三聚氰胺包合法分离不饱和脂肪酸

doi:10.3969/j.issn.0253-2417.2019.02.017

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (2): 115-121.doi: 10.3969/j.issn.0253-2417.2019.02.017

三聚氰胺包合法分离不饱和脂肪酸

王培燕¹,黄元波^1,*(),刘守庆¹,郑志锋^1,²,宁德鲁³

1. 林业生物质资源高效利用技术国家地方联合工程研究中心；西南地区林业生物质资源高效利用国家林业和草原局重点实验室；云南省生物能源国际联合研究中心，西南林业大学，云南昆明 650224
2. 福建省生物质高值化技术工程研究中心；厦门市现代农业生物质高值化技术重点实验室；厦门大学能源学院，福建厦门 361102
3. 云南省林业科学院经济林木研究所，云南昆明 650201

收稿日期:2018-11-24 出版日期:2019-04-25 发布日期:2019-05-08
通讯作者: 黄元波 E-mail:youthshow@163.com
作者简介:王培燕(1991—)，女，河南焦作人，硕士生，主要从事吸附剂的制备及分离脂肪酸研究
基金资助:
国家重点研发计划资助(2016YFD0600802);云南省重大科技专项计划(2018ZG003);云南省教育厅科学研究基金项目资助(2018Y119)

Separation of Unsaturated Fatty Acids by Melamine Inclusion Method

Peiyan WANG¹,Yuanbo HUANG^1,*(),Shouqing LIU¹,Zhifeng ZHENG^1,²,Delu NING³

1. National-Local Joint Engineering Research Center for Highly-Efficient Utilization Technology of Forest Biomass Resources; Key Laboratory for Highly-Efficient Utilization of Forest Biomass Resources in the Southwest China, National Forestry and Grassland Administration; Yunnan Provincial International Joint Research Center for Bio- energy, Southwest Forestry University, Kunming 650224, China
2. Fujian Engineering and Research Center of Clean and High-valued Technologies for Biomass; Xiamen Key Laboratory of High-valued Conversion Technology of Agricultural Biomass; College of Energy, Xiamen University, Xiamen 361102, China
3. Economic Forest Research Institute, Yunnan Academy of Forestry, Kunming 650201, China

Received:2018-11-24 Online:2019-04-25 Published:2019-05-08
Contact: Yuanbo HUANG E-mail:youthshow@163.com
Supported by:
国家重点研发计划资助(2016YFD0600802);云南省重大科技专项计划(2018ZG003);云南省教育厅科学研究基金项目资助(2018Y119)

摘要/Abstract

摘要：

采用三聚氰胺包合法从混合脂肪酸中分离不饱和脂肪酸(UFAs)，探讨了三聚氰胺/脂肪酸质量比、晶化包合温度、包合时间对包合效果的影响，并采用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)和核磁共振(NMR)对三聚氰胺包合物进行了表征。研究结果表明：饱和脂肪酸可以在低温下被三聚氰胺包合；当脂肪酸20 g，96 mL 95%乙醇溶液，三聚氰胺/脂肪酸(M/F)质量比为0.9:1，在75 ℃条件下溶解，并在9 ℃下晶化包合7 h，脂肪酸得率60.83%、不饱和脂肪酸纯度为93.75%、包合率为87.23%。采用气相色谱(GC)分析发现：与尿素包合法相比，经三聚氰胺包合后分离获得的不饱和脂肪酸纯度、包合率均较高，且可将单不饱和与多不饱和脂肪酸同时分离。结构分析表明：与三聚氰胺晶体相比，饱和脂肪酸的三聚氰胺包合物晶体结构未发生改变，饱和脂肪酸能够进入三聚氰胺晶体片层之间形成稳定的结晶包合物，且三聚氰胺包合后可回收再利用，其分离不饱和脂肪酸的纯度仍可达86.28%。

关键词: 脂肪酸, 分离, 三聚氰胺包合法

Abstract:

