莱鲍迪苷A溶解度与介稳区宽度的测定及其结晶过程研究

doi:10.11949/0438-1157.20201933

摘要/Abstract

摘要：

莱鲍迪苷A是极为重要的新型甜味剂，由于缺乏合理的溶解度数据且其成核机理不明确，导致现存的结晶工艺得到的结晶产品存在细晶多、粒度分布不均等问题。为此，首先利用激光动态法测定了莱鲍迪苷A在甲醇-水、乙醇-水、正丙醇-水、丙酮-水中的溶解度及在甲醇-水中的介稳区宽度，并利用Wilson方程对溶解度进行模型验证；研究了溶剂组成、饱和温度、搅拌速率与冷却速率对介稳区宽度的影响，研究表明，莱鲍迪苷A的介稳区宽度随溶剂中甲醇含量与冷却速率的增加而变宽，随饱和温度与搅拌速率的增加而变窄；基于经典成核理论与相关模型，计算了莱鲍迪苷A的固液界面能γ与临界Gibbs自由能 $Δ G c r i t$ 等成核参数；根据表观成核级数m分析可知，初始温度高于318.15 K时，连续成核是莱鲍迪苷A主导的成核方式；基于上述研究优化了莱鲍迪苷A冷却结晶过程，得到了粒度分布均一的结晶产品。

关键词: 莱鲍迪苷A, 溶解度, 介稳区宽度, 成核, 粒度分布

Abstract:

Rebaudioside A is an extremely important new sweetener. Nevertheless, there are some quality problems of its crystal products obtained by existing crystallization process such as too many fine crystals and large crystal size distribution. In order to solve the above problems, a comprehensive study about crystallization of rebaudioside A was carried out. Firstly, the solubility of rebaudioside A in several binary mixed solvents including methanol-water, ethanol-water, n-propanol-water and acetone-water as well as the metastable zone width in methanol-water mixed solvents were determined by means of laser dynamic technology and the experimental solubility data was verified by Wilson model subsequently. Besides, the influences of solvent composition, agitation rate and cooling rate on metastable zone width were explored and the result showed that the metastable zone width would increase with the increment of the content of methanol in mixed solvents or the increment of cooling rate while would become narrow with the incensement of initial saturation temperature and stirring rate. In addition, on the basis of the classical nucleation theory and corresponding metastable zone model, the nucleation parameters such as interfacial energy between solid and liquid γ and critical Gibbs free energy $Δ G c r i t$ of rebaudioside A were calculated. Furthermore, according to the calculated value of apparent nucleation order m, progressive nucleation was the dominant nucleation mechanism of rebaudioside A when the initial crystallization temperature was higher than 318.15 K. At last, the crystallization process was optimized and the high quality rebaudioside A product with uniform particle size was obtained.

Key words: rebaudioside A, solubility, metastable zone width, nucleation, particle size distribution

中图分类号:

TS 202.3

郭盛争, 吴送姑, 苏鑫, 高伟, 牛志平, 龚俊波. 莱鲍迪苷A溶解度与介稳区宽度的测定及其结晶过程研究[J]. 化工学报, 2021, 72(8): 3997-4008.

Shengzheng GUO, Songgu WU, Xin SU, Wei GAO, Zhiping NIU, Junbo GONG. Determination of solubility and metastable zone width of rebaudioside A and study on its crystallization process[J]. CIESC Journal, 2021, 72(8): 3997-4008.

图/表 20

表1 实验试剂

Table 1 The list of chemicals

药品名称	质量分数	摩尔质量/ (g·mol^-1)	来源
莱鲍迪苷A	≥0.980	967.01	晨光生物科技股份有限公司
甲醇	≥0.998	32.04	天津市康科德科技有限公司
乙醇	≥0.997	46.07	天津市康科德科技有限公司
正丙醇	≥0.995	60.1	天津市康科德科技有限公司
丙酮	≥0.995	58.08	天津福晨化学试剂有限公司
去离子水	≥0.995	18.02	实验室自制

表2 实验设备

Table 2 The list of experimental facilities

仪器名称	型号/规格	生产厂家
分析天平	AL204	瑞士Mettler-Toledo公司
水浴恒温槽	CF41	优莱博仪器有限公司
夹套结晶器	200 ml	天津易普佳玻璃仪器有限公司
数显机械搅拌	ZNCL-BS140	天津星科仪器有限公司
Pixact在线颗粒成像系统	PCM	北京海菲尔格科技有限公司
激光发射仪	JDW3-200	北京大学物理系
激光测量仪	JG2	北京大学物理系

图1 莱鲍迪苷A溶解度与介稳区测定装置图1—水浴恒温槽;2—水银温度计; 3—数显机械搅拌; 4—夹套结晶器; 5—升降台; 6—激光发射器; 7—激光接收器; 8—激光记录仪

Fig.1 Sketch of the apparatus for measurement of solubility and metastable zone of rebaudioside A

