Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways
- Low-carbon Chemistry and Chemical Engineering Vol. 49, Issue 1, Pages: 42-51(2024)
- 作者机构：
1.太原理工大学 化学学院，山西 太原 030600
2.太原理工大学 化学工程与技术学院 省部共建煤基能源清洁高效利用国家重点实验室，山西 太原 030024
- 作者简介：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20230152
CLC：
扫 描 看 全 文
靳珲青,石晓丹,靳刘艳等.DMO经两种反应路径加氢制乙醇催化剂研究进展[J].低碳化学与化工,2024,49(01):42-51.
JIN Huiqing,Xiaodan SHI,JIN Liuyan,et al.Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):42-51.
靳珲青,石晓丹,靳刘艳等.DMO经两种反应路径加氢制乙醇催化剂研究进展[J].低碳化学与化工,2024,49(01):42-51. DOI： 10.12434/j.issn.2097-2547.20230152.
JIN Huiqing,Xiaodan SHI,JIN Liuyan,et al.Research progress on catalysts for dimethyl oxalate hydrogenation to ethanol via two reaction pathways[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):42-51. DOI： 10.12434/j.issn.2097-2547.20230152.
摘要
煤基合成气经草酸二甲酯（DMO）加氢制乙醇（EtOH）是合成气间接制EtOH的一条重要路径。在DMO加氢反应过程中，同时存在经乙二醇（EG）中间体加氢制EtOH和经乙酸甲酯（MA）中间体加氢制EtOH两种不同的反应路径。分析了两种不同反应路径的特点，并总结了DMO加氢制EtOH两种不同反应路径所用催化剂及其影响EtOH选择性的关键因素。DMO经EG中间体加氢制EtOH的反应路径通常需要较高的反应温度和多活性位点协同催化，可从载体结构、制备方法以及添加助剂3个方面对常用的Cu基催化剂的催化活性进行调控。DMO经MA中间体加氢制EtOH的反应温度相对较低，常用催化剂以过渡金属碳化物（Mo基和Fe基）为主，但仍存在催化剂加氢能力不足的问题。所总结内容有助于加深对DMO加氢制EtOH两条路径的系统认识，并为未来合理设计和制备高稳定、低成本的DMO加氢制EtOH的催化剂提供参考。
Abstract
One significant route for producing ethanol (EtOH) indirectly from syngas is the hydrogenation of coal-based syngas to EtOH via dimethyl oxalate (DMO) intermediates. There are two reaction pathways for DMO hydrogenation to EtOH: hydrogenation to EtOH via ethylene glycol (EG) intermediates and hydrogenation to EtOH via methyl acetate (MA) intermediates. The characteristics of two reaction pathways for DMO hydrogenation to EtOH were analyzed, and the catalysts commonly utilized in these pathways and the key factors affecting selectivity of EtOH were summarized. DMO hydrogenation to EtOH via EG intermediates typically requires high reaction temperature and synergistic catalysis of multiple active sites. The catalytic activity of commonly used Cu-based catalysts can be regulated from three aspects: support structure, preparation method and additive addition. The reaction temperature of DMO hydrogenation to EtOH via MA intermediates is relatively low, and commonly used catalysts are mainly transition metal carbides (Mo-base and Fe-base), but the hydrogenation capacity of catalysts is still insufficient. It helps to deepen the systematic understanding of the two pathways for DMO hydrogenation to EtOH and provides reference for the rational design and preparation of highly stable and low-cost catalysts for DMO hydrogenation to EtOH in the future.
关键词
草酸二甲酯加氢乙醇反应路径合成气催化剂
Keywords
dimethyl oxalatehydrogenationethanolreaction pathwayssyngascatalysts
references
YUE H R, ZHAO Y J, ZHAO L, et al. Hydrogenation of dimethyl oxalate to ethylene glycol on a Cu/SiO2/cordierite monolithic catalyst: Enhanced internal mass transfer and stability [J]. AIChE Journal, 2012, 58(9): 2798-2809.
GOLDEMBERG J. Ethanol for a sustainable energy future [J]. Science, 2007, 315(5813): 808-810.
YIN A Y, WEN C, GUO X Y, et al. Influence of Ni species on the structural evolution of Cu/SiO2 catalyst for the chemoselective hydrogenation of dimethyl oxalate [J]. Journal of Catalysis, 2011, 280(1): 77-88.
SONG Y B, ZHANG J, LV J, et al. Hydrogenation of dimethyl oxalate over copper-based catalysts: Acid-base properties and reaction paths [J]. Industrial & Engineering Chemistry Research, 2015, 54(40): 9699-9707.
ABBAS M, ZHANG J, CHEN Z, et al. Sonochemical synthesis of Zn-promoted porous MgO-supported lamellar Cu catalysts for selective hydrogenation of dimethyl oxalate to ethanol and their long-term stability [J]. New Journal of Chemistry, 2018, 42(21): 17553-17562.
SUBRAMANI V, GANGWAL S K G. A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol [J]. Energy & Fuels, 2008, 22(2): 814-839.
