甲醇-水溶剂中L-苯丙氨酸结晶热力学

doi:10.11949/j.issn.0438-1157.20180893

化工学报 ›› 2019, Vol. 70 ›› Issue (4): 1255-1262.DOI: 10.11949/j.issn.0438-1157.20180893

甲醇-水溶剂中L-苯丙氨酸结晶热力学

曹小雪¹(),吉绍长²,匡雯婕¹,廖安平¹,蓝平¹,张金彦¹()

1. 广西民族大学化学化工学院，广西多糖材料与改性重点实验室，广西高校化学与生物转化过程新技术重点实验室，广西南宁 530006
2. 广西烟草专卖局，广西南宁 530006

收稿日期:2018-08-03 修回日期:2018-11-01 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 张金彦
作者简介:<named-content content-type="corresp-name">曹小雪</named-content>（1992—），女，硕士，<email>cxx818221@163.com</email>|张金彦（1984—），女，博士，副教授，<email>zjy_03@126.com</email>
基金资助:
国家自然科学基金项目(21606056);广西自然科学基金项目(2017GXNSFAA198091, 2014GXNSFBA118037);广西生物多糖分离纯化及改性研究平台建设项目(桂科ZY18076005);广西民族大学相思湖创新团队项目(2016);广西民族大学研究生教育创新计划项目(gxun-chxzs2017128)

Crystallization thermodynamics of L-phenylalanine in methanol-water solvent

Xiaoxue CAO¹(),Shaochang JI²,Wenjie KUANG¹,Anping LIAO¹,Ping LAN¹,Jinyan ZHANG¹()

1. Guangxi Key Laboratory for Polysaccharide Materials and Modifications，Key Laboratory of Chemical and Biological Transformation Process of Guangxi Higher Education Institutes, College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, Guangxi, China
2. Guangxi Tobacco Monopoly Bureau, Nanning 530006, Guangxi, China

Received:2018-08-03 Revised:2018-11-01 Online:2019-04-05 Published:2019-04-05
Contact: Jinyan ZHANG

摘要/Abstract

摘要：

在293.15~322.15 K温度范围内，研究L-苯丙氨酸无水物在甲醇-水混合溶剂中溶解度和超溶解度特性，得到L-苯丙氨酸无水物结晶介稳区，计算了成核级数及成核速率，考察了不同初始温度和降温速率对介稳区宽度的影响，并通过研究L-苯丙氨酸297.15 K和302.15 K的转晶水活度，依据溶解度特性绘制L-苯丙氨酸-甲醇-水在该温度下的三元相图。溶解度数据用Apelblat方程、λh方程关联、van t Hoff方程拟合。结果表明，L-苯丙氨酸无水物溶解度随温度的升高而增大，随甲醇体积分数的增加而减小；L-苯丙氨酸无水物结晶介稳区宽度在相同条件下，随初始温度的升高，降温速率的降低变窄；L-苯丙氨酸转晶水活度随温度的升高而增大。

关键词: L-苯丙氨酸, 溶解度, Apelblat方程, 三元相图, 介稳区

Abstract:

The solubility and supersolubility of L-phenylalanine anhydrate in methanol-water mixed solvent were studied in the temperature range of 293.15—322.15 K, and the crystalline metastable zone of L-phenylalanine anhydrate was obtained. The nucleation order and rate was calculated. Meanwhile, the in?uences of temperature and cooling rate on the width of metastable zone were explored. The water activity of transformation at 297.15 K and 302.15 K were measured, the phase diagram of L-phenylalanine-methanol-water at that temperature was obtained through solubility property. The solubility data were correlated by the modified Apelblat equation, λh equation and van t Hoff equation. The results showed that the solubility of L-phenylalanine obviously increased with the increase of temperature and the decrease of the methanol content; the width of metastable zone decreased with increasing temperature and decreasing cooling rate; the water activity of transformation increased with the increase of temperature.

Key words: L-phenylalanine, solubility, Apelblat equation, ternary phase diagram, metastable zone

中图分类号:

TQ 026.5

曹小雪, 吉绍长, 匡雯婕, 廖安平, 蓝平, 张金彦. 甲醇-水溶剂中L-苯丙氨酸结晶热力学[J]. 化工学报, 2019, 70(4): 1255-1262.