表3 莱鲍迪苷A在不同二元混合溶剂中的摩尔溶解度

Table 3 Experimental solubility x1exp of rebaudioside A in different binary mixed solvents at different temperatures （P = 0.1 MPa）

Solvents	$x 1 e x p$ ×10³
Solvents	283.15 K	288.15 K	293.15 K	298.15 K	303.15 K	308.15 K	313.15 K	318.15 K	323.15 K	328.15 K
methanol-water
x_a= 0.4^①	0.312	0.450	0.597	0.861	1.151	1.483	1.938	2.653	3.731	4.793
x_a = 0.5	0.279	0.392	0.496	0.655	0.886	1.196	1.555	2.175	2.915	3.805
x_a = 0.6	0.229	0.306	0.417	0.561	0.756	0.993	1.272	1.632	2.270	2.772
x_a = 0.7	0.203	0.263	0.344	0.446	0.580	0.723	0.934	1.189	1.461	1.810
ethanol-water
x_b = 0.5	1.868	2.239	2.640	2.962	3.556	4.117	4.772	5.474	6.271	7.154
x_b = 0.6	1.338	1.573	1.822	2.020	2.378	2.711	3.094	3.498	3.950	4.444
x_b = 0.7	0.638	0.751	0.891	1.051	1.253	1.463	1.661	1.955	2.230	2.555
n-propanol-water
x_c = 0.4	1.931	2.296	2.756	3.287	3.867	4.574	5.425	6.392	7.330	8.475
x_c = 0.5	0.945	1.147	1.407	1.713	2.149	2.472	2.974	3.452	4.194	5.090
x_c = 0.6	0.471	0.555	0.650	0.804	1.002	1.237	1.430	1.773	2.091	2.591
acetone-water
x_d = 0.3	0.344	0.463	0.619	0.820	1.073	1.340	1.819	2.294	2.909	3.663
x_d = 0.4	0.240	0.319	0.420	0.583	0.671	0.875	1.119	1.406	1.792	2.182
x_d = 0.6	0.036	0.053	0.078	0.123	0.157	0.222	0.299	0.416	0.618	0.766

表3 莱鲍迪苷A在不同二元混合溶剂中的摩尔溶解度

Table 3 Experimental solubility x1exp of rebaudioside A in different binary mixed solvents at different temperatures （P = 0.1 MPa）

Solvents	$x 1 e x p$ ×10³
Solvents	283.15 K	288.15 K	293.15 K	298.15 K	303.15 K	308.15 K	313.15 K	318.15 K	323.15 K	328.15 K
methanol-water
x_a= 0.4^①	0.312	0.450	0.597	0.861	1.151	1.483	1.938	2.653	3.731	4.793
x_a = 0.5	0.279	0.392	0.496	0.655	0.886	1.196	1.555	2.175	2.915	3.805
x_a = 0.6	0.229	0.306	0.417	0.561	0.756	0.993	1.272	1.632	2.270	2.772
x_a = 0.7	0.203	0.263	0.344	0.446	0.580	0.723	0.934	1.189	1.461	1.810
ethanol-water
x_b = 0.5	1.868	2.239	2.640	2.962	3.556	4.117	4.772	5.474	6.271	7.154
x_b = 0.6	1.338	1.573	1.822	2.020	2.378	2.711	3.094	3.498	3.950	4.444
x_b = 0.7	0.638	0.751	0.891	1.051	1.253	1.463	1.661	1.955	2.230	2.555
n-propanol-water
x_c = 0.4	1.931	2.296	2.756	3.287	3.867	4.574	5.425	6.392	7.330	8.475
x_c = 0.5	0.945	1.147	1.407	1.713	2.149	2.472	2.974	3.452	4.194	5.090
x_c = 0.6	0.471	0.555	0.650	0.804	1.002	1.237	1.430	1.773	2.091	2.591
acetone-water
x_d = 0.3	0.344	0.463	0.619	0.820	1.073	1.340	1.819	2.294	2.909	3.663
x_d = 0.4	0.240	0.319	0.420	0.583	0.671	0.875	1.119	1.406	1.792	2.182
x_d = 0.6	0.036	0.053	0.078	0.123	0.157	0.222	0.299	0.416	0.618	0.766

