Selective hydrogenolysis of glycerol to 1,2-propanediol on the modified ultrastable Y-type zeolite dispersed copper catalyst

Niu, Lei; Wei, Ruiping; Jiang, Feng; Zhou, Minghao; Liu, Chuanying; Xiao, Guomin

doi:10.1007/s11144-014-0745-8

Cited by 11 publications

(20 citation statements)

References 26 publications

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“…In this situation, biodiesel industry has achieved rapid development, giving a rise to the excessive supply of glycerol as the main byproduct in biodiesel production process and making glycerol a cheap raw material in the chemical 45 market. Therefore, extensive studies on the conversion of glycerol to more valuable chemicals have been carried out for the last several years [1][2][3][4][5] . However, most of the studies focus on the reaction of glycerol hydrogenation and dehydration, and few on the transformation of glycerol to aromatics.…”

Section: Introductionmentioning

confidence: 99%

Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol

2015

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A series of hierarchical HZSM-5 zeolites were prepared by post-synthesis modification of conventional bulk crystals of HZSM-5 zeolite with NaOH solution at different concentrations. These micro-mesoporous composite molecular sieves were characterized by powder Xray diffraction (XRD), Transmission electron microscopy (TEM), N 2 adsorption, Fourier transform infrared (FT-IR) spectroscopy techniques and pyridine FT-IR to investigate the changes in crystallinity, acidity, morphology and textural property of HZSM-5 zeolite 10 before and after alkaline treatment. The catalytic performances of these hierarchical HZSM-5 zeolites were evaluated by the aromatization of glycerol with methanol as the solvent, which was a promising route to convert renewable glycerol and methanol into high valuable aromatics. Substantial mesoporosity with sizes centered at around 4 nm could be generated for HZSM-5 zeolites after treated by mild NaOH solution (≤0.4 M), coupled with better retained microporosity, resulting in great improvements in catalytic life time and selectivity to BTX aromatics during the reaction of glycerol to aromatics. Though the larger mesopore surface areas were 15 achieved when treated NaOH concentrations were higher than 0.5 M, the HZSM-5 structure was partly damaged, leading to the reduction of catalytic life time and selectivity to BTX aromatics. The HZSM-5 treated with 0.3 M NaOH solution was found as the optimum catalyst for the transformation of glycerol/methanol to aromatics, producing nearly twofold increase in BTX aromatics (carbon yields of 25.18%) and threefold improvement in catalyst life time (12.5 h) than the parent microporous HZSM-5 (13.9% carbon yields of BTX aromatics and 4h). These improved catalytic performances are mainly attributed to the optimized bimodal micro-mesoporous HZSM-5 20 zeolite during the alkali treatment, which retained sufficient micropores that have the capacity of aromatization while created more mesopores that could shorten the average diffusion path lengths, increase the accessibility to the acid sites and facilitate the transportation of large molecular (e.g. glycerol and carbon precursors) during the aromatization of glycerol.

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Section: Introductionmentioning

confidence: 99%

Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol

2015

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“…Dehydration of glycerol to acetol occurs in weak acid sites of alumina, which are considered as Lewis acid sites. Once acetol is formed, hydrogenation takes place on metal active sites (Cu) to yield 1,2-PDO [24]. Zheng et al [22] reported that the presence of Cu 0 in the catalyst is responsible for its high activity and selectivity to 1,2-PDO.…”

Section: Glycerol Hydrogenolysismentioning

confidence: 99%

“…Sato et al [38] stated that alumina-supported copper catalysts boost glycerol dehydration to acetol and further hydrogenation to 1,2-PDO, which is catalyzed by Cu 0 . Niu et al [24] concluded that glycerol dehydration takes place in weak acid sites. Then, 1,2-PDO is formed from hydrogenation of acetol that is carried out in metal sites (Cu 0 ).…”

Section: Glycerol Hydrogenolysismentioning

confidence: 99%

“…Niu et al [24] also proposed that in presence of mild or/and strong acid sites, dehydration of glycerol leads to 3-hydroxypropionaldehyde as intermediate. The hydrogenolysis of glycerol on Cu-based catalysts possesses the same characteristics of a bifunctional catalytic mechanism [26].…”

Section: Glycerol Hydrogenolysismentioning

confidence: 99%

“…It is currently accepted that Cu-based catalysts enhance the hydrogenation activity for the double bond of C=O [23]. Dealuminated ultrastable Y-type zeolite supported copper catalysts enhanced a glycerol conversion of 78 % with 98 % of selectivity to 1,2-PDO [24]. Cu/ZnO-USY catalysts have been used in the glycerol hydrogenolysis with a glycerol conversion of 95 % [25].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of 1,2-propanediol through glycerol hydrogenolysis on Cu–Al mixed oxides

Valencia

Tirado

Sotelo

et al. 2015

Reac Kinet Mech Cat

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Cu-Al mixed oxides derived from hydrotalcite-like precursors having an atomic ratio of 3:1 and calcined at 300, 400, and 500°C were synthesized. The samples were further reduced under hydrogen atmosphere and its catalytic activity was tested in glycerol hydrogenolysis in a batch reactor. Several techniques such as N 2 physisorption, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy were used in order to characterize the synthesized mixed oxides. The most active catalyst in the glycerol hydrogenolysis was that calcined at 500°C. Reaction variables were analyzed in order to determine their influence on glycerol hydrogenolysis.

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Cu/ZnO-USY: an efficient bifunctional catalyst for the hydrogenolysis of glycerol

Niu

Wei

Liu

et al. 2015

Reac Kinet Mech Cat

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Selective hydrogenolysis of glycerol to 1,2-propanediol on the modified ultrastable Y-type zeolite dispersed copper catalyst

Cited by 11 publications

References 26 publications

Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol

Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol

Synthesis of 1,2-propanediol through glycerol hydrogenolysis on Cu–Al mixed oxides

Cu/ZnO-USY: an efficient bifunctional catalyst for the hydrogenolysis of glycerol

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