催化剂制备方法对Ni-Ag/SiO<sub>2</sub>催化草酸二甲酯加氢制乙醇酸甲酯性能的影响

方笛; 罗祖伟; 曹约强; 周静红; 李伟

doi:10.19906/j.cnki.JFCT.2024020

催化剂制备方法对Ni-Ag/SiO₂催化草酸二甲酯加氢制乙醇酸甲酯性能的影响

doi: 10.19906/j.cnki.JFCT.2024020

方笛^{1, 2,},
罗祖伟^2,,
曹约强^{1, 2,},
周静红^{1, 2, ,},
李伟^2,

1.
华东理工大学化学工程联合国家重点实验室, 上海 200237
2.
华东理工大学化工学院, 上海 200237

基金项目: 国家自然科学基金(22178102)资助

详细信息

通讯作者:
Tel: 021-64252169, E-mail: jhzhou@ecust.edu.cn

中图分类号: TQ032.4
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- 被引次数: 0
出版历程
- 收稿日期: 2024-03-10
- 修回日期: 2024-04-18
- 录用日期: 2024-04-20
- 网络出版日期: 2024-05-22

Influence of Ni-Ag/SiO₂ catalyst preparation method on its performance in hydrogenation of dimethyl oxalate to methyl glycolate

FANG Di^{1, 2
,},
LUO Zuwei^2
,,
CAO Yueqiang^{1, 2
,},
ZHOU Jinghong^{1, 2
, ,},
LI Wei^2
,

1.
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Funds: National Natural Science Foundation of China(22178102).

摘要

摘要: 本研究采用均匀沉淀-浸渍和浸渍-浸渍两种分步法分别制备了Ni-Ag/SiO₂-p和Ni-Ag/SiO₂-i两种Ni-Ag双金属催化剂，用于催化草酸二甲酯(DMO)选择性加氢制乙醇酸甲酯(MG)。利用X射线衍射、红外光谱、透射电镜、N₂物理吸附、程序升温脱附实验和X射线光电子能谱表征技术对两种催化剂进行了系统的表征和结构解析，发现催化剂的制备方法对双金属催化剂的结构和性能有着重要影响，Ni-Ag/SiO₂-p催化剂中由于层状硅酸镍结构的存在，Ag、Ni活性物种的金属分散度相比于Ni-Ag/SiO₂-i催化剂更高，这促进了反应物H₂和DMO的吸附与活化；催化剂性能评价结果表明，均匀沉淀-浸渍法制备的Ag负载量仅为0.48%的Ni-Ag/SiO₂-p催化剂显著提升了DMO加氢活性，在220 ℃、2.0 MPa、液时空速0.5 h^-1、氢酯比50的条件下，DMO转化率和MG选择性达到了99.1%和87.6%。研究结果可为设计和优化DMO加氢制MG催化剂提供一定借鉴。
- 草酸二甲酯 /
- 加氢 /
- 催化剂制备 /
- 乙醇酸甲酯
Abstract: Methyl glycolate (MG), as a high value-added organic chemical intermediate, possesses broad prospects for downstream applications. In this study, nickel-silver bimetallic catalysts, denoted as Ni-Ag/SiO₂-p and Ni-Ag/SiO₂-i, were synthesized via homogenous precipitation-impregnation and impregnation-impregnation methods, respectively, for selective hydrogenation of dimethyl oxalate (DMO) to MG. Various characterization techniques, including X-ray diffraction, infrared spectroscopy, transmission electron microscopy, N₂ physisorption, and X-ray photoelectron spectroscopy, were employed to extensively analyze the catalysts' structures. The results unveiled that the Ni-Ag/SiO₂-p catalyst, prepared through the precipitation of the nickel precursor followed by impregnation of the silver precursor, exhibited a laminated nickel silicate structure and a higher specific surface area compared to the Ni-Ag/SiO₂-i catalyst, synthesized via sequential impregnation of both metal precursors over SiO₂. This enhanced surface area facilitated improved metal-support interaction and the reduction of smaller metal particles, thereby Ni-Ag/SiO₂-p demonstrated superior metal dispersion compared to Ni-Ag/SiO₂-i, providing more active sites for adsorption and activation of reactant molecules. Specifically, Ni species with small particle sizes facilitated the adsorption and activation of DMO molecules , while the introduction of Ag not only promoted the adsorption of DMO molecules but also significantly enhanced the adsorption and activation capacity of H₂. This resulted in H₂ predominating in competitive adsorption with DMO molecules, substantially augmenting the hydrogenation activity of DMO on the catalyst. Remarkably, Ni-Ag/SiO₂-p achieved outstanding results with a low Ag loading of 0.48% under operating conditions of 220 ℃, 2.0 MPa, a liquid hourly space velocity of 0.5 h^-1, and a hydrogen-to-ester ratio of 50. Specifically, Ni-Ag/SiO₂-p catalyst demonstrated DMO conversion and MG selectivity of 99.1% and 87.6%, respectively. These findings underscore the substantial impact of catalyst preparation method on the structure and catalytic performance of bimetallic catalysts, offering valuable insights for the design and optimization of catalysts for DMO hydrogenation to MG.
- dimethyl oxalate /
- hydrogenation /
- catalyst preparation /
- methyl glycolate