Separation of unsaturated fatty acids (UFAs), including monounsaturated (MUFAs) and polyunsaturated fatty acids (PUFAs) from mixed fatty acids (FAs) by melamine inclusion method were investigated. Effects of melamine/FAs mass ratio, crystallization inclusion temperature and inclusion time on yield, purification, and inclusion rate of UFAs were discussed. The melamine inclusion complex was characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy. Results showed that saturated fatty acids (SFAs) could be employed to form the inclusion crystallization (complex) in ethanol at low temperature by melamine. The optimized conditions were FAS 20 g, 95% ethand 96 mL, mass ratio of melanine and FAs (M/F) 0.9:1, dissolving at 75 ℃, inclusion at 9 ℃ for 7 h. Under these conditions, the maximum UFAs (yield of 60.83%, purity of 93.75%, and inclusion rate of 87.23%) were obtained. Compared with the ureainclusion method, the purity and inclusion rate of UFAs were higher, and MUFAs and PUFAs could be separated together from SFAs by melamine inclusion method. Compared with melamine crystals by structural analysis, the crystal structure of melamine inclusion complex with SFAs did not change, and SFAs could enter into melamine crystalline lamellae to form stable crystalline inclusion complex. After inclusion, melamine could be recycled, which would be promoted the further development of fatty acids separation.

Key words: fatty acids, separation, melamine inclusion method

中图分类号:

TQ35
TQ645

王培燕,黄元波,刘守庆,郑志锋,宁德鲁. 三聚氰胺包合法分离不饱和脂肪酸[J]. 林产化学与工业, 2019, 39(2): 115-121.

Peiyan WANG,Yuanbo HUANG,Shouqing LIU,Zhifeng ZHENG,Delu NING. Separation of Unsaturated Fatty Acids by Melamine Inclusion Method[J]. Chemistry and Industry of Forest Products, 2019, 39(2): 115-121.

