Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用

doi:10.11949/0438-1157.20190395

化工学报 ›› 2019, Vol. 70 ›› Issue (12): 4625-4634.DOI: 10.11949/0438-1157.20190395

• 催化、动力学与反应器 • 上一篇下一篇

Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用

王志苗^1,²(),张洪起¹,周立超¹,李芳^1,²,薛伟^1,²(),王延吉^1,²()

1. 河北工业大学化工学院，河北省绿色化工与高效节能重点实验室，天津 300130
2. 天津市本质安全化工技术重点实验室，天津 300130

收稿日期:2019-04-16 修回日期:2019-08-23 出版日期:2019-12-05 发布日期:2019-12-05
通讯作者: 薛伟,王延吉
作者简介:王志苗（1985—），女，硕士，实验师，wangzhimiao@hebut.edu.cn
基金资助:
国家自然科学基金项目(21776057);天津市自然科学基金项目(17JCYBJC20100);河北省留学人员科技活动择优资助项目(CL201605)

Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate

Zhimiao WANG^1,²(),Hongqi ZHANG¹,Lichao ZHOU¹,Fang LI^1,²,Wei XUE^1,²(),Yanji WANG^1,²()

1. Hebei Provincial Key Laboratory of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
2. Tianjin Key Laboratory of Chemical Process Safety, Tianjin 300130, China

Received:2019-04-16 Revised:2019-08-23 Online:2019-12-05 Published:2019-12-05
Contact: Wei XUE,Yanji WANG

摘要/Abstract

摘要：

采用微乳液法制备了Ce为助剂的Pd-Ce-O/SiO₂催化剂，用于苯酚氧化羰基化合成碳酸二苯酯（DPC）反应。活性评价结果显示，催化剂性能随着Ce用量的增加而提高，当Ce/Pd摩尔比为10/1时，苯酚转化率为64.4%，碳酸二苯酯选择性为83.4%。利用XRD表征发现，部分Ce⁴⁺进入到PdO晶格中，使得失活Pd原子中的电子更容易向Ce转移，从而易于再生，表现出更好的催化性能。根据上述结果，设计制备了Pd-O/CeO₂催化剂用于本反应，苯酚转化率和碳酸二苯酯选择性分别仅为24.0%和23.3%。表征发现，在Pd-Ce-O/SiO₂催化剂表面，Pd物种主要是PdO，而Pd-O/CeO₂表面的Pd物种则以PdO₂为主。由于苯酚氧化羰基化反应的活性中心为Pd(Ⅱ)，所以Pd-O/CeO₂催化性能较差。并且，由于Pd与CeO₂之间存在强相互作用，催化剂表面Pd含量较低，这也是Pd-O/CeO₂催化活性较差的原因之一。

关键词: 碳酸二苯酯, 氧化羰基化, 多相反应, 催化剂, 载体, 二氧化铈

Abstract:

A Pd-Ce-O/SiO₂ catalyst with Ce as auxiliary was prepared by microemulsion method for oxidative carbonylation of phenol to synthesize diphenyl carbonate (DPC). The activity evaluation results showed that the catalyst performance increased with the increase of the amount of Ce. When the Ce/Pd molar ratio was 10/1, the phenol conversion rate was 64.4%, and the diphenyl carbonate selectivity was 83.4%. The XRD results showed that part of Ce⁴⁺ entered into PdO crystal lattice, therefore the electrons of deactivated Pd could easily be transferred to Ce. So the Pd-Ce-O/SiO₂ catalyst could be easily regenerated and showed better performance. According to the above mentioned results, Pd-O/CeO₂ was designed and prepared for oxidative carbonylation of phenol. However, unlike Pd-Ce-O/SiO₂, Pd-O/CeO₂ showed poor catalytic performance. The phenol conversion and DPC selectivity was only 24.0% and 23.3% respectively. The characterization results showed that PdO was the main species of Pd on the surface of Pd-Ce-O/SiO₂, but there was more PdO₂ on Pd-O/CeO₂. Because Pd(Ⅱ) is the active site for oxidative carbonyation, Pd-O/CeO₂ exhibited inferior activity to Pd-Ce-O/SiO₂. In addition, in Pd-O/CeO₂ catalyst, the surface Pd content was lower than that of other catalyst because of the strong interaction between Pd species and CeO₂. That s one of the reasons for the poor activity of Pd-O/CeO₂.

Key words: diphenyl carbonate, oxidative carbonlyation, heterogeneous reaction, catalyst, support, ceria

中图分类号:

O 643

王志苗, 张洪起, 周立超, 李芳, 薛伟, 王延吉. Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用[J]. 化工学报, 2019, 70(12): 4625-4634.

