葡萄柚精油“除萜赋香”工艺的优化研究

doi:10.3969/j.issn.1004-1524.2021.11.15

浙江农业学报 ›› 2021, Vol. 33 ›› Issue (11): 2128-2136.DOI: 10.3969/j.issn.1004-1524.2021.11.15

葡萄柚精油“除萜赋香”工艺的优化研究

杨颖¹(), 施迎春¹^,², 邢建荣¹, 刘哲¹, 郑美瑜¹, 陆胜民¹^,^*()

1.浙江省农业科学院食品科学研究所,浙江杭州 310021
2.南京农业大学食品科技学院,江苏南京 210095

收稿日期:2020-09-01 出版日期:2021-11-25 发布日期:2021-11-26
通讯作者: 陆胜民
作者简介:*陆胜民,E-mail: lushengmin@hotmail.com
杨颖(1978—),女,山东潍坊人,博士,副研究员,主要从事农产品加工与综合利用研究。E-mail: ying_yang4535@sina.com
基金资助:
农业部公益性行业科研专项经费(201303076-05)

Optimization of “terpenoids removing and aroma enhancing” process for grapefruit essential oil

YANG Ying¹(), SHI Yingchun¹^,², XING Jianrong¹, LIU Zhe¹, ZHENG Meiyu¹, LU Shengmin¹^,^*()

1. Institute of Food Science, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China
2. College of Food Science and Technology, Nanjing Agricultural University, Nanjing 210095, China

Received:2020-09-01 Online:2021-11-25 Published:2021-11-26
Contact: LU Shengmin

摘要/Abstract

摘要：

葡萄柚精油中的主要化学成分柠檬烯易氧化呈异味,是影响货架期和赋香性能的主要原因。为解决这一问题,本文以温度和压力为影响因子,以馏出物中的柠檬烯含量(Y₁)、馏余浓缩物中的柠檬烯(Y₂)、芳樟醇(Y₃)及葵醛含量(Y₄)为响应值,采用气相色谱技术检测各组分含量,设计中心组合试验对分子蒸馏工艺进行响应面优化,分离去除原油中的柠檬烯,制备高倍浓缩精油。结果表明:温度和压力对Y₂、Y₃、Y₄均有显著影响,响应面模型的优化温度为44.89 ℃,压力为500 Pa,Y₁、Y₂、Y₃、Y₄的预测值分别为94.84%、49.75%、1.63%、2.39%,对应实际值分别为94.89%、49.72%、1.59%、2.34%,与预测值基本吻合,验证了该模型的合理性。浓缩后的精油呈棕褐色,香气更加醇厚、柔润,氧化物含量从3.41%上升到29.31%,实现了8.6倍浓缩。本研究可为其他柑橘类精油的浓缩提供参考。

关键词: 葡萄柚精油, 除萜赋香, 分子蒸馏, 响应面分析, 柠檬烯

Abstract:

Limonene, the main component of grapefruit essential oil, is easy to be oxidized and presents a peculiar smell, which will affect the shelf life and aroma profile. In this study, molecular distillation technology was adopted to partially remove the limonene from raw oil and prepare highly concentrated essential oil. Molecular distillation process was optimized using central composite design with temperature and pressure as variables. Limonene contents in distillated fraction (Y₁), limonene contents in residual concentrated fractions (Y₂), linalool (Y₃) and decanal (Y₄) in residual concentrated fractions were set as response values. The concentrations of limonene, linalool, and decanal were determined by GC. The results of response surface analysis indicated that Y₂, Y₃ and Y₄ were significantly affected by temperature and pressure, the optimized conditions were 44.89 ℃ for temperature and 500 Pa for pressure, under which the predicted values of Y₁, Y₂, Y₃ and Y₄ were 94.84%, 49.75%, 1.63% and 2.39%, respectively. Further verification experiments confirmed the validity of the predicted model (Y₁, Y₂, Y₃ and Y₄ values were 94.89%, 49.72%, 1.59% and 2.34%, respectively). The color of concentrated oil was dark brown and its odor was much more mellow, richer and softer than that of raw oil. Total content of oxygenated compounds increased from 3.41% to 29.31%, which indicated that 8.6 folds concentrated grapefruit essential oil was obtained through molecular distillation. This study can provide a reference for the concentration of other citrus essential oils.

Key words: grapefruit essential oil, terpenoids-removed and aroma-enhanced, molecular distillation, response surface analysis, limonene

中图分类号:

TS201

杨颖, 施迎春, 邢建荣, 刘哲, 郑美瑜, 陆胜民. 葡萄柚精油“除萜赋香”工艺的优化研究[J]. 浙江农业学报, 2021, 33(11): 2128-2136.

YANG Ying, SHI Yingchun, XING Jianrong, LIU Zhe, ZHENG Meiyu, LU Shengmin. Optimization of “terpenoids removing and aroma enhancing” process for grapefruit essential oil[J]. Acta Agriculturae Zhejiangensis, 2021, 33(11): 2128-2136.

