助剂对于Cu/ZnO催化剂结构特征及催化草酸二甲酯加氢反应性能影响研究

孔祥鹏; 游新明; 元培红; 吴跃焕; 王瑞虹; 陈建刚

doi:10.1016/S1872-5813(22)60073-2

助剂对于Cu/ZnO催化剂结构特征及催化草酸二甲酯加氢反应性能影响研究

doi: 10.1016/S1872-5813(22)60073-2

孔祥鹏^1, ,,
游新明^{1, 2},
元培红³,
吴跃焕¹,
王瑞虹¹,
陈建刚^4, ,

1.
太原工业学院化学与化工系, 山西太原, 030008
2.
中北大学化学与化工学院, 太原山西, 030051
3.
中铁三局集团疾病预防控制中心, 太原山西, 030006
4.
中国科学院山西煤化所煤转化国家重点实验室, 太原山西, 030001

基金项目: 山西省高等学校科技创新项目(Grant STIP 2019L0928, 2020L0658)；山西省1331工程资助

详细信息

作者简介:
孔祥鹏(1983-)，男，博士，副教授，研究方向为催化加氢。E-mail：yekong1999@126.com

通讯作者:
KONG Xiangpeng, E-mail: yekong1999@126.com

CHEN Jiangang, E-mail: chenjg@sxicc.ac.cn

中图分类号: TK6
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- 文章访问数: 21
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出版历程
- 收稿日期: 2022-07-31
- 录用日期: 2022-10-09
- 修回日期: 2022-09-30
- 网络出版日期: 2022-11-16

Hydrogenation of dimethyl oxalate to ethylene glycol over the Cu-M/ZnO (M=Zr^{4 +}, Al^{3 +}, Mg^{2 +}) catalysts: Role of the dopants in the structure and catalytic features

1.
Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China
2.
School of Chemistry and Chemical Engineering and Technology, North University of China, Taiyuan 030051, China
3.
Center for Disease Control and Prevention, The Third Engineer Group Co., LTD of China Railway, Taiyuan 030012, China
4.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the financial support from the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (Grant STIP 2019L0928, 2020L0658) and Shanxi’s 1331 Project

摘要

摘要: 采用共沉淀法成功合成了掺杂不同助剂的Cu-M/ZnO (Cu: ZnO物质的量比=5∶4，M = Zr^{4 +}、Al^{3 +}、Mg^{2 +}，助剂含量为4.0%)用于催化草酸二甲酯(Dimethyl oxalate , DMO)选择加氢反应催化剂。结果表明，微量掺杂Al^{3 +}、Mg^{2 +}助剂嵌入于ZnO晶相，Zr^{4 +}助剂嵌入Cu晶相均能显著促进Cu/ZnO催化剂中铜分散；其中，Mg^{2 +}助剂能够有效增强Cu、ZnO物相间相互作用，Zr^{4 +}助剂能够有效增强Cu、ZrO₂物相间相互作用。催化DMO加氢选择加氢反应，Cu/ZnO催化剂乙二醇(Ethylene glycol，EG)收率仅为75.0%，Cu-Al/ZnO、Cu-Zr/ZnO和Cu-Mg/ZnO催化剂的EG收率分别为85.0%、90.0%、95.0%。相比Cu/ZnO和Cu-Al/ZnO催化剂易于失活，Cu-Zr/ZnO和Cu-Mg/ZnO催化剂显现出优异稳定性，稳定反应时长超过100 h。催化剂构-效关系表明，Cu/ZnO和Cu-Mg/ZnO催化剂表面较高Cu⁺活性位以及充足Cu⁰活性位协同效应是其显现优异催化活性的主要因素。此外，Cu-Zr/ZnO和Cu-Mg/ZnO中较强的金属/氧化物相互作用能够有效抑制催化剂中铜纳米粒子于强放热反应中发生迁移、烧结，赋予催化剂优异的稳定性。
- 助剂 /
- Cu/ZnO催化剂 /
- 草酸二甲酯 /
- 加氢 /
- 乙二醇
Abstract: The Cu-M/ZnO catalysts (M = Zr^{4 +}, Al^{3 +} and Mg^{2 +}) for dimethyl oxalate (DMO) selective hydrogenation to ethylene glycol (EG) have been synthesized by the co-precipitation method. The texture properties of the as-synthesized catalysts were systematically characterized by the N₂-physisorption, N₂O-titration, XRD, H₂-TPR, CO₂-TPD, SEM, FT-IR and XPS focusing on the functions of the dopants. It is found that the incorporated dopants can significantly promote the Cu dispersion. Particularly, a trace of Mg^{2 +} dopants can effectively strengthen the interaction between Cu and ZnO phases by embedding into the ZnO lattice, while the Cu/ZrO₂ interaction could be reinforced with the Zr^{4 +} dopant introduced. For DMO gas-phase hydrogenation, the EG yield of the Cu/ZnO catalyst increased from 75.0% to 85.0% and 90.0% in presence of Zr^{4 +} and Al^{3 +} dopants, respectively. Particularly, the EG selectivity of Cu-Mg/ZnO catalyst can reach up to 95.0% with DMO completely converted for more than 100 h. The correlation between the catalytic behavior and physicochemical features suggested that the Cu⁺ sites should be vital for the catalytic behavior of the Cu/ZnO based catalysts with adequate Cu⁰ sites. Additionally, the strengthened Cu/oxide interaction favors the outstanding stability of the Cu-Zr/ZnO and Cu-Mg/ZnO catalyst in DMO hydrogenation.
- cu/zno catalyst /
- dopant /
- dimethyl oxalate /
- hydrogenation /
- ethylene glycol

