Cu-Zr复合氧化物催化耦合甘油和CO<sub>2</sub>合成碳酸甘油酯

徐换换; 柯义虎

doi:10.1016/S1872-5813(23)60384-6

Cu-Zr复合氧化物催化耦合甘油和CO₂合成碳酸甘油酯

doi: 10.1016/S1872-5813(23)60384-6

徐换换^{1, 2,},
柯义虎^{1, 2, ,}

1.
北方民族大学国家民委化工技术基础重点实验室，宁夏银川 750021
2.
北方民族大学宁夏太阳能化学转化技术重点实验室，宁夏银川 750021

基金项目: 国家自然科学基金 (21862001); 宁夏餐厨废油资源化利用技术研发创新团队(2022QCXTD03)，宁夏低品质资源高值化利用技术研发人才小高地。

详细信息

通讯作者:
Tel: 13895397566, E-mail: keyihu123@nmu.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-08-08
- 修回日期: 2023-09-04
- 录用日期: 2023-09-05
- 网络出版日期: 2023-10-12

Synthesis of Glycerol Carbonate from Glycerol and CO₂ Catalyzed by Cu-Zr Complex Oxide

XU Huanhuan^{1, 2
,},
KE Yihu^{1, 2
, ,}

1.
Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan, 750021, China
2.
Ningxia Key Laboratory of Solar Chemical Conversion Technology, North Minzu University, Yinchuan 750021, China

Funds: The project was supported by National Natural Science Foundation of China (21862001), the Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals (grant number 2022QCXTD03) and the Ningxia Low-Grade Resource High Value Utilization and Environmental Chemical Integration Technology Innovation Team Project, China.

摘要

摘要: 采用水热法合成了一系列Cu-Zr物质的量比的Cu_1−xZr_xO₂双金属氧化物，以此为催化剂，将生物柴油生产过程副产物甘油与温室气体CO₂耦合反应制备精细化工产品碳酸甘油酯。结果表明，Zr掺杂量不同，催化剂对甘油羰基化反应效果呈现明显差距，最佳反应条件下，Cu_0.99Zr_0.01O₂催化剂具有最佳催化性能，甘油转化率和碳酸甘油酯选择性分别达到64.1%和85.9%。并且发现与纯CuO和纯ZrO₂相比，Cu_1−xZr_xO₂复合氧化物在甘油与CO₂耦合反应体系中表现出更强的催化活性，结合X-射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X-射线光电子能谱（XPS）、N₂吸附-脱附、程序升温还原（H₂-TPR）、程序升温脱附（TPD）、傅里叶变换红外光谱（FT-IR）等表征手段，推测高活性与Zr在CuO表面的分散程度、催化剂表面氧物种含量及酸碱性位点数量有关。此外，为了研究催化剂的稳定性，以Cu_0.99Zr_0.01O₂催化剂作为基准进行了循环性能测试，结果表明，经过六次循环后，甘油的转化率和碳酸甘油酯的选择性未发生明显变化，说明该催化剂优良的稳定性。
- 甘油 /
- 碳酸甘油酯 /
- 二氧化碳 /
- 复合氧化物 /
- 2-氰基吡啶
Abstract: A series of Cu_1−xZr_xO₂ bimetallic oxides with different Cu-Zr molar ratios were synthesized by hydrothermal method. At the same time, these catalysts were used for the catalytic conversion of glycerol. Glycerol carbonate is a fine chemical made from glycerol, a by-product of the biodiesel synthesis process and greenhouse gas CO₂. The experiment found that the effect of the catalyst on the carbonylation reaction of glycerol was significantly different with different Zr doping amounts. Under the optimal reaction conditions, Cu_0.99Zr_0.01O₂ catalyst had the best catalytic performance, the conversion of glycerol and the selectivity of glycerol carbonate reached 64.1% and 85.9%, respectively. It was found that Cu_1−xZr_xO₂ complex oxide exhibited stronger catalytic activity in the coupling reaction system of glycerol and CO₂ compared with pure CuO and pure ZrO₂. The structures, morphologies and surface properties of the catalysts were characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N₂ adsorption and desorption, Temperature programmed reduction (H₂-TPR), Programmed temperature Desorption (TPD), Fourier Transform Infrared Spectroscopy (FT-IR). It is speculated that the high activity is related to the degree of dispersion of Zr on the surface of CuO, the content of oxygen species on the catalyst surface and the number of acidic-basic sites. In addition, we investigated the stability of Cu_0.99Zr_0.01O₂ catalyst. The results showed that the conversion of glycerol and the selectivity of glycerol carbonate did not change significantly after 6 cycles, indicating the excellent stability of the catalyst.
- glycerol /
- glycerol carbonate /
- carbon dioxide /
- complex oxide /
- 2-cyanopyridine