图/表 11

图1 柠檬烯(a)、芳樟醇(b)及葵醛(c)的标准曲线

Fig.1 Standard curves of limonene(a), linalool(b) and decanal(c)

表1 中心组合设计的实验因素及水平编码

Table 1 Factors and levels of central composite design experiment

水平 Levels	因素Factors
水平 Levels	温度 θ(X₁)/℃	压力 Pressure(X₂)/Pa
-1.414	38	459
-1	40	500
0	45	600
1	50	700
1.414	52	742

图2 温度对葡萄柚精油浓缩效率的影响

Fig.2 Effects of temperatures on concentrating efficacy of grapefruit essential oil

图3 压力对葡萄柚精油浓缩效率的影响

Fig.3 Effects of pressure on concentrating efficacy of grapefruit essential oil

表2 中心组合设计方案与响应值

Table 2 Central composite design and response values

序号 No.	自变量Independent variable		响应值Response value
序号 No.	X₁	X₂	Y₁/%	Y₂/%	Y₃/%	Y₄/%
1	0	0	94.30	52.89	1.46	2.85
2	0	0	94.56	53.39	1.61	2.18
3	1	-1	94.85	36.40	0.84	1.89
4	1	1	95.18	57.40	1.20	2.20
5	1.414	0	94.79	35.80	0.82	1.88
6	-1	-1	95.73	55.96	1.91	2.25
7	-1	1	95.20	86.96	0.67	0.94
8	0	0	93.31	58.91	1.49	2.12
9	0	1.414	94.02	75.94	1.12	1.28
10	0	0	95.52	65.92	1.67	2.14
11	-1.414	0	94.20	87.70	0.83	0.89
12	0	0	95.92	56.32	1.54	2.15
13	0	-1.414	95.35	53.76	1.46	2.27

表3 Y2、Y3、Y4响应模型的方差分析

Table 3 Variance analysis of response models for Y2, Y3 and Y4

模型 Model	来源 Origin	平方和 SS	自由度 df	均方 MS	F值 F value	P值 P value	显著性 Significance
	模型 Model	2 745.73	2	1 372.86	39.06	<0.000 1	**
Y₂	失拟 Misconduct	239.00	6	39.83	1.42	0.383 7	NS
	纯误差 Pure error	112.47	4	28.12
	合计 Sum	3 097.20	12
	模型 Model	1.67	4	0.42	18.18	0.000 4	**
Y₃	失拟 Misconduct	0.15	4	0.038	4.87	0.077 1	NS
	纯误差 Pure error	0.031	4	0.007 8
	合计 Sum	1.85	12
	模型 Model	2.99	4	0.75	7.33	0.008 7	**
Y₄	失拟 Misconduct	0.43	4	0.11	1.11	0.461 2	NS
	纯误差 Pure error	0.39	4	0.097
	合计 Sum	3.8	12

表4 Y2、Y3、Y4模型的回归方程系数的方差分析

Table 4 Variance analysis for regression coefficients of Y2, Y3, Y4 models equations

模型 Model	来源 Origin	平方和 SS	自由度 df	均方 MS	F值 F value	P值 P value	显著性 Significance
Y₂	X₁	1 876.91	1	1 876.91	53.40	<0.000 1	**
	X₂	868.82	1	868.82	24.72	0.000 6	**
	X₁	40	1	0.040	1.73	0.225 3	NS
Y₃	X₂	0.23	1	0.23	10.05	0.013 2	*
	X₁ X₂	0.64	1	0.64	27.89	0.000 7	**
	$X 12$	0.76	1	0.76	33.06	0.000 4	**
	X₁	0.66	1	0.66	6.51	0.034 1	NS
Y₄	X₂	0.72	1	0.72	7.07	0.028 9	*
	X₁ X₂	0.65	1	0.65	6.41	0.035 1	*
	$X 12$	0.95	1	0.95	9.32	0.015 7	*

表4 Y2、Y3、Y4模型的回归方程系数的方差分析

Table 4 Variance analysis for regression coefficients of Y2, Y3, Y4 models equations

模型 Model	来源 Origin	平方和 SS	自由度 df	均方 MS	F值 F value	P值 P value	显著性 Significance
Y₂	X₁	1 876.91	1	1 876.91	53.40	<0.000 1	**
	X₂	868.82	1	868.82	24.72	0.000 6	**
	X₁	40	1	0.040	1.73	0.225 3	NS
Y₃	X₂	0.23	1	0.23	10.05	0.013 2	*
	X₁ X₂	0.64	1	0.64	27.89	0.000 7	**
	$X 12$	0.76	1	0.76	33.06	0.000 4	**
	X₁	0.66	1	0.66	6.51	0.034 1	NS
Y₄	X₂	0.72	1	0.72	7.07	0.028 9	*
	X₁ X₂	0.65	1	0.65	6.41	0.035 1	*
	$X 12$	0.95	1	0.95	9.32	0.015 7	*

图4 温度与压力对Y1(A)、Y2(B)、Y3(C)及Y4(D)影响的响应曲面

Fig.4 Response surfaces for effects of temperature and pressure on Y1(A), Y2(B), Y3(C) and Y4(D)

表5 响应面模型的优化参数设置

Table 5 Parameters setting for the optimization of response surface models

参数 Parameters	最小值 Minimum value	最大值 Maximum value	重要性 Importance
温度θ/℃	40	50	5
压力Pressure/Pa	500	700	5
Y₁/%	94	97	2
Y₂/%	30	60	5
Y₃/%	1.3	2.5	4
Y₄/%	1.5	2.8	4

图5 葡萄柚原油(左)、馏出物(中)及馏余浓缩物(右)的表观特征

Fig.5 Apparent properties of raw oil (left), distillated fraction (middle) and residual fraction (right)

图6 蒸馏前后主要烯烃类化合物(A)与氧化物(B)的含量变化

Fig.6 Contents of olefin compounds (A) and oxides (B) of grapefruit essential oil before and after the condensation

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葡萄柚精油“除萜赋香”工艺的优化研究

Optimization of “terpenoids removing and aroma enhancing” process for grapefruit essential oil

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