Xiaoxue CAO, Shaochang JI, Wenjie KUANG, Anping LIAO, Ping LAN, Jinyan ZHANG. Crystallization thermodynamics of L-phenylalanine in methanol-water solvent[J]. CIESC Journal, 2019, 70(4): 1255-1262.

图/表 12

图1 L-苯丙氨酸的分子结构式

Fig.1 Structure of L-Phe

图2 L-苯丙氨酸在甲醇水混合溶剂中的溶解度

Fig.2 Mole fraction of L-Phe in methanol-water solvent mixtures

表1 L-苯丙氨酸在甲醇-水混合溶剂中的溶解度

Table 1 Experimental solubility of L-Phe in methanol-water solvent mixtures

T/K	x ^exp×10³	x ^cal,Apel×10³	x ^cal, ^λh ×10³	x ^{cal,van’t Hoff} ×10³	T/K	x ^exp ×10³	x ^cal,Apel ×10³	x ^cal, ^λh ×10³	x ^{cal,van’t Hoff} ×10³
V _methanol∶V _water =4∶6					V _methanol∶V _water =2∶8
322.15	3.29	3.27	3.37	3.33	322.15	3.49	3.52	3.67	3.62
317.15	2.97	3.00	3.02	3.00	317.15	3.36	3.32	3.34	3.32
312.15	2.70	2.72	2.71	2.70	312.15	3.09	3.08	3.03	3.02
307.15	2.46	2.45	2.42	2.42	307.15	2.78	2.82	2.75	2.75
302.15	2.20	2.18	2.15	2.16	302.15	2.53	2.54	2.49	2.50
297.15	1.94	1.92	1.91	1.92	297.15	2.27	2.25	2.24	2.26
293.15	1.68	1.72	1.73	1.74	293.15	2.02	2.02	2.06	2.08
V _methanol∶V _water =3∶7					V _methanol∶V _water =15∶85
322.15	3.42	3.43	3.52	3.48	322.15	3.57	3.59	3.66	3.64
317.15	3.18	3.15	3.17	3.15	317.15	3.38	3.36	3.38	3.36
312.15	2.85	2.87	2.85	2.85	312.15	3.15	3.13	3.11	3.10
307.15	2.55	2.59	2.56	2.56	307.15	2.86	2.89	2.85	2.86
302.15	2.38	2.32	2.29	2.29	302.15	2.64	2.64	2.62	2.62
297.15	2.03	2.05	2.04	2.05	297.15	2.40	2.40	2.39	2.40
293.15	1.83	1.84	1.85	1.86	293.15	2.20	2.20	2.23	2.22
V _methanol∶V _water =25∶75					V _methanol∶V _water =1∶9
322.15	3.46	3.47	3.60	3.55	322.15	3.62	3.66	3.70	3.69
317.15	3.24	3.21	3.24	3.21	317.15	3.52	3.44	3.45	3.44
312.15	2.93	2.94	2.91	2.90	312.15	3.21	3.22	3.20	3.21
307.15	2.62	2.65	2.60	2.60	307.15	2.99	3.00	2.98	2.98
302.15	2.38	2.36	2.32	2.33	302.15	2.74	2.78	2.76	2.76
297.15	2.09	2.08	2.07	2.08	297.15	2.56	2.55	2.56	2.56
293.15	1.84	1.85	1.88	1.89	293.15	2.40	2.38	2.40	2.40

表2 Apelblat 模型拟合参数及均方差

Table 2 Regressed parameters and calculated root-mean-square deviation (RMSD) for L-Phe in methanol-water solvent mixtures by Apelblat equation

V _methanol∶V _water	A	B	C	R ²	RMSD
4∶6	169.60	?9805.76	?25.09	0.9970	3.49×10^?5
3∶7	178.46	?10150.70	?26.43	0.9949	1.67×10^?5
25∶75	246.33	?13260.89	?36.51	0.9983	2.63×10^?5
2∶8	315.16	?16202.01	-46.84	0.9926	1.86×10^?5
15∶85	149.99	?8473.50	?22.39	0.9981	3.15×10^?5
1∶9	80.57	?5137.36	?12.16	0.9903	2.37×10^?5