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图 1 Cu_1−xZr_xO₂催化剂的XRD谱图

Figure 1 XRD pattern of Cu_1−xZr_xO₂ catalyst

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图 2 Cu_1−xZr_xO₂催化剂的SEM图像

Figure 2 SEM images of Cu_1−xZr_xO₂ catalysts (a) CuO (b) ZrO₂ (c) Cu_0.99Zr_0.01O₂ (d) Cu_0.95Zr_0.05O₂ (e) Cu_0.75Zr_0.25O₂ (f) Cu_0.60Zr_0.40O₂ (j) Cu_0.40Zr_0.60O₂

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图 3 Cu_0.99Zr_0.01O₂催化剂（a）、（b）TEM图像、（c）HRTEM图像和（d）SAED图像

Figure 3 (a)、(b) TEM, (c) HRTEM and (d) SAED of Cu_0.99Zr_0.01O₂ catalyst

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图 4 Cu_0.99Zr_0.01O₂催化剂的TEM-Mapping图像

Figure 4 TEM-Mapping image of Cu_0.99Zr_0.01O₂ catalyst

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图 5 Cu_1−xZr_xO₂催化剂的XPS谱图

Figure 5 XPS spectra of Cu_1−xZr_xO₂ catalysts (a) full spectra (b) Cu 2p (c) Zr 3d (d) O 1s

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图 6 Cu_1−xZr_xO₂催化剂的（a）N₂吸附-脱附和（b）孔径分布

Figure 6 (a) N₂ adsorption-desorption isotherms and (b) pore size distribution of Cu_1−xZr_xO₂ catalysts

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图 7 Cu_1−xZr_xO₂催化剂的H₂-TPR谱图

Figure 7 H₂-TPR diagram of Cu_1−xZr_xO₂ catalyst

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图 8 Cu_1−xZr_xO₂催化剂的TPD谱图

Figure 8 TPD of Cu_1−xZr_xO₂ catalysts (a) NH₃-TPD (b) CO₂-TPD

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图 9 Cu_1−xZr_xO₂催化剂的FT-IR谱图

Figure 9 FT-IR spectra of Cu_1−xZr_xO₂ catalysts

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图 10 反应条件对Cu_0.99Zr_0.01O₂催化剂催化活性的影响

Figure 10 Effect of reaction conditions on catalytic activity of Cu_0.99Zr_0.01O₂ catalyst

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图 11 催化剂的重复使用性测试

Figure 11 Reusability test of catalyst

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图 12 甘油在催化剂上的羧化作用和2-氰基吡啶的水化作用

Figure 12 Carboxylation of glycerol on the catalyst and hydration of 2-cyanopyridine

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表 1 Cu_1−xZr_xO₂样品表面氧种类含量

Table 1 Surface oxygen species content of Cu_1−xZr_xO₂ samples

Sample	Surface oxygen species content /%
Sample	O_Ⅰ	O_Ⅱ	O_Ⅲ	O_Ⅰ(O_Ⅱ + O_Ⅲ)
CuO	99.14	0.61	0.24	11.66
Cu_0.99Zr_0.01O₂	57.78	29.85	12.36	1.37
Cu_0.95Zr_0.05O₂	54.9	30.14	14.90	1.22
Cu_0.75Zr_0.25O₂	47.01	43.06	9.93	0.89
Cu_0.60Zr_0.40O₂	34.78	38.91	26.31	0.53
Cu_0.40Zr_0.60O₂	64.60	26.92	8.48	1.82
ZrO₂	74.74	15.05	10.22	2.96

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表 2 Cu_1−xZr_xO₂催化剂的织构性质

Table 2 Texture properties of Cu_1−xZr_xO₂ catalysts

Sample	S_BET/(m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore size/nm
CuO	8.2	0.027	12.9
Cu_0.99Zr_0.01O₂	14.3	0.044	11.2
Cu_0.95Zr_0.05O₂	18.3	0.067	12.1
Cu_0.75Zr_0.25O₂	55.3	0.152	9.0
Cu_0.60Zr_0.40O₂	59.5	0.128	7.5
Cu_0.40Zr_0.60O₂	106.6	0.194	5.8
ZrO₂	118.5	0.249	6.5

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表 3 不同Zr含量Cu_1−xZr_xO₂催化剂催化活性

Table 3 Evaluation of catalytic activity of Cu_1−xZr_xO₂ catalysts with different Zr contents

Sample	Conversion of glycerol /%	Selectivity of GC /%	Yield of GC /%
Blank	34.3	11.7	4.0
CuO	67.9	73.9	50.2
Cu_0.99Zr_0.01O₂	64.1	85.9	55.1
Cu_0.95Zr_0.05O₂	61.1	85.2	52.1
Cu_0.75Zr_0.25O₂	59.7	79.3	47.3
Cu_0.60Zr_0.40O₂	65.6	74.4	48.8
Cu_0.40Zr_0.60O₂	51.3	91.0	46.7
ZrO₂	34.0	11.8	4.0
Reaction conditions: glycerol 0.92 g, 2-cyanopyridine 3.26 g, DMF 10 mL, 120 ℃, 5 h, p(CO₂) = 3 MPa.

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