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图 1 Cu/ZnO和Cu-M/ZnO (M = Zr^{4 +}、Al^{3 +}、Mg^{2 +})催化剂的吸附-脱附等温曲线(a)和孔径分布曲线(b)

Figure 1 N₂ adsorption-desorption isotherms (a) and pore size distribution curves (b) calculated by BJH equation in desorption branch of the Cu/ZnO and Cu-M/ZnO (M = Zr^{4 +}, Al^{3 +}, Mg^{2 +}) catalysts

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图 2 焙烧和还原后Cu/ZnO基催化剂的XRD谱图

Figure 2 XRD patterns of the calcined and reduced Cu/ZnO based catalysts

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图 3 Cu/ZnO和Cu-M/ZnO (M = Zr^{4 +}、Al^{3 +}、Mg^{2 +})催化剂SEM谱图

Figure 3 SEM images of the reduced Cu/ZnO and Cu-M/ZnO samples

(a, b) CuO/ZnO, (c, d) CuO-Zr/ZnO, (e, f CuO-Al/ZnO, (g, h) CuO-Mg/ZnO

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图 4 CuO/ZnO和Cu-M/ZnO (M = Zr^{4 +}、Al^{3 +}、Mg^{2 +})催化剂H₂-TPR谱图

Figure 4 H₂-TPR profiles of as-synthesized CuO/ZnO and CuO-M/ZnO (M = Zr^{4 +}、Al^{3 +}、Mg^{2 +}) catalysts

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图 5 CuO/ZnO和添加不同助剂Cu-M/ZnO (M= Zr^{4 +}、Al^{3 +}和Mg^{2 +} )催化剂CO₂-TPD谱图

Figure 5 CO₂-TPD profiles of the reduced Cu/ZnO and Cu-M/ZnO (M= Zr^{4 +}、Al^{3 +} and Mg^{2 +} ) catalysts

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图 6 焙烧CuO/ZnO和CuO-M/ZnO (M= Zr^{4 +}、Al^{3 +}和Mg^{2 +})催化剂的FT-IR谱图

Figure 6 FT-IR spectra of the as-prepared CuO/ZnO and CuO-M/ZnO (M= Zr^{4 +}、Al^{3 +} and Mg^{2 +}) catalysts

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图 7 还原活化Cu/ZnO和Cu-M/ZnO(M= Zr^{4 +}、Al^{3 +}和Mg^{2 +} )催化剂O1s (a), Zn2p (b), Cu2p (c)和Cu LMM XAES (d)谱图

Figure 7 O1s (a), Zn2p (b), Cu2p (c) XPS and Cu LMM XAES (d) spectra of the activated Cu/ZnO and Cu-M/ZnO(M= Zr^{4 +}、Al^{3 +} or Mg^{2 +} ) catalysts

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图 8 Cu/ZnO和Cu-M/ZnO (M=Mg^{2 +}、Al^{3 +}、Zr^{4 +})催化剂的催化反应性能。