表3 λh模型拟合参数及均方差

Table 3 Regressed parameters and calculated root-mean-square deviation (RMSD) for L-Phe in methanol-water solvent mixtures by λh equation

V _methanol∶V _water	λ	h	R ²	RMSD
4∶6	0.042	48.74	0.9889	4.85×10^?5
3∶7	0.038	50.96	0.9908	5.22×10^?5
25∶75	0.041	48.55	0.9913	5.88×10^?5
2∶8	0.028	60.38	0.9865	7.45×10^?5
15∶85	0.018	78.15	0.9950	4.02×10^?5
1∶9	0.012	96.40	0.9945	4.15×10^?5

表4 van’t Hoff模型拟合参数及均方差

Table 4 Regressed parameters and calculated root-mean-square deviation (RMSD) for L-Phe in methanol-water solvent mixtures by van’t Hoff equation

V _methanol∶V _water	a	b	R ²	RMSD
4∶6	2110.23	0.84	0.9922	3.26×10^?5
3∶7	2037.10	0.66	0.9919	4.41×10^?5
25∶75	2050.55	0.73	0.9922	4.70×10^?5
2∶8	1813.77	0.0097	0.9858	6.31×10^?5
15∶85	1595.19	-0.66	0.9954	3.28×10^?5
1∶9	1399.38	-1.26	0.9932	3.83×10^?5

表5 L-苯丙氨酸在混合溶剂中的摩尔分数数据及稳定性晶型

Table 5 Molar fraction data and stable crystal form of L-Phe in mixed solvents

溶液水体积分数/%	x×10³	稳定晶型	溶液水体积分数/%	x×10³	稳定晶型
297.15 K			302.15 K
40	1.79	anhydrous	70	2.38	anhydrous
50	1.81	anhydrous	75	2.38	anhydrous
60	1.93	anhydrous	80	2.53	anhydrous
65	1.97	anhydrous	85	2.64	anhydrous
70	2.03	anhydrous	87	2.67	anhydrous
75	2.08	anhydrous	90	2.74	anhydrous
80	2.27	anhydrous	93	2.83	anhydrous
81	2.30	anhydrous	94	2.88	anhydrous
82	2.34	anhydrous	95	2.92	anhydrous
83	2.36	anhydrous	96	2.89	anhydrous+monohydrate
84	2.38	anhydrous	97	2.94	monohydrate
85	2.40	anhydrous	99	2.98	monohydrate
86	2.47	anhydrous	100	3.01	monohydrate
88	2.50	anhydrous
89	2.37	anhydrous+monohydrate
90	2.46	monohydrate
100	2.57	monohydrate

表6 Wilson 方程参数

Table 6 Parameters of Wilson equation

体系	(g ₁₂?g ₁₁)/(J/mol)	(g ₂₁?g ₂₂)/(J/mol)	$V 1 L$ /(cm³/mol)	$V 2 L$ /(cm³/mol)
甲醇+水	107.3832	469.5509	18.018883	39.57286

表6 Wilson 方程参数

Table 6 Parameters of Wilson equation

体系	(g ₁₂?g ₁₁)/(J/mol)	(g ₂₁?g ₂₂)/(J/mol)	$V 1 L$ /(cm³/mol)	$V 2 L$ /(cm³/mol)
甲醇+水	107.3832	469.5509	18.018883	39.57286

图3 L-苯丙氨酸-甲醇-水三元相图

Fig.3 Ternary phase diagram of L-Phe-methanol-water at 297.15 K and 302.15 K(All axis scales are in mass percentage)

图4 初始温度对L-苯丙氨酸介稳区的影响

Fig.4 Effect of temperature on metastable zone

图5 L-苯丙氨酸成核动力学参数拟合曲线

Fig.5 Linear dependence lgΔT max with lgb for L-Phe

图6 L-苯丙氨酸成核速率随降温速率的变化趋势

Fig.6 Dependence of nucleation rate on cooling rate for L-Phe

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甲醇-水溶剂中L-苯丙氨酸结晶热力学

Crystallization thermodynamics of L-phenylalanine in methanol-water solvent

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