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《山东大学学报(理学版)》 ›› 2024, Vol. 59 ›› Issue (11): 85-92.doi: 10.6040/j.issn.1671-9352.0.2024.316

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酶法催化高酸值米糠油脱臭馏出物甲酯化

周游(),李攀登,贺雷雨,孙丽慧*()   

  1. 大连理工大学化工海洋与生命学院,辽宁 盘锦 124221
  • 收稿日期:2024-09-13 出版日期:2024-11-20 发布日期:2024-11-29
  • 通讯作者: 孙丽慧 E-mail:2337151048@qq.com;sunlihui@dlut.edu.cn
  • 作者简介:周游(1998—),男,硕士研究生,研究方向为生物催化与转化. E-mail: 2337151048@qq.com
  • 基金资助:
    辽宁省自然科学基金项目(2019-MS-044)

Enzymatic catalysis for methyl esterification of high acid value rice bran oil deodorized distillate

You ZHOU(),Pandeng LI,Leiyu HE,Lihui SUN*()   

  1. School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin 124221, Liaoning, China
  • Received:2024-09-13 Online:2024-11-20 Published:2024-11-29
  • Contact: Lihui SUN E-mail:2337151048@qq.com;sunlihui@dlut.edu.cn

摘要:

为了提高米糠油脱臭馏出物的利用率,本研究采用脂肪酶Eversa Transform 2.0催化米糠油脱臭馏出物甲酯化,以酯化率和体系中游离脂肪酸的含量为指标,通过单因素实验研究反应时间、加酶量、醇油摩尔比和含水量的影响,在此基础上采用响应面实验对甲酯化条件进行优化。结果表明米糠油脱臭馏出物甲酯化的最佳反应条件:酶添加量为1.2%;醇油摩尔比为5.9 ∶1;含水量为11.8%;反应时间为9.6 h。在此条件下酯化率为97.37%。综上,廉价的液体脂肪酶Eversa Transform 2.0催化米糠油脱臭馏出物甲酯化,可以得到较高的酯化率,为体系中植物甾醇、维生素E等活性成分的分离提取提供了绿色高效的预处理方法。

关键词: 米糠油脱臭馏出物, 高酸值油, 酶催化, 响应面法, 甲酯化

Abstract:

In order to improve the utilization rate of rice bran oil deodorized distillate, methyl esterification of rice bran oil deodorized distillate was catalyzed by the liquid lipase Eversa Transform 2.0. The esterification rate and the content of free fatty acids in the system were used as the evaluation indicators. The effects of reaction time, enzyme amount, molar ratio of alcohol to oil, and water content on the esterification rate were studied by single factor experiments. On this basis, the response surface experiment was used to optimize the esterification conditions. The results showed that the optimal conditions for methyl esterification of rice bran oil deodorized distillate were 1.2% enzyme addition, 5.9 ∶1 molar ratio of alcohol to oil, 11.8% water content, and 9.6 h reaction time. Under these conditions, the esterification rate was 97.37%. In summary, the low-cost liquid lipase Eversa Transform 2.0 catalyzed the esterification of rice bran oil deodorized distillate, which could obtain a high esterification rate and provide a green and efficient pretreatment method for the separation and extraction of phytosterols, vitamin E, and other active components in the system.

Key words: rice bran oil deodorized distillate, high acid value oil, enzyme catalysis, response surface methodology, methyl esterification

中图分类号: 

  • Q503

表1

Box-Behnken因素水平表"

水平 X1/h X2/% X3 X4/%
-1 2 0.2 2∶1 6
0 6 0.6 4∶1 10
1 10 1.0 6∶1 14

图1

反应时间对酯化的影响"

图2

加酶量对酯化的影响"

图3

醇油摩尔比对酯化的影响"

图4

含水量对酯化的影响"

表2

Box-Behnken试验设计及响应值"

编号 X1/h X2/% X3 X4/% rest/%   编号 X1/h X2/% X3 X4/% rest/%
1 2 0.2 5 10 53.91   16 6 1.4 8 10 83.84
2 10 0.2 5 10 77.42 17 2 0.8 2 10 59.63
3 2 1.4 5 10 75.56 18 10 0.8 2 10 66.72
4 10 1.4 5 10 94.75 19 2 0.8 8 10 53.45
5 6 0.8 2 4 63.29 20 10 0.8 8 10 82.49
6 6 0.8 8 4 58.48 21 6 0.2 5 4 58.31
7 6 0.8 2 16 62.54 22 6 1.4 5 4 73.84
8 6 0.8 8 16 73.52 23 6 0.2 5 16 59.17
9 2 0.8 5 4 55.73 24 6 1.4 5 16 92.10
10 10 0.8 5 4 72.11 25 6 0.8 5 10 95.56
11 2 0.8 5 16 65.26 26 6 0.8 5 10 93.86
12 10 0.8 5 16 80.83 27 6 0.8 5 10 94.62
13 6 0.2 2 10 58.12 28 6 0.8 5 10 94.42
14 6 1.4 2 10 71.80 29 6 0.8 5 10 92.24
15 6 0.2 8 10 56.16            

