Verification of propylene glycol preparation from glycerol via the acetol pathway by<i>in situ</i>hydrogenolysis

Maglinao, Randy L.; He, B. Brian

doi:10.4155/bfs.12.65

Cited by 13 publications

(17 citation statements)

References 13 publications

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“…This could also explain the decline in glucose selectivity. On further increasing the Ru loading to 12%, the 1,2-PG and glycerol selectivity decrease may be caused by two reasons: the direct hydrogenation of glucose to sorbitol, which was consistent with the observed increase in sorbitol selectivity, and excessive Ru causing further hydrogenolysis of 1,2-PG to ethanol, methanol, and methane. , …”

Section: Resultssupporting

confidence: 73%

“…On further increasing the Ru loading to 12%, the 1,2-PG and glycerol selectivity decrease may be caused by two reasons: the direct hydrogenation of glucose to sorbitol, which was consistent with the observed increase in sorbitol selectivity, and excessive Ru causing further hydrogenolysis of 1,2-PG to ethanol, methanol, and methane. 42,43 After demonstrating that the Fe 3 O 4 @SiO 2 /10%Ru-20%WO x catalyst was highly selective toward 1,2-PG in the conversion of cellulose, we further investigated the effect of reaction temperature and time on the selectivity for 1,2-PG. The dependence of the hydrogenolysis of the cellulose reaction on temperature is presented in Figure S8.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Magnetically Recoverable Bifunctional Catalysts for the Conversion of Cellulose to 1,2-Propylene Glycol

Xin

Yin

et al. 2020

ACS Sustainable Chem. Eng.

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The use of cellulose instead of oil to produce 1,2-propylene glycol (1,2-PG) is of great significance for building a sustainable world. Herein, we synthesize Fe3O4@SiO2/Ru-WO x core–shell magnetically recoverable catalysts containing both Lewis acid and metal active sites using well-shaped Fe3O4@SiO2 core–shell magnetic nanospheres as the substrate. We investigated the catalytic performances of the bimetallic catalysts with various metals as well as different metal contents and WO x loadings for the conversion of cellulose to 1,2-PG. The results showed that Fe3O4@SiO2/10%Ru-20%WO x was more favorable for 1,2-PG production, with a 1,2-PG selectivity of 32.4% and a cellulose conversion of 96.8%. Our characterization and activity tests suggested that WO x on the Fe3O4@SiO2 nanospheres produced abundant Lewis acid sites to effectively promote glucose isomerization to fructose before glucose undergoes the retro-aldol condensation reaction. Moreover, the Ru further hydrogenated the C3 intermediate to 1,2-PG. It was notable that the catalyst can be separated through a simple magnetic separation after the end of the reaction, and it still maintained high catalytic activity after 5 uses.

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Section: Resultssupporting

confidence: 73%

Section: ■ Results and Discussionmentioning

confidence: 99%

Magnetically Recoverable Bifunctional Catalysts for the Conversion of Cellulose to 1,2-Propylene Glycol

Xin

Yin

et al. 2020

ACS Sustainable Chem. Eng.

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“…Figure shows the flowsheet of the process. In the simulation, we implement the reaction mechanism presented by Maglinao et al, , where methanol, ethanol and propanol are generated as byproducts. The reaction takes place at 240 °C and 20 bar using a glycerol solution 50 wt %.…”

Section: Process Descriptionmentioning

confidence: 99%

“…Over the past decade, different studies have analyzed the production of PG from renewable sources such as glycerol, sorbitol or biomass. ,, Among these options, catalytic hydrogenolysis of glycerol to PG has been put forward as a sustainable production route and studied under several operating conditions. Some of the alternatives evaluated include systems at high or atmospheric pressure, ,, isothermal or nonisothermal conditions, ,− external or in situ generated hydrogen − and liquid or vapor phase reactions. − However, little focus has been placed on the design and evaluation of the process at an industrial level, which plays a crucial role in the development of a feasible bioeconomy in terms of economic, environmental and social impacts.…”

Section: Introductionmentioning

confidence: 99%

High-Value Propylene Glycol from Low-Value Biodiesel Glycerol: A Techno-Economic and Environmental Assessment under Uncertainty

González-Garay¹,

González‐Miquel

Guillén‐Gosálbez³

2017

ACS Sustainable Chem. Eng.

