烯体系在313.15 K条件下估算值与实验值的相对挥发度的相对偏差

Fig.10 Relative deviation between calculated values and experimental data of relative volatility of camphene+(+)-3-carene system at 313.15 K

图11 莰烯+(+)-3-蒈烯体系在373.15 K条件下估算值与实验值的相对挥发度的相对偏差

Fig.11 Relative deviation between calculated values and experimental data of relative volatility of camphene+(+)-3-carene system at 373.15 K

图12 莰烯+(+)-3-蒈烯体系在433.15 K条件下相对挥发度的估算值与实验值的相对偏差

Fig.12 Relative deviation between calculated values and experimental data of relative volatility of camphene+(+)-3-carene system at 433.15 K

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