Ce改性MgO催化硬脂酸甘油三酯甘油解制备单甘酯的研究

doi:10.3969/j.issn.2097-2806.2023.05.004

摘要/Abstract

摘要：

为提高产品中单甘酯（简称MAGs）的含量，采用自制Ce改性MgO催化剂催化硬脂酸甘油三酯甘油解制备单甘酯。以氧化镁和硝酸铈为原料，采用水热合成法先制备MgO载体，再采用等体积浸渍法制备Ce改性MgO催化剂。设计了反应时间、反应温度、催化剂用量三因素三水平的正交试验，并考察了Ce的添加量对粗产品中单甘酯含量的影响。利用BET，XRD和CO₂-TPD对催化剂进行表征。实验结果表明，在选定影响MAGs含量的三个试验因素中，反应温度显著性水平最高，当Ce添加量为0.3%，催化剂用量为0.5%（占甘油和硬脂酸甘油三酯总质量），甘油与硬脂酸甘油三酯摩尔比为2∶1，反应温度为220 ℃，反应时间为2 h时，粗产品中单甘酯含量达42.0%。表征结果表明，Ce含量小于0.3%时，Ce的添加对催化剂比表面积、孔容、孔径影响不大，但催化剂碱性增强，当Ce含量大于0.5%时，催化剂的比表面积、孔容、孔径和碱性均明显下降。

关键词: 单甘酯, 制备, 硬脂酸甘油三酯, Ce改性MgO催化剂

Abstract:

To improve the content of monoglycerides （MAGs） in the product, the preparation of MAGs by glycerolysis of triglyceride catalyzed by Ce modified MgO catalysts was studied. MgO support was prepared by hydrothermal method with magnesium oxide as raw material, and Ce modified MgO catalyst was prepared by constant-volume impregnation method with cerium nitrate and MgO support as raw materials. The orthogonal test was designed, in which reaction time, reaction temperature and catalyst dosage were optimized. The effect of Ce addition on the content of MAGs in crude products was also investigated. The structure of Ce modified MgO catalysts was analyzed by BET, XRD and CO₂-TPD. The experimental results show that the reaction temperature has the highest significance level among the three selected factors affecting the content of MAGs. When the amount of Ce is 0.3%, catalyst dosage is 0.5% （of the total mass of glycerol and glyceryl tristearate）, the molar ratio of glycerol to glyceryl tristearate is 2∶1, the reaction temperature is 220 ℃, and the reaction time is 2 h, the content of MAGs is 42.0%. The characterization results show that, the addition of Ce has little effect on the specific surface area, pore volume and pore size of the catalyst when the Ce content is less than 0.3%, but the catalyst will be more alkaline. When the Ce content is more than 0.5%, the specific surface area, pore volume, pore size and alkalinity of the catalyst are significantly decreased.

Key words: monoglycerides, preparation, glyceryl tristearate, Ce modified MgO catalyst

中图分类号:

TQ423

孔令鸟, 洪郑, 方银军. Ce改性MgO催化硬脂酸甘油三酯甘油解制备单甘酯的研究[J]. 日用化学工业（中英文）, 2023, 53(5): 517-522.

Kong Lingniao, Hong Zheng, Fang Yinjun. Preparation of monoglyceride by glycerolysis of glyceryl tristearate catalyzed by Ce modified MgO[J]. China Surfactant Detergent & Cosmetics, 2023, 53(5): 517-522.

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催化剂	BET分析			XRD分析
催化剂	比表面积/（m²/g）	孔容/（cm³/g）	平均孔径/?	粒径/?
MgO（市售）	23	0.003	184	254
MgO-500	279	0.35	78	236
Ce-MgO-0.1	268	0.38	65	181
Ce-MgO-0.3	203	0.30	82	243
Ce-MgO-0.5	126	0.13	198	263
Ce-MgO-1.0	53	0.004	253	305

催化剂	CO₂脱附峰面积
催化剂	峰1	峰2	峰3	峰4	总面积
MgO-500	0.55	2.34	14.19		17.08
Ce-MgO-0.1	1.07	5.57	6.56	4.59	17.79
Ce-MgO-0.3	1.37	11.1	1.37	4.65	18.49
Ce-MgO-0.5	0.69	3.00	5.36	5.27	14.32
Ce-MgO-1.0	0.71	2.12	4.01	4.21	11.05

	A（催化剂用量/%）	B（反应温度/℃）	C（反应时间/h）	单甘酯含量/%
1	1（0.5）	1（200）	1（1）	29.1
2	1	2（220）	2（2）	33.1
3	1	3（240）	3（3）	36.7
4	2（1.0）	1	2	31.2
5	2	2	3	35.4
6	2	3	1	36.0
7	3（1.5）	1	3	33.5
8	3	2	1	36.4
9	3	3	2	34.3
k₁	33.0	31.3	33.8
k₂	34.2	35.0	32.9
k₃	34.7	35.7	35.2
R	1.7	4.4	2.3

方差来源	平方和	自由度	均方	F值	F_α	显著性水平
催化剂用量	4.9	2	2.5	0.924	F_0.05（2，2）=19.0
反应温度	33.5	2	16.8	6.321	F_0.01（2，2）=99.0	0.20
反应时间	8.2	2	4.1	1.547	F_0.1（2，2）=9.0
误差	5.3	2	2.6		F_0.2（2，2）=4.0

催化剂	Ce添加量/%	单甘酯含量/%
MgO-500	0.0	35.0
Ce-MgO-0.1	0.1	35.4
Ce-MgO-0.3	0.3	42.0
Ce-MgO-0.5	0.5	37.5
Ce-MgO-1.0	1.0	36.9