Fe3O4负载ZnO催化剂的制备及其催化合成松香甘油酯的研究

doi:10.3969/j.issn.0253-2417.2020.06.002

摘要/Abstract

摘要：

以Fe₃O₄作磁性中心，负载ZnO制备了一系列磁性催化剂，并通过TEM、XRD和XPS对其结构和组成进行了表征，经过筛选得出Fe₃O₄@SiO₂-ZnO催化效果最佳，远优于其他催化剂，且具有较好的稳定性能。同时还考察了锌源及其负载量，以及不同反应条件对松香甘油酯合成的影响，结果表明：在以乙酸锌为锌源，锌源理论负载量为0.25 g得到的Fe₃O₄@SiO₂-ZnO（ZnAc₂）为催化剂，反应温度为240℃，反应时间为5 h及催化剂用量为0.2 g时，产物松香甘油酯的酯化率为81.5%，酸值为38.6 mg/g。催化剂Fe₃O₄@SiO₂-ZnO（ZnAc₂）具有较好的稳定性，重复使用5次后，酯化率保持80%以上。

关键词: 松香, 酯化反应, 磁性催化剂, 酸催化

Abstract:

A series of magnetic catalysts were prepared with Fe₃O₄ as magnetic center and ZnO as activity center, and the structures and compositions were characterized by TEM, XRD and XPS. The catalytic performances of the prepared catalysts were studied. The results showed that Fe₃O₄@SiO₂-ZnO was of the best catalytic activity and stability. At the same time, the influences of factors on the synthesis of rosin glyceride, such as zinc source and its loading amount, different reaction conditions, were investigated. The results showed that when Fe₃O₄@SiO₂-ZnO(ZnAc₂)(zinc acetate as the zinc source, the theoretical load of zinc source 0.25 g) was catalyst, the reaction temperature was 240 ℃, the reaction time was 5 h, and the catalyst dosage was 0.2 g, the esterification rate and the acid value of rosin glyceride was 81.5% and 38.6 mg/g, respectively. The catalyst Fe₃O₄@SiO₂-ZnO₂(ZnAc₂) had good stability. After repeated use for 5 times, the esterification rate remained above 80%.

Key words: rosin, esterification reaction, magnetic catalyst, acid catalysis

中图分类号:

TQ35

于世涛, 邹昊学, 李娅娅, 张慧敏, 王宇婧. Fe₃O₄负载ZnO催化剂的制备及其催化合成松香甘油酯的研究[J]. 林产化学与工业, 2020, 40(6): 8-14.

Shitao YU, Haoxue ZOU, Yaya LI, Huimin ZHANG, Yujing WANG. Preparation of Rosin Glyceride Catalyzed by Fe₃O₄ Supported ZnO[J]. Chemistry and Industry of Forest Products, 2020, 40(6): 8-14.

图/表 9

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序号 No.	温度/℃ temperature	时间/h time	催化剂用量/g catalyst amount	锌源负载量/g zinc source loading	酸值/(mg·g^-1) acid value	酯化率/% esterification rate
1	240	5	0.30	0.10	187.0	9.0
2	240	5	0.30	0.25	57.2	72.3
3	240	5	0.30	0.60	109.1	47.2
4	240	5	0.20	0.25	38.2	81.5
5	240	5	0.25	0.25	75.3	63.5
6	240	5	0.35	0.25	62.3	69.8
7	240	5	0.40	0.25	55.6	73.1
8	240	3	0.20	0.25	96.4	53.3
9	240	4	0.20	0.25	87.1	57.8
10	240	6	0.20	0.25	40.9	80.2
11	240	7	0.20	0.25	39.9	81.0
12	220	5	0.20	0.25	89.4	56.7
13	230	5	0.20	0.25	65.7	68.2
14	250	5	0.20	0.25	43.6	78.9
15	260	5	0.20	0.25	41.2	80.1

项目 items		单位总酸量¹⁾/mmol total acid per unit	酸值/(mg·g^-1) acid value	酯化率/% esterification rate
对照 contrast	— ZnO		109.4 83.2	47.0 59.7
催化剂类型 catalyst type	Fe₃O₄-ZnO(ZnAc₂) Fe₃O₄@SiO₂-ZnO(ZnAc₂)	7.5 56.3	46.0 38.6	77.7 81.5
锌源 zinc sources	ZnAc₂ ZnCl₂ ZnSO₄ Zn(NO₃)₂	56.3(0.5) 44.2(0.1) 50.8(0.2) 49.1(0.1)	38.6 74.3 54.1 59.6	81.5 64.0 73.8 71.1
ZnAc₂负载量 loading of ZnAc₂	0.10 g 0.25 g 0.45 g 0.60 g	0 56.3 34.9 30.4	109 38.6 52.6 73.6	47 81.5 74.5 64.4

回收次数 recycling times	酸值/(mg·g^-1) acid value	酯化率/% esterification rate
1	38.6	81.3
2	39.7	80.8
3	40.2	80.5
4	39.0	81.1
5	39.1	81.1

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Fe₃O₄负载ZnO催化剂的制备及其催化合成松香甘油酯的研究

Preparation of Rosin Glyceride Catalyzed by Fe₃O₄ Supported ZnO

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