Zhimiao WANG, Hongqi ZHANG, Lichao ZHOU, Fang LI, Wei XUE, Yanji WANG. Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate[J]. CIESC Journal, 2019, 70(12): 4625-4634.

图/表 12

图1 Pd-M-O/SiO2催化苯酚氧化羰基化反应性能（M=Co、Mn、Cu、Ce, M/Pd摩尔比为10/1）

Fig.1 Catalytic performance of Pd-M-O/SiO2 for oxidative carbonylation of phenol(reaction conditions: 100℃, 6.6 MPa, CO/O2=10/1, others were listed in Section 1.4)

图2 Ce/Pd摩尔比对Pd-Ce-O/SiO2催化苯酚氧化羰基化反应的影响

Fig.2 Effect of Ce/Pd molar ratio on oxidative carbonylation of phenol over Pd-Ce-O/SiO2(reaction conditions: 100℃, 6.6 MPa, CO/O2=10/1, others were listed in Section 1.4)

图3 具有不同Ce/Pd摩尔比Pd-Ce-O/SiO2催化剂的XRD谱图

Fig.3 XRD patterns of Pd-Ce-O/SiO2 catalyst with different Ce/Pd molar ratio

表1 具有不同Ce/Pd摩尔比Pd-Ce-O/SiO2催化剂中PdO(101)晶面间距和晶格参数 with different Ce/Pd molar ratio

Table 1 Interplanar spacing and lattice parameters of PdO(101) in Pd-Ce-O/SiO2 catalyst with different Ce/Pd molar ratio

Pd-Ce-O/SiO₂催化剂中Ce/Pd摩尔比	PdO(101)晶面间距 / nm	晶格参数 / nm
Pd-Ce-O/SiO₂催化剂中Ce/Pd摩尔比	PdO(101)晶面间距 / nm	a	b	c
不加Ce	0.26032	0.30330	0.30330	0.53849
1∶1	0.26283	0.30413	0.30413	0.53347
2∶1	0.26360	0.30392	0.30392	0.53595
5∶1	0.26404	0.30423	0.30423	0.53322
10∶1	0.26572	0.30398	0.30398	0.54006

表2 Pd基催化剂物理化学性质及催化苯酚氧化羰基化反应性能 for oxidative carbonylation of phenol

Table 2 Physicochemical properties of Pd-based catalysts and their catalytic performance for oxidative carbonylation of phenol

催化剂	Pd 含量/% (质量)		比表面积/(m²/g)	催化反应性能^②
催化剂	XPS	理论含量	比表面积/(m²/g)	苯酚转化率/%	DPC选择性/%
Pd-O/CeO₂	0.58	1.0	14.5	24.0	23.3
Pd-O/SiO₂	0.90	1.0	37.1	38.4	85.4
Pd-Ce-O/SiO₂^①	0.74	1.0	49.6	64.4	83.4

图4 Pd-Ce-O/SiO2、Pd-O/CeO2和Pd-O/SiO2的XRD谱图

Fig.4 XRD patterns of Pd-Ce-O/SiO2 (Ce/Pd=10/1 in molar ratio), Pd-O/CeO2 and Pd-O/SiO2 catalysts

图5 Pd-O/SiO2、Pd-Ce-O/SiO2和Pd-O/CeO2催化剂的Pd 3d XPS谱图

Fig.5 Pd 3d XPS spectra of Pd-O/SiO2, Pd-Ce-O/SiO2 and Pd-O/CeO2 catalysts

图6 Pd-O/CeO2、Pd-Ce-O/SiO2和Pd-O/SiO2催化剂的TPR曲线

Fig.6 TPR profiles of Pd-O/CeO2, Pd-Ce-O/SiO2 and Pd-O/SiO2 catalysts

图7 Pd-O/SiO2、Pd-Ce-O/SiO2和Pd-O/CeO2的TEM图

Fig.7 TEM images of Pd-O/SiO2, Pd-Ce-O/SiO2 and Pd-O/CeO2

图8 Pd-O/CeO2的HAADF-STEM图和EDS mapping图

Fig.8 HAADF-STEM and EDS mapping images of Pd-O/CeO2

图9 Pd-Ce-O/SiO2的Pd 3d XPS谱图

Fig.9 Pd 3d XPS spectra of Pd-Ce-O/SiO2

图10 Pd-Ce-O/SiO2的Ce 3d XPS谱图

Fig.10 Ce 3d XPS spectra of Pd-Ce-O/SiO2

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Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用

Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate

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