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Recent governmental policies that promote a biobased economy have led to an increasing production of biodiesel, resulting in large amounts of waste glycerol being generated as low-cost and readily available feedstock. Here, the production of high-value biobased propylene glycol as an alternative chemical route to valorize biodiesel glycerol was studied and assessed considering economic and life cycle environmental criteria. To this end, the conventional industrial process for propylene glycol production, which uses petroleum-based propylene oxide as feedstock, was compared against three different hydrogenolysis routes based on biodiesel glycerol using process modeling and optimization tools. The environmental impact of each alternative was evaluated following Life Cycle Assessment principles, whereas the main uncertainties were explicitly accounted for via stochastic modeling. Comparison among the various cases reveals that there are process alternatives based on biodiesel glycerol that outperform the current propylene glycol production scheme simultaneously in profit and environmental impact (i.e., 90% increment in profit and 74% reduction in environmental impact under optimum process conditions). Overall, this work demonstrates the viability to develop sustainable biorefinery schemes that convert waste glycerol into high-value commodity chemicals, like propylene glycol, thereby promoting holistic bioeconomy frameworks.

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“…This hydrogen generated in situ could be used for the hydrogenation of acetol to form propylene glycol in metal sites. Furthermore, ethanol can be produced from the propylene glycol hydrogenolysis [ 80 , 83 ] whereas acrolein may form by excessive dehydration of glycerol [ 84 , 85 ].…”

Section: Resultsmentioning

confidence: 99%

The Effect of Ni Addition onto a Cu-Based Ternary Support on the H2 Production over Glycerol Steam Reforming Reaction

et al. 2018

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In the present study, Ni/Ce-Sm-xCu (x = 5, 7, 10 at.%) catalysts were prepared using microwave radiation coupled with sol-gel and followed by wetness impregnation method for the Ni incorporation. Highly dispersed nanocrystallites of CuO and NiO on the Ce-Sm-Cu support were found. Increase of Cu content seems to facilitate the reducibility of the catalyst according to the H2 temperature-programmed reduction (H2-TPR). All the catalysts had a variety of weak, medium and strong acid/basic sites that regulate the reaction products. All the catalysts had very high XC3H8O3 for the entire temperature (400–750 °C) range; from ≈84% at 400 °C to ≈94% at 750 °C. Ni/Ce-Sm-10Cu catalyst showed the lowest XC3H8O3-gas implying the Cu content has a detrimental effect on performance, especially between 450–650 °C. In terms of H2 selectivity (SH2) and H2 yield (YH2), both appeared to vary in the following order: Ni/Ce-Sm-10Cu > Ni/Ce-Sm-7Cu > Ni/Ce-Sm-5Cu, demonstrating the high impact of Cu content. Following stability tests, all the catalysts accumulated high amounts of carbon, following the order Ni/Ce-Sm-5Cu < Ni/Ce-Sm-7Cu < Ni/Ce-Sm-10Cu (52, 65 and 79 wt.%, respectively) based on the thermogravimetric analysis (TGA) studies. Raman studies showed that the incorporation of Cu in the support matrix controls the extent of carbon graphitization deposited during the reaction at hand.

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Verification of propylene glycol preparation from glycerol via the acetol pathway byin situhydrogenolysis

Cited by 13 publications

References 13 publications

Magnetically Recoverable Bifunctional Catalysts for the Conversion of Cellulose to 1,2-Propylene Glycol

Magnetically Recoverable Bifunctional Catalysts for the Conversion of Cellulose to 1,2-Propylene Glycol

High-Value Propylene Glycol from Low-Value Biodiesel Glycerol: A Techno-Economic and Environmental Assessment under Uncertainty

The Effect of Ni Addition onto a Cu-Based Ternary Support on the H2 Production over Glycerol Steam Reforming Reaction

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