Mediatory role of K, Cu and Mo over Ru/SiO2 catalysts for glycerol hydrogenolysis

Liao, Xiaoyuan; Li, Kewen; Xiang, Xiaomin; Wang, Shengguang; She, Xuegong; Zhu, Yulei; Li, Yongwang

doi:10.1016/j.jiec.2011.10.004

Cited by 23 publications

(8 citation statements)

References 12 publications

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“…According to the bibliography, the oxophilicity of W enhances the direct hydrogenolysis mechanism through a triple-action: (1) it acts as a strong anchoring site for the terminal OH group/s of glycerol forming a terminal alkoxide, (2) it provides the necessary Brönsted acid sites to protonate the internal OH group of glycerol, and (3) it stabilizes the secondary carbocation formed, avoiding the degradation of the 1,3-PDO product [12,60]. Nevertheless, although the Mo based system could also be susceptible to performing this triple effect, results observed are far from those obtained for W. In this sense, Liao et al [61] described that the presence of Mo in the Ru catalyst can reduce the metal function activity. Assuming that something similar may occur with our catalyst, the dehydration-hydrogenation mechanism would be favored instead of direct hydrogenolysis, thus leading to 1,2-PDO as the main reaction product.…”

Section: Resultsmentioning

confidence: 99%

Influence of Boron, Tungsten and Molybdenum Modifiers on Zirconia Based Pt Catalyst for Glycerol Valorization

et al. 2019

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The influence of boron, tungsten and molybdenum modifiers on zirconia-based Pt catalyst was studied for glycerol valorization. Zirconia modified supports were prepared by impregnation of ZrO2 with either boric, silicontungstic or phosphomolybdic acids to obtain supports with enhanced Brönsted acidic properties. The modified supports were subsequently impregnated with chloroplatinic acid to obtain Pt-based catalysts. Pt incorporation resulted in the increase in Lewis acidity of the solids, being more significant for the Pt//W/ZrO2 catalyst. Reduced Pt catalysts were tested for the liquid-phase glycerol hydrogenolysis, observing a synergistic effect between catalyst acid sites and metal function that proved to be crucial in glycerol hydrogenolysis. The Pt//W/ZrO2 catalyst was the most active catalyst in this reaction, being the only leading to 1,3-PDO (45% sel., 160 °C) while Pt//Mo/ZrO2 is the best option for 1,2-PDO (49% sel., 180 °C). Reusability studies carried out for Pt//W/ZrO2 showed that catalytic activity dropped after the first use, remaining constant for the second and subsequent ones. Selectivity to reaction products also changes during reuses. Therefore, the selectivity to 1,2 PDO increases in the first reuse in detriment to the selectivity to n-propanol whereas the selectivity to 1,3-PDO remains constant along the uses. This behavior could be associated to the lixiviation of W species and/or catalyst fouling during reaction runs.

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Section: Resultsmentioning

confidence: 99%

Influence of Boron, Tungsten and Molybdenum Modifiers on Zirconia Based Pt Catalyst for Glycerol Valorization

et al. 2019

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“…In order to make glycerol hydrogenolysis processes more efficient and economical, a variety of efforts have been made in developing flow reactors (30)(31)(32)(33)(34)(35). It is obvious that the production of PG in a continuous-flow reactor using heterogeneous catalysts is advantageous as the process has advantages of both high heat and mass transfer efficiency, ease of scale-up from laboratory to industrial scale, and high surface to volume ratios (36).…”

Section: Development In Reaction Processesmentioning

confidence: 99%

Recent advancements in catalytic conversion of glycerol into propylene glycol: A review

et al. 2016

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The renewability of bio-glycerol has made it an attractive platform for the production of diverse compounds. Selective hydrogenolysis of glycerol to propylene glycol (PG) is one of the most promising routes for glycerol valorization, since this compound is an important chemical intermediate in a number of applications. In this article, advancements in the catalytic conversion of glycerol into propylene glycol are reviewed, which include advances in process development, effects of preparation and activation methods on catalytic activity and stability, and the performance of various types of catalysts. The feasibility of using bio-hydrogen and the challenges of utilizing crude glycerol for glycerol hydrogenolysis are also discussed. ARTICLE HISTORY

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“…The production of lower alcohols is of industrial interest since ethanol is a renewable fuel and fuel additive, and methanol and 1-propanol are used as solvents in the paint and cosmetic industries . 1,2-Propanediol (1,2-PDO) and ethylene glycol (EG) which are also formed during this process have an important use as antifreeze liquids and additives in liquid detergent. − One of the processes that has potential in obtaining these lower alcohols from glycerol is hydrogenolysis. − Platinum group metals are the most effective catalysts in hydrogenolysis; − however, they are very expensive and can only be used in small amounts. Therefore, the use of metals such as molybdenum and tungsten could provide a cost-effective hydrogenolysis process.…”

Section: Introductionmentioning

confidence: 99%

“…Supported molybdenum catalysts in the hydrogenolysis of glycerol have also been reported. ,,, Koso et al reported a Rh-MoO x /SiO 2 catalyst of hydrogen pressure at 8.0 MPa and a reaction temperature of 393 K, to give 1,3-PDO, 1,2-PDO, 1-propanol, and 2-propanol, with the selectivity to 1,2-PDO being the highest at 41%. Liao et al, on the other hand, used Mo as a modifier for Ru/SiO 2 catalysts in the hydrogenolysis of glycerol.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrogenolysis of Glycerol to Monoalcohols over Supported Mo and W Catalysts

Shozi

Dasireddy

Singh

et al. 2016

ACS Sustainable Chem. Eng.

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MoO3 and WO3 were supported on γ-Al2O3 and SiO2 with nominal loadings of 10 wt % via wet impregnation. The catalysts were characterized using XRD, TPR, Pulse TPD, Raman, TEM, and BET surface area. The alumina supported catalysts were found to contain higher Brønsted acidity compared to those supported on silica. These catalysts were evaluated in the hydrogenolysis of glycerol in a continuous flow fixed bed reactor in a temperature range of 250−325 °C and a H2 pressure of 60 bar. All catalysts were active, with activity increasing with temperature as well as Brønsted acidity. The selectivity to ethylene glycol and 1,2-propanediol decreased with increase in temperature. In parallel, the selectivity to lower alcohols such as methanol, ethanol, 2-propanol, and 1-propanol increased with temperature as the ethylene glycol and 1,2propanediol reacted further to these products due to C−C bond cleavage. The total selectivity to lower alcohols was 34.6, 64.8, 70.6, and 54.6% over Mo/Al2O3, Mo/SiO2, W/Al2O3, and W/SiO2 respectively. The total selectivity to lower alcohols increased to 73.6, 72.8, 85.3, and 66.1% over Mo/Al2O3, Mo/SiO2, W/Al2O3, and W/SiO2 respectively when the H2:glycerol ratio was doubled.

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Mediatory role of K, Cu and Mo over Ru/SiO2 catalysts for glycerol hydrogenolysis

Cited by 23 publications

References 12 publications

Influence of Boron, Tungsten and Molybdenum Modifiers on Zirconia Based Pt Catalyst for Glycerol Valorization

Influence of Boron, Tungsten and Molybdenum Modifiers on Zirconia Based Pt Catalyst for Glycerol Valorization

Recent advancements in catalytic conversion of glycerol into propylene glycol: A review

Hydrogenolysis of Glycerol to Monoalcohols over Supported Mo and W Catalysts

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