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参考文献 21

1	SHAHIDI F.贝雷油脂化学与工艺学:第六卷:油脂的工业产品与非食用产品[M].6版.王兴国,金青哲,译.北京:中国轻工业出版社, 2016.
	SHAHIDI F. Bailey's Industrial Oil and Fat Products: Volume 6: Industrial and Nonedible Products from Oils and Fats[M]. 6th ed. WANG X G, JIN Q Z, translation. Beijing: China Light Industry Press, 2016.
2	SAVALIYA M L , DHORAJIYA B D , DHOLAKIYA B Z . Current trends in separation and purification of fatty acid methyl ester[J]. Separation & Purification Reviews, 2015, 44 (1): 28- 40.
3	孙永利, 卢伟, 肖晓明, 等. C16、C18混合脂肪酸分离技术研究进展[J]. 化工进展, 2014, 33 (12): 3139- 3143.
	SUN Y L , WEI L , XIAO X M , et al. Development of C16 and C18 fatty acid mixtures separation technology[J]. Chemical Industry & Engineering Progress, 2014, 33 (12): 3139- 3143.
4	LIN W , WU F W , YUE L , et al. Combination of urea complexation and molecular distillation to purify DHA and EPA from sardine oil ethyl esters[J]. Journal of the American Oil Chemists' Society, 2014, 91 (4): 687- 695. doi: 10.1007/s11746-013-2402-1
5	PERPÊTUO G J , JANCZAK J . Solid-state supramolecular architectures formed by co-crystallization of melamine and 2-, 3- and 4-fluorophenylacetic acids[J]. Journal of Molecular Structure, 2018, 1152, 237- 247. doi: 10.1016/j.molstruc.2017.09.099
6	PIANA S , REYHANI M , GALE J D . Simulating micrometer-scale crystal growth from solution[J]. Nature, 2005, 438 (3): 70- 73.
7	BERGLUND K A . Analysis and Measurement of Crystallization Utilizing the Population Balance[J]. Handbook of Industrial Crystallization, 2002, 101- 113.
8	STROCCHI A , BONAGA G . Correlation between urea inclusion compounds and conformational structure of unsaturated C₁₈ fatty-acid methyl-esters[J]. Chemistry and Physics of Lipid, 1975, 15 (2): 87- 94. doi: 10.1016/0009-3084(75)90033-X
9	WU M Y , DING H , WANG S , et al. Optimizing conditions for the purification of linoleic acid from sunflower oil by urea complex fractionation[J]. Journal of the American Oil Chemists' Society, 2008, 85 (7): 677- 684. doi: 10.1007/s11746-008-1245-7
10	TARIQ M , ALI S , AHMAN F , et al. Identification, FT-IR, NMR (¹H and ¹³C) and GC/MS studies of fatty acid methyl esters in biodiesel from rocket seed oil[J]. Fuel Processing Technology, 2011, 92 (3): 336- 341. doi: 10.1016/j.fuproc.2010.09.025
11	LI G L , ZHAO G . Efficient Acetylation of alcohols and phenols catalyzed by recyclable lithium bis(perfluoroalkylsulfonyl) imide[J]. Synthetic Communications, 2013, 43 (1): 34- 43. doi: 10.1080/00397911.2011.589563
12	JANCZAK J , PERPETUO GJ . Melaminium chloride hemihydrate[J]. Acta Crystallographica, 2001, 57 (Pt 9): 1120- 1122.
13	JANCZAK J , PERPETUO GJ . Melaminium maleate monohydrate[J]. Acta Crystallographica, 2004, 60 (Pt 3): 211- 214.
14	MONTEIRO M R , AMBROZIN A R P , LIAO L M , et al. Determination of biodiesel blend levels in different diesel samples by ¹H NMR[J]. Fuel, 2009, 88 (4): 691- 696. doi: 10.1016/j.fuel.2008.10.010
15	SAMIOS D , PEDROTTI F , NICOLAU A , et al. A transesterification double step process:TDSP for biodiesel preparation from fatty acids triglycerides[J]. Fuel Processing Technology, 2009, 90 (4): 599- 605. doi: 10.1016/j.fuproc.2008.12.011
16	KNOTHE G . Monitoring a progressing transesterification reaction by fiber-optic near infrared spectroscopy with correlation to ¹H nuclear magnetic resonance spectroscopy[J]. Journal of the American Oil Chemists' Society, 2000, 77 (5): 489- 493. doi: 10.1007/s11746-000-0078-5
17	LI J , ZHAO X L , LIU Y X , et al. ¹H NMR-based metabolomic profile of rats with experimental acute pancreatitis[J]. BMC Gastroenterology, 2014, 14 (1): 1- 7.
18	金立维, 王春鹏, 储富祥, 等. E1级MDF用三聚氰胺改性脲醛树脂的定量¹³C-NMR结构研究[J]. 林产工业, 2006, 33 (6): 38- 41. doi: 10.3969/j.issn.1001-5299.2006.06.009
	JIN L W , WANG C P , CHU F X , et al. The quantitative ⁽¹³⁾C-NMR analysis of melamine-modified UF resin for E1 type MDF[J]. China Forest Products Industry, 2006, 33 (6): 38- 41. doi: 10.3969/j.issn.1001-5299.2006.06.009
19	MELLO V M , OLIVEIRA F C , FRAGA W G , et al. Determination of the content of fatty acid methyl esters (FAME) in biodiesel samples obtained by esterification using ¹H-NMR spectroscopy[J]. Magnetic Resonance in Chemistry, 2010, 46 (11): 1051- 1054.
20	GELBARD G , BRES O , VARGAS R M , et al. ¹H nuclear magnetic resonance determination of the yield of the transesterification of rapeseed oil with methanol[J]. Journal of the American Oil Chemists' Society, 1995, 72 (10): 1239- 1241. doi: 10.1007/BF02540998
21	BARBARA J , IRRAN E , JURGEN S , et al. Melem (2, 5, 8-Triamino-tri-s-triazine), an important intermediate during condensation of melamine rings to graphitic carbon nitride: Synthesis, structure determination by X-ray powder diffractometry, solid-state NMR, and theoretical studies[J]. Journal of the American Chemical Society, 2003, 125 (34): 10288- 10300. doi: 10.1021/ja0357689

%
样品 samples	棕榈酸 (C₁₆:0)palmitic acid	硬脂酸 (C₁₈:0)stearic acid	油酸 (C₁₈:1)oleic acid	亚油酸 (C₁₈:2) linoleic acid	亚麻酸 (C₁₈:3) linolenic acid	纯度 purity	得率 yield	包合率 inclusion rate
原料material	24.90	9.72	35.19	26.33	3.86	65.38	—	—
尿素包合法urea inclusion method	6.92	15.14	25.35	46.62	5.97	77.94	60.50	72.11
三聚氰胺包合法melamine inclusion method	4.68	1.57	50.62	37.79	5.34	93.75	60.83	87.23

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三聚氰胺包合法分离不饱和脂肪酸

Separation of Unsaturated Fatty Acids by Melamine Inclusion Method

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