贺佳. 草酸酯加氢合成乙醇金属碳化物催化剂的研究[D]. 天津: 天津大学, 2017.
HE J. Study on metal carbide catalysts for the hydrogenation of dimethyl oxalate to ethanol [D]. Tianjin: Tianjin University, 2017.
ZHU J, SUN W D, WANG S, et al. A Ni-foam-structured MoNi4-MoOx nanocomposite catalyst for hydrogenation of dimethyl oxalate to ethanol [J]. Chemical Communications, 2020, 56(5): 806-809.
ZHU Y F, KONG X, ZHU S, et al. Construction of Cu/ZrO2/Al2O3 composites for ethanol synthesis: Synergies of ternary sites for cascade reaction [J]. Applied Catalysis B: Environmental, 2015, 166: 551-559.
GREY R A, PEZ G P, WALLO A, et al. Homogeneous catalytic hydrogenation of carboxylic acid esters to alcohols [J]. Chemical Communications, 1980: 783-784.
HE Z, LIN H Q, HE P, et al. Effect of boric oxide doping on the stability and activity of a Cu/SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol [J]. Journal of Catalysis, 2011, 277(1): 54-63.
YIN A Y, GUO X Y, DAI W L, et al. High activity and selectivity of Ag/SiO2 catalyst for hydrogenation of dimethyl oxalate [J]. Chemical Communications, 2010, 46(24): 4348-4350.
XU Y X, KONG L X, HUANG H J, et al. Promotional effect of indium on Cu/SiO2 catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol [J]. Catalysis Science & Technology, 2021, 11(20): 6854-6865.
YE R P, LIN L, WANG L C, et al. Perspectives on the active sites and catalyst design for the hydrogenation of dimethyl oxalate [J]. ACS Catalysis, 2020, 10(8): 4465-4490.
YUE H R, MA X B, GONG J L. An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol [J]. Accounts of Chemical Research, 2014, 47(5): 1483-1492.
MA X B, CHI H W, YUE H R, et al. Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu-MCM-41 catalysts [J]. AIChE Journal, 2013, 59(7): 2530-2539.
YU X B, BURKHOLDER M, KARAKALOS S G, et al. Hydrogenation of dimethyl oxalate to ethylene glycol over Cu/KIT-6 catalysts [J]. Catalysis Science & Technology, 2021, 11(7): 2403-2413.
GONG J L, YUE H R, ZHAO Y J, et al. Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites [J]. Journal of the American Chemical Society, 2012, 134(34): 13922-13925.
YUE H R, ZHAO Y J, ZHAO S, et al. A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions [J]. Nature Communications, 2013, 4(1): 2339.
POLSHETTIWAR V, CHA D, ZHANG X X, et al. High-surface-area silica nanospheres (KCC-1) with a fibrous morphology [J]. Angewandte Chemie International Edition, 2010, 49(50): 9652-9656.
AI P P, JIN H Q, NIU J C, et al. Synergistic effect of urchin-like spherical Cu-based catalyst for enhanced dimethyl oxalate hydrogenation capacity [J]. Fuel, 2023, 333: 126330.
AI P P, TAN M H, ISHIKURO Y, et al. Design of an autoreduced copper in carbon nanotube catalyst to realize the precisely selective hydrogenation of dimethyl oxalate [J]. ChemCatChem, 2017, 9(6): 1067-1075.
ABBAS M, CHEN Z, CHEN J G. Shape-and size-controlled synthesis of Cu nanoparticles wrapped on RGO nanosheet catalyst and their outstanding stability and catalytic performance in the hydrogenation reaction of dimethyl oxalate [J]. Journal of Materials Chemistry A, 2018, 6(39): 19133-19142.
ZHU Y F, KONG X, LI X Q, et al. Cu nanoparticles inlaid mesoporous Al2O3 as a high-performance bifunctional catalyst for ethanol synthesis via dimethyl oxalate hydrogenation [J]. ACS Catalyis, 2014, 4(10): 3612-3620.
SHI J Z, HE Y, MA K, et al. Cu active sites confined in MgAl layered double hydroxide for hydrogenation of dimethyl oxalate to ethanol [J]. Catalysis Today, 2021, 365: 318-326.
GIORGIANNI G, MEBRAHTU C, PERATHONER S, et al. Hydrogenation of dimethyl oxalate to ethylene glycol on Cu/SiO2 catalysts prepared by a deposition-decomposition method: Optimization of the operating conditions and pre-reduction procedure [J]. Catalysis Today, 2022, 390: 343-353.
TOUPANCE T, KERMAREC M, LAMBERT J F, et al. Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption [J]. Journal of Physical Chemistry B, 2002, 106(9): 2277-2286.
ZHAO Y J, LI S M, WANG Y, et al. Efficient tuning of surface copper species of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J]. Chemical Engineering Journal, 2017, 313: 759-768.
ZHAO Y J, ZHAO S, GENG Y C, et al. Ni-containing Cu/SiO2 catalyst for the chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate [J]. Catalysis Today, 2016, 276: 28-35.