HTML全文

图 1 Ni-Ag/SiO₂和Ni/SiO₂前驱体的H₂-TPR谱图

Figure 1 H₂-TPR profiles of Ni-Ag/SiO₂ and Ni/SiO₂ precursors

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图 2 SiO₂和Ni-Ag/SiO₂催化剂的（a）N₂物理吸附-脱附等温线及（b）孔径分布图

Figure 2 (a) N₂ physisorption isotherms and (b) corresponding pore size distributions of SiO₂ and Ni-Ag/SiO₂ catalysts

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图 3 Ni-Ag/SiO₂催化剂的（a）XRD谱图和（b）FT-IR谱图

Figure 3 (a) XRD patterns and (b) FT-IR spectra of Ni-Ag/SiO₂ catalysts

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图 4 （a）Ni-Ag/SiO₂-p和（b）Ni-Ag/SiO₂-i催化剂的TEM图像和金属粒径分布

Figure 4 TEM images and histograms of metal particle size distribution of (a) Ni-Ag/SiO₂-p and (b) Ni-Ag/SiO₂-i catalysts

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图 5 还原后Ni-Ag/SiO₂催化剂的（a）Ni 2p和（b）Ag 3d XPS谱图

Figure 5 (a) Ni 2p and (b) Ag 3d XPS spectra of reduced Ni-Ag/SiO₂ catalysts

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图 6 Ni-Ag/SiO₂催化剂性能

Figure 6 Catalytic performances of Ni-Ag/SiO₂ catalysts Reaction conditions: (a)−(c) 0.5 h⁻¹, 220 ℃, 2.0 MPa; (d)−(f) 0.5 h⁻¹, 220 ℃, 2.0 MPa, H₂/DMO = 50 mol/mol.

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图 7 催化剂的（a）H₂-TPD 和（b）DMO-TPD谱图

Figure 7 (a) H₂-TPD and (b) DMO-TPD profiles of catalysts

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图 8 Ni-Ag/SiO₂催化剂的（a）MG-TPD和（b）CO-TPD谱图

Figure 8 (a) MG-TPD and (b) CO-TPD profiles of Ni-Ag/SiO₂ catalysts

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表 1 SiO₂和Ni-Ag/SiO₂催化剂的理化特征

Table 1 Physicochemical properties of SiO₂ and Ni-Ag/SiO₂ catalysts

Sample	Loading^a w/%		S_BET^b/ (m²·g⁻¹)	v_pore^c/ (cm³·g⁻¹)	d_BJH^c/ nm	d_metal^d/ nm	Q_CO^e/ (mmol·g⁻¹)	$Q_{\Delta {\mathrm{H}}_2} $^f/ (mmol·g⁻¹)
Sample	Ni	Ag	S_BET^b/ (m²·g⁻¹)	v_pore^c/ (cm³·g⁻¹)	d_BJH^c/ nm	d_metal^d/ nm	Q_CO^e/ (mmol·g⁻¹)	$Q_{\Delta {\mathrm{H}}_2} $^f/ (mmol·g⁻¹)
SiO₂	−	−	248	0.27	3.72	−	−	−
Ni-Ag/SiO₂-p	8.9	0.48	267	0.58	7.86	3.4	0.0041	0.077
Ni-Ag/SiO₂-i	9.3	0.51	173	0.20	3.96	7.6	0.0017	0.026
^a: Ni content and Ag content determined by ICP; ^b: Specific surface area calculated by BET method; ^c: Pore volume and pore size calculated by BJH method; ^d: Average size of metal particles determined by TEM; ^e: CO adsorption amount was determined by CO-chem; ^f: H₂ consumption of Ag was determined by the difference between the H₂ consumption for H₂-TPR test after the oxidation by N₂O and the CO adsorption amount for CO-Chem.

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