表4 基于Wilson方程拟合得到的参数结果

Table 4 The parameter results based on the fitting of Wilson equation

x	V₂/(cm³·mol^-1)	Δg₁₂/ (J·mol^-1)	Δg₂₁/ (J·mol^-1)	RMSD	R²
x_a =0.4	27.52	-7803	7105	6.74×10^-5	0.9984
x_a =0.5	29.79	-7820	7533	6.70×10^-5	0.9966
x_a =0.6	32.01	-7833	8181	3.54×10^-5	0.9993
x_a =0.7	34.19	-8569	12530	8.05×10^-6	0.9998
x_b =0.5	37.88	-13094	89986	7.12×10^-4	0.9992
x_b =0.6	41.81	-11714	87851	6.28×10^-4	0.9992
x_b =0.7	45.74	-9892	88789	3.16×10^-4	0.9997
x_c =0.4	39.83	-3269	91951	5.76×10^-4	0.9997
x_c =0.5	45.33	-11369	88705	2.61×10^-4	0.9988
x_c =0.6	50.92	-9237	91732	1.47×10^-4	0.9962
x_d =0.3	35.83	-8949	8691	2.02×10^-5	0.9997
x_d =0.4	41.76	-8562	12163	1.84×10^-5	0.9983
x_d =0.6	53.37	-423	4922	1.47×10^-5	0.9982

图2 采用Wilson方程对莱鲍迪苷A在不同混合溶剂中的溶解度数据的拟合结果

Fig.2 The solubility of rebaudioside A in different mixed solvents according to the Wilson equation

图3 溶剂组成对莱鲍迪苷A介稳区的影响

Fig.3 The effect of different solvents on metastable zone of rebaudioside A at different saturation temperature

图4 搅拌速率对莱鲍迪苷A介稳区的影响

Fig.4 The effect of different stirring rate on metastable zone of rebaudioside A at different saturation temperature

图5 冷却速率对莱鲍迪苷A介稳区的影响

Fig.5 The effect of different cooling rate on metastable zone of rebaudioside A at different saturation temperature

图6 不同饱和温度下冷却速率与介稳区的关系(由式(12)拟合得到)

Fig.6 Experimental MSZW as a function of cooling rate at different saturation temperature according to Eq.(12)

表5 基于自洽Nyvlt介稳区方程拟合的相关系数及动力学参数

Table 5 Regression cofficient and kinetics parameters calculated by self-consistent Nyvlt-like equation

T₀/K	Slope	Intercept	m	K	R²
313.15	0.354	-3.880	2.83	9.46×10²⁶	0.9997
318.15	0.301	-4.164	3.32	4.17×10²⁷	0.9982
323.15	0.277	-4.366	3.61	1.32×10²⁸	0.9974
328.15	0.255	-4.472	3.93	3.38×10²⁸	0.9976

图7 不同冷却速率下饱和温度与介稳区的关系(由式(16)拟合得到)

Fig.7 Experimental MSZW as a function of saturation temperature at different cooling rate according to Eq. (16)

表6 采用修正后的Sangwal模型计算得到的动力学参数

Table 6 Regression cofficient and kinetics parameters calculated by modified Sangwal's model

R/ (K·h^-1)	Modified Sangwal’s model
R/ (K·h^-1)	Slope	Intercept	γ/(mJ·m^-2)	A	R²
2.5	-102.2	-1168	0.315	3.39×10²³	0.9972
5	-70.26	-802.6	0.357	6.81×10²³	0.9899
10	-49.38	-563.9	0.402	1.37×10²⁴	0.9843
20	-32.54	-371.2	0.462	2.76×10²⁴	0.9736

图8 基于改进后的Sangwal介稳区模型得到的冷却速率与指前因子A的关系

Fig.8 Relationship between cooling rate and pre-exponential factor (A) by modified Sangwal’s model

图9 由式(25)得到的过饱和度比S与临界Gibbs自由能ΔGcrit关系

Fig.9 Relationship between critical Gibbs free energy (ΔGcrit) and supersaturation ratio (S) according to Eq.(25)

表7 搅拌速率对莱鲍迪苷A结晶产品尺寸的影响

Table 7 Effect of different stirring rate on particle size of rebaudioside A

搅拌转速/ (r·min^-1)	平均粒径/μm	粒径标准偏差/μm	粒径横纵比	变异系数(CV)
100	154.9	65.7	0.217	42.4
200	171.9	72.0	0.231	41.8
300	201.3	83.1	0.242	41.2
400	149.7	65.9	0.267	43.9
500	117.3	50.8	0.292	43.3

图10 搅拌速率对莱鲍迪苷A结晶产品形貌与粒度分布的影响

Fig.10 Effect of different stirring rate on morphology and particle size distribution of rebaudioside A crystal products

图11 莱鲍迪苷A冷却结晶程序降温曲线

Fig.11 The programmed cooling curve for crystallization of rebaudioside A

表8 冷却速率对莱鲍迪苷A结晶产品尺寸的影响

Table 8 Effect of different cooling rate on particle size of rebaudioside A

冷却速率	平均粒径/μm	粒径标准偏差/μm	粒径横纵比	变异系数值(CV)
2.5 K·h^-1 (线性)	118.3	41.1	0.258	34.75
5 K·h^-1 (线性)	91.9	32.5	0.230	35.37
程序降温	134.0	46.3	0.236	34.52

图12 冷却速率对莱鲍迪苷A结晶产品形貌与粒度分布的影响

Fig.12 Effect of different cooling rate on morphology and particle size distribution of rebaudioside A crystal products

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