表3

Eversa Transform 2.0催化RBODD甲酯化回归模型的方差分析"

方差来源 总方差和 自由度 均方 F p 显著性
Model 5 969.24 14 426.37 105.39 < 0.000 1 ***
X1 649.96 1 649.96 160.65 < 0.000 1 ***
X2 607.76 1 607.76 150.22 < 0.000 1 ***
X3 1 453.35 1 1 453.35 359.23 < 0.000 1 ***
X4 204.31 1 204.31 50.50 < 0.000 1 ***
X1 X2 4.67 1 4.67 1.15 0.301 0  
X1 X3 120.45 1 120.45 29.77 < 0.000 1 ***
X1 X4 0.164 0 1 0.164 0 0.040 5 0.843 3  
X2 X3 49.00 1 49.00 12.11 0.003 7 **
X2 X4 75.69 1 75.69 18.71 0.000 7 ***
X3 X4 62.33 1 62.33 15.41 0.001 5 **
X12 791.60 1 791.60 195.66 < 0.000 1  
X22 514.61 1 514.61 127.20 < 0.000 1  
X32 1 880.02 1 1 880.02 464.69 < 0.000 1  
X42 1 250.03 1 1 250.03 308.97 < 0.000 1  
残差 56.64 14 4.05      
失拟项 50.63 10 5.06 3.37 0.126 6  
纯误差 6.01 4 1.50      
总和 6 025.88 28        

图5

各因素交互的响应面图"

