CaO/KIT-6固体碱催化剂的制备及其在酯交换反应中的催化性能

刘同慧; 刘宏乾; 褚格; 毕世楠; 于峰; 潘大海; 范彬彬; 李瑞丰

doi:10.1016/S1872-5813(21)60024-5

CaO/KIT-6固体碱催化剂的制备及其在酯交换反应中的催化性能

doi: 10.1016/S1872-5813(21)60024-5

太原理工大学化学化工学院，山西太原 030024

基金项目: 国家自然科学基金（21706176，21975174，21878203），山西省自然科学研究基金（201701D121027，201801D121057，201801D121061）和山西省科技创新重点团队项目（2014131006）资助

详细信息

作者简介:
刘同慧：liutonghui0023@163.com

通讯作者:
E-mail：yufeng@tyut.edu.cn

中图分类号: TQ426.6
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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-03
- 修回日期: 2020-11-24
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Preparation of CaO/KIT-6 solid base catalyst and its catalytic performance in transesterification

College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by the National Natural Science Foundation of China (21706176, 21975174, 21878203), Natural Science Research Foundation of Shanxi Province (201701D121027, 201801D121057, 201801D121061) and Shanxi Science and Technology Innovation Key Team Project (2014131006)

摘要

摘要: 采用浸渍法将活性氧化钙颗粒负载在介孔二氧化硅（KIT-6）表面，制备了酯交换反应催化剂CaO/KIT-6，并研究了其在大豆油与甲醇酯交换制备生物柴油反应中的催化性能。通过X射线衍射（XRD）、X射线光电子能谱（XPS）、CO₂程序升温脱附（CO₂-TPD）等测试手段对催化剂进行表征。在酯交换反应中，当醇油物质的量比为12、反应温度为65 °C、催化剂用量为8%、Ca/Si原子比为0.4、反应时间为2 h时，生物柴油转化率达到99.9%，CaO/KIT-6重复使用五次后催化活性仍保持在90%以上。与CaO及其他负载型催化剂相比，CaO/KIT-6催化剂在较低醇油物质的量之比、较短反应时间展现出更高的催化性能和良好的重复使用性。
- 生物柴油 /
- 氧化钙 /
- KIT-6 /
- 固体碱催化剂 /
- 酯交换
Abstract: CaO/KIT-6 was successfully prepared by loading activated calcium oxide particles on the surface of mesoporous silica (KIT-6) by post-synthesis method and tested for the transesterification of soybean oil with methanol. The catalyst was characterized by XRD, XPS, CO₂-TPD, N₂ adsorption-desorption and TEM. It is found that when the molar ratio of methanol to oil is 12, the reaction temperature is 65 °C, the addition of catalyst is 8% and the Ca/Si atomic ratio is 0.4, the conversion of soybean oil exceeds 99.9% at 2 h. After 5 cycles, the catalytic activity decreases slightly and the conversion is still up to 90%. Compared with CaO and other supported catalysts, CaO/KIT-6 catalyst exhibits higher catalytic performance and good reusability at lower methanol-to-oil molar ratio.
- biodiesel /
- calcium oxide /
- KIT-6 /
- solid base catalyst /
- transesterification

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图 1 KIT-6的结构图

Figure 1 Structure of KIT-6

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图 2 样品的XRD谱图

Figure 2 XRD patterns of the samples

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图 3 CaK-0.4的XPS谱图

Figure 3 XPS spectra of CaK-0.4

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图 4 样品的CO₂-TPD谱图

Figure 4 CO₂-TPD profiles of the samples

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图 5 样品的N₂吸附-脱附等温线和由DFT吸附理论计算得到的孔径分布图

Figure 5 N₂ adsorption-desorption isotherms and pore size distribution calculated from the DFT adsorption theory branch

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图 6 样品的TEM照片

Figure 6 TEM images of (a) KIT-6, (b) CaK-0.2, (c) CaK-0.4, (d) CaK-0.6

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图 7 反应参数对CaK-0.4在酯交换反应中的催化活性的影响

Figure 7 Effects of reaction parameters on the catalytic activities of CaK-0.4 for the transesterification reaction: (a): effect of molar ratio of methanol to oil (reaction temperature 65 °C, mass ratio of catalyst to oil 8%, Ca/Si atomic ratio 0.4, reaction time 2 h) (b): effect of reaction time (reaction temperature 65 °C, molar ratio of methanol to oil 12, Ca/Si atomic ratio 0.4, mass ratio of catalyst to oil 8%) (c): effect of Ca/Si atomic ratio (reaction temperature 65 °C, mass ratio of catalyst to oil 8%, molar ratio of methanol to oil 12, reaction time 2 h) (d): effect of mass ratio of catalyst to oil (reaction temperature 65 °C, Ca/Si atomic ratio 0.4, molar ratio of methanol to oil 12, reaction time 2 h)

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图 8 重复使用次数对大豆油转化率的影响

Figure 8 Effect of repeat use of catalyst on transesterification activity

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表 1 催化剂的结合能

Table 1 Binding energies of the catalysts

	Enerrgy E/eV
	Si 2p	O 1s		Ca 2p
CaK-0.2	101.9	531.9	530.9	346.8	350.4
CaK-0.4	101.3	529.9	531.6	346.6	350.1
CaK-0.6	100.8	529.9	531.5	346.6	350.1

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表 2 催化剂的结构特性

Table 2 Textural properties of the catalysts

Sample	S_BET/(m²·g⁻¹)	v_p/(cm³·g⁻¹)	d_p(av)/nm
KIT-6	798	0.74	3.7
CaK-0.2	93	0.28	6.8
CaK-0.4	29	0.10	4.1
CaK-0.6	20	0.10	6.3
CaO	10	0.02	4.9

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表 3 氧化钙和负载型催化剂制备生物柴油的催化性能比较

Table 3 Comparison of the activity of calcium oxide and supported catalysts for biodiesel production

Catalyst	Feedstock	Catalyst characterizations	Operation conditions	Results	Ref.
CaO	soybeanoil	S_BET = 0.56 m²·g⁻¹	t = 65 °C, t = 3 h, methanol/ oil = 12:1, catalyst content = 8%	FAME yield = 95%	[28]
CaO	sunflower oil	Not reported	t = 60 °C, t = 100 min, methanol/oil =13:1	conversion = 94%	[14]
CaO/n-Al₂O₃	soybean oil	S_BET = 26 m²·g⁻¹	t = 150 °C, t = 6 h, methanol/oil = 9:1, Ca loading = 20 mmol_metal/g_support, catalyst content = 3%	FAME yield = 90%	[29]
CaO/SBA-15	sunflower oil	S_BET = 7.4 m²·g⁻¹,v_total = 0.019 cm³·g⁻¹	t = 60 °C, t = 5 h, methanol/ oil = 12:1, CaO content = 14%, catalyst content = 1%	conversion = 95%	[18]
CaO/KIT-6	soybean oil	S_BET = 29.4 m²·g⁻¹,v_total = 0.098 cm³·g⁻¹	t = 65 °C, t = 2 h, methanol/ oil = 12:1, Ca/Si atomic ratio= 0.4, catalyst content = 8%	conversion = 99.9%	present work

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