Figure 8 Catalytic behavior of the Cu/ZnO and Cu-M/ZnO (M=Mg^{2 +}、Al^{3 +}、Zr^{4 +}) catalysts. Reaction conditions: 2.5 MPa, 220 ℃, H₂/DMO=100 (mol/mol), LHSV=2.0 h⁻¹

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表 1 Cu/ZnO和添加不同助剂Cu-M/ZnO催化剂的织构参数

Table 1 Textures and copper dispersion of Cu-M/ZnO catalysts with different dopants

Catalyst	S_BET/(m²﹒g⁻¹)^a	vp/(cm³﹒g⁻¹)^a	Dp/nm^a	Crystallitesize/nm^b	Cu dispersion/%^c	S_Cu⁰/m²﹒g⁻¹^c
Cu/ZnO	50.3	0.21	16.4	11.3	13.0	2.40
Cu-Zr/ZnO	72.2	0.27	15.1	8.6	60.1	7.00
Cu-Al/ZnO	76.0	0.44	23.1	7.4	42.3	3.69
Cu-Mg/ZnO	93.1	0.27	11.4	11.1	13.4	2.45
^a S_BET: specific surface area; vp: pore volume; Dp: average pore determined by N₂ physical adsorption; ^b Cu crystallite size determined by Scherrer Formula; ^c Cu dispersion and S_Cu⁰(Cu surface area) determined by the N₂O titration

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表 2 还原活化催化剂还原后的XPS测试及拟合参数

Table 2 Surface Cu component of the reduced samples based on Cu LMM deconvolution

Catalyst	E_B(eV)		E_B of Cu 2p_3/2/eV	Cu⁺/% ^a	S_{Cu +}/(m²·g⁻¹) ^b
Catalyst	Cu⁺	Cu⁰	E_B of Cu 2p_3/2/eV	Cu⁺/% ^a	S_{Cu +}/(m²·g⁻¹) ^b
Cu/ZnO	916.2	918.6	933.0	38.6	0.9
Cu-Zr/ZnO	915.7	918.1	935.6	45.5	3.1
Cu-Al/ZnO	914.5	917.0	932.0	49.6	1.9
Cu-Mg/ZnO	913.7	916.1	934.0	55.2	2.7
a: Cu⁺/(Cu⁺ + Cu⁰) intensity ratio obtained by deconvolution of Cu LMM XAES spectra, b: Calculated based on xCu^＋ and $S_{{\rm{Cu}}}^{0}$ assuming that the Cu⁺ ion occupies the same area and has the same atomic sensitivity factor as those of the Cu⁰ atom

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助剂对于Cu/ZnO催化剂结构特征及催化草酸二甲酯加氢反应性能影响研究

doi: 10.1016/S1872-5813(22)60073-2

作者简介:
孔祥鹏(1983-)，男，博士，副教授，研究方向为催化加氢。E-mail：yekong1999@126.com

通讯作者:
KONG Xiangpeng, E-mail: yekong1999@126.com

CHEN Jiangang, E-mail: chenjg@sxicc.ac.cn

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Hydrogenation of dimethyl oxalate to ethylene glycol over the Cu-M/ZnO (M=Zr^{4 +}, Al^{3 +}, Mg^{2 +}) catalysts: Role of the dopants in the structure and catalytic features

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助剂对于Cu/ZnO催化剂结构特征及催化草酸二甲酯加氢反应性能影响研究

doi: 10.1016/S1872-5813(22)60073-2

作者简介: 孔祥鹏(1983-)，男，博士，副教授，研究方向为催化加氢。E-mail：yekong1999@126.com

通讯作者: KONG Xiangpeng, E-mail: yekong1999@126.com CHEN Jiangang, E-mail: chenjg@sxicc.ac.cn

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Hydrogenation of dimethyl oxalate to ethylene glycol over the Cu-M/ZnO (M=Zr4 + , Al3 + , Mg2 + ) catalysts: Role of the dopants in the structure and catalytic features

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出版历程

目录

作者简介:
孔祥鹏(1983-)，男，博士，副教授，研究方向为催化加氢。E-mail：yekong1999@126.com

通讯作者:
KONG Xiangpeng, E-mail: yekong1999@126.com

CHEN Jiangang, E-mail: chenjg@sxicc.ac.cn

Hydrogenation of dimethyl oxalate to ethylene glycol over the Cu-M/ZnO (M=Zr^{4 +}, Al^{3 +}, Mg^{2 +}) catalysts: Role of the dopants in the structure and catalytic features