1 张欢, 贾怡文, 陈小威, 等. 稻米油脱臭馏出物中角鲨烯分离与纯化工艺的研究[J]. 河南工业大学学报(自然科学版), 2022, 43 (6): 30- 36.
ZHANG Huan , JIA Yiwen , CHEN Xiaowei , et al. Separation and purification of squalene from rice oil deodorizer distillate[J]. Journal of Henan University of Technology (Natural Science Edition), 2022, 43 (6): 30- 36.
2 汪金宇. 米糠油脱臭馏出物的综合利用[D]. 北京: 北京化工大学, 2016.
WANG Jinyu. Comprehensive utilization of deodorized distillate from rice bran oil[D]. Beijing: Beijing University of Chemical Technology, 2016.
3 甘欢华, 刘钟栋, 吴凯, 等. 大豆油脱臭馏出物酶法甲酯化工艺研究[J]. 中国油脂, 2020, 45 (7): 78-81, 92.
GAN Huanhua , LIU Zhongdong , WU Kai , et al. Enzymatic methyl esterification of soybean oil deodorized distillate[J]. China Oils and Fats, 2020, 45 (7): 78-81, 92.
4 武文华, 关国华, 蒋一鸣, 等. 响应面法优化生物酶法催化脱臭馏出物甲酯化[J]. 中国油脂, 2022, 47 (11): 143- 146.
WU Wenhua , GUAN Guohua , JIANG Yiming , et al. Optimization of bioenzyme-catalyzed methyl esterification of deodorized distillates by response surface methodology[J]. China Oils and Fats, 2022, 47 (11): 143- 146.
5 吴雪辉, 蓝梧涛, 容欧. 响应面优化油茶籽油脱臭馏出物中维生素E的提取工艺研究[J]. 中国油脂, 2018, 43 (5): 113- 116.
WU Xuehui , LAN Wutao , RONG Ou . Optimization of extraction of vitamin E from deodorizer distillate of oil-tea camellia seed oil by response surface methodology[J]. China Oils and Fats, 2018, 43 (5): 113- 116.
6 许超群. 大豆油脱臭馏出物中提取天然维生素E的工艺研究[D]. 杭州: 浙江工业大学, 2022.
Xu Chaoqun. Process study on the extraction of natural vitamin E from deodorized soybean oil distillate[D]. Hangzhou: Zhejiang University of Technology, 2022.
7 代志凯, 王义永, 赵健, 等. 棕榈油脱臭馏出物的甲酯化工艺研究[J]. 中国油脂, 2015, 40 (9): 46- 49.
DAI Zhikai , WANG Yiyong , ZHAO Jian , et al. Methyl esterification of palm oil deodorizer distillate[J]. China Oils and Fats, 2015, 40 (9): 46- 49.
8 金斐. 大豆脱臭馏出物中浓缩天然VE的酯化工艺研究[D]. 杭州: 浙江工业大学, 2017.
JIN Fei. Study on esterification technology of concentrated natural VE in soybean deodorizer distillate[D]. Hangzhou: Zhejiang University of Technology, 2017.
9 CESARINI S , DIAZ P , NIELSEN P M . Exploring a new, soluble lipase for FAMEs production in water-containing systems using crude soybean oil as a feedstock[J]. Process Biochemistry, 2013, 48 (3): 484- 487.
doi: 10.1016/j.procbio.2013.02.001
10 CHANG M Y , CHAN E S , SONG C P . Biodiesel production catalysed by low-cost liquid enzyme Eversa® Transform 2.0: effect of free fatty acid content on lipase methanol tolerance and kinetic model[J]. Fuel, 2021, 283, 119266.
doi: 10.1016/j.fuel.2020.119266
11 BHATT C , NIELSEN P M , RANCKE-MADSEN A , et al. Combining technology with liquid-formulated lipases for in-spec biodiesel production[J]. Biotechnology and Applied Biochemistry, 2022, 69 (1): 7- 19.
doi: 10.1002/bab.2074
12 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准食品中酸价的测定: GB 5009.229—2016[S]. 北京: 中国标准出版社, 2017.
National Health and Family Planning Commission of the People's Republic of China. National food safety standard determination of acid value in foods: GB 5009.229—2016[S]. Beijing: Standards Press of China, 2017.
13 ZENG L P , HE Y J , JIAO L C , et al. Preparation of biodiesel with liquid synergetic lipases from rapeseed oil deodorizer distillate[J]. Applied Biochemistry and Biotechnology, 2017, 183 (3): 778- 791.
doi: 10.1007/s12010-017-2463-y
14 MONTEIRO R R C , ARANA-PE A S , DA ROCHA T N , et al. Liquid lipase preparations designed for industrial production of biodiesel. Is it really an optimal solution?[[J]. Renewable Energy, 2021, 164, 1566- 1587.
doi: 10.1016/j.renene.2020.10.071
15 SUN S D , GUO J J , CHEN X W . Biodiesel preparation from Semen Abutili (Abutilon theophrasti Medic.) seed oil using low-cost liquid lipase Eversa® Transform 2.0 as a catalyst[J]. Industrial Crops and Products, 2021, 169, 113643.
doi: 10.1016/j.indcrop.2021.113643
16 LOH J M , AMELIA , GOURICH W , et al. Improved biodiesel production from sludge palm oil catalyzed by a low-cost liquid lipase under low-input process conditions[J]. Renewable Energy, 2021, 177, 348- 358.
doi: 10.1016/j.renene.2021.05.138
17 ZHOU Y X , LI K Y , SUN S D . Simultaneous esterification and transesterification of waste phoenix seed oil with a high free fatty acid content using a free lipase catalyst to prepare biodiesel[J]. Biomass and Bioenergy, 2021, 144, 105930.
doi: 10.1016/j.biombioe.2020.105930
18 GULDHE A , SINGH B , MUTANDA T , et al. Advances in synthesis of biodieselvia enzyme catalysis: novel and sustainable approaches[J]. Renewable and Sustainable Energy Reviews, 2015, 41, 1447- 1464.
doi: 10.1016/j.rser.2014.09.035
19 LOTTI M , PLEISS J , VALERO F , et al. Effects of methanol on lipases: molecular, kinetic and process issues in the production of biodiesel[J]. Biotechnology Journal, 2015, 10 (1): 22- 30.
doi: 10.1002/biot.201400158
20 AMELIA , SONG C P , CHANG M Y , et al. Retention of high-value tocols during enzymatic esterification of palm fatty acid distillate using liquid lipase for improving the economics and sustainability of biodiesel production[J]. Industrial Crops and Products, 2023, 194, 116271.
doi: 10.1016/j.indcrop.2023.116271
21 ROSSET D V , WANCURA J H C , UGALDE G A , et al. Enzyme-catalyzed production of FAME by hydroesterification of soybean oil using the novel soluble lipase NS 40116[J]. Applied Biochemistry and Biotechnology, 2019, 188 (4): 914- 926.
doi: 10.1007/s12010-019-02966-7
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