LI Z, LI Y H, WANG X P, et al. Hydrogenation of dimethyl oxalate to ethanol over Mo-doped Cu/SiO2 catalyst [J]. Chemical Engineering Journal, 2023, 454: 140001.
SHU G Q, MA K, TANG S Y, et al. Highly selective hydrogenation of diesters to ethylene glycol and ethanol on aluminum-promoted CuAl/SiO2 catalysts [J]. Catalysis Today, 2021, 368: 173-180.
AI P P, TAN M H, YAMANE N, et al. Synergistic effect of a boron‐doped carbon‐nanotube‐supported Cu catalyst for selective hydrogenation of dimethyl oxalate to ethanol [J]. Chemistry—A European Journal, 2017, 23(34): 8252-8261.
WANG M L, YAO D W, LI A T, et al. Enhanced selectivity and stability of Cu/SiO2 catalysts for dimethyl oxalate hydrogenation to ethylene glycol by using silane coupling agents for surface modification [J]. Industrial & Engineering Chemistry Research, 2020, 59(20): 9414-9422.
YANG D L, YE R P, LIN L, et al. Boron modified bifunctional Cu/SiO2 catalysts with enhanced metal dispersion and surface acid sites for selective hydrogenation of dimethyl oxalate to ethylene glycol and ethanol [J]. Nanomaterials, 2021, 11(12): 3236.
DING J, WANG M H, LIU H M, et al. Effect of Cu content on Ce-doping CuO/ZrO2 catalysts for low-temperature hydrogenation of dimethyl oxalate to ethanol [J]. Asia-Pacific Journal of Chemical Engineering, 2021, 16(5): e2692.
ABBAS M, ZHANG J, CHEN Z, et al. Sonochemical synthesis of Zn-promoted porous MgO-supported lamellar Cu catalysts for selective hydrogenation of dimethyl oxalate to ethanol and their long-term stability [J]. New Journal of Chemistry, 2018, 42(21): 17553-17562.
YIN A Y, GUO X Y, DAI W L, et al. High activity and selectivity of Ag/SiO2 catalyst for hydrogenation of dimethyl oxalate [J]. Chemical Communications, 2010, 46(24): 4348-4350.
OUYANG M, WANG J, PENG B, et al. Effect of Ti on Ag catalyst supported on spherical fibrous silica for partial hydrogenation of dimethyl oxalate [J]. Applied Surface Science, 2019, 466: 592-600.
CHEN H M, TAN J J, ZHU Y L, et al. An effective and stable Ni2P/TiO2 catalyst for the hydrogenation of dimethyl oxalate to methyl glycolate [J]. Catalysis Communications, 2016, 73: 46-49.
ZHU J, CAO L Q, LI C Y, et al. Nanoporous Ni3P evolutionarily structured onto a Ni foam for highly selective hydrogenation of dimethyl oxalate to methyl glycolate [J]. ACS Applied Materials & Interfaces, 2019, 11(41): 37635-37643.
LIU Y T, DING J, SUN J Q, et al. Molybdenum carbide as an efficient catalyst for low-temperature hydrogenation of dimethyl oxalate [J]. Chemical Communications, 2016, 52(28): 5030-5032.
LIU Y T, DING J, BI J C, et al. Effect of Cu-doping on the structure and performance of molybdenum carbide catalyst for low-temperature hydrogenation of dimethyl oxalate to ethanol [J]. Applied Catalysis A:General, 2017, 529: 143-155.
HE J, ZHAO Y J, WANG Y, et al. A Fe5C2 nanocatalyst for the preferential synthesis of ethanol via dimethyl oxalate hydrogenation [J]. Chemical Communications, 2017, 53(39): 5376-5379.
SUN Y N, MA Q X, GE Q J, et al. Tunable synthesis of ethanol or methyl acetate via dimethyl oxalate hydrogenation on confined iron catalysts [J]. ACS Catalysis, 2021, 11(8): 4908-4919.
ABBAS M, ZHANG J, CHEN J G. Sonochemical engineering of highly efficient and robust Au nanoparticle-wrapped on Fe/ZrO2 nanorods and their controllable product selectivity in dimethyl oxalate hydrogenation [J]. Catalysis Science & Technology, 2020, 10(4): 1125-1134.
CAO M, HUANG H J, ZHENG Y T, et al. Enhanced effect of the mesoporous carbon on iron carbide catalyst for hydrogenation of dimethyl oxalate to ethanol [J]. ChemCatChem, 2022, 14(20): e202200500.
0
Views
0
下载量
0
CSCD
- L-PDFDownload
- WORDDownload
- Meta-XMLDownload
- BibTeXDownload
- EndnoteDownload
- RefMan Download
- NoteExpressDownload
- NoteFirstDownload
Publicity Resources
Related Articles
Related Author
Related Institution
- Postal code：610225
- Tel：028-85964717 Email：dthxyhg@swchem.com
- Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10
蜀公网安备51012202001533 - It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
- Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
- Total Visits：48404 Visits Today：175
