Effect of the surface acid sites of tungsten trioxide for highly selective hydrogenation of cellulose to ethylene glycol

Li, Naixu; Ji, Zhongxiang; Wei, Lingfei; Zheng, Yu; Shen, Quanhao; Ma, Quanhong; Tan, Meng-Lu; Zhan, Mengmeng; Zhou, Jiancheng

doi:10.1016/j.biortech.2018.05.026

Cited by 28 publications

(16 citation statements)

References 49 publications

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“…Ni–W/AC and Ni–W/M showed similar broad desorption peaks, indicating acid-site heterogeneity, with the centers of the maximum desorption peaks located at ∼700 and ∼820 °C, respectively, representing strongly acidic sites. Surface acidity is considered to play a critical role in cellulose conversion processes because strong acidic sites are conducive to heterogeneous catalytic reactions, promote cellulose hydrolysis process, and availably increase the yield of EG. , The strong acid sites of Ni–W/M catalyst derive from polytungstate species on the catalyst surface . The acidity of these polytungstate species is stronger than that of WO 3 crystals, indicating that highly dispersed WO x clusters can produce more strong acid sites …”

Section: Resultsmentioning

confidence: 99%

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Enhanced Ni/W/Ti Catalyst Stability from Ti–O–W Linkage for Effective Conversion of Cellulose into Ethylene Glycol

Liu

Zhou

et al. 2020

ACS Sustainable Chem. Eng.

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Direct conversion of cellulose into ethylene glycol is a promising route for transforming sustainable biomass resources into high-value chemicals. Although numerous attempts have been made to exploit tungsten-based hydrogenolysis catalysts in the catalytic conversion of cellulose to ethylene glycol for high conversion rate and selectivity, maintaining catalyst stability remains challenging. Herein, we have developed a Ni−W/M catalyst with good catalytic performance and stability, which were obtained by calcining Ni−W/MIL-125(Ti) precursor. The synthesized catalyst showed good cellulose conversion rate (100%) and ethylene glycol yield (68.7%). The tungsten species was linked to the TiO 2 support by Ti−O−W bonds to reduce loss of the active tungsten component. The formation of new bonds enhanced the catalyst stability and durability, enabling the catalysts to retain high catalytic activity during recycling.

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Section: Resultsmentioning

confidence: 99%

“…12,58 The strong acid sites of Ni−W/M catalyst derive from polytungstate species on the catalyst surface. 59 The acidity of these polytungstate species is stronger than that of WO 3 crystals, indicating that highly dispersed WO x clusters can produce more strong acid sites. 60 Evaluation of Catalytic Performance.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Enhanced Ni/W/Ti Catalyst Stability from Ti–O–W Linkage for Effective Conversion of Cellulose into Ethylene Glycol

Liu

Zhou

et al. 2020

ACS Sustainable Chem. Eng.

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“…The authors determined that this kinetic analysis allows one to forecast the maximum selectivity ratio of PG to EG (2.5) with the maximum PG yield of ~ 71% (Table 1). Li et al synthesized Ru-containing catalysts based on WO 3 nanocrystals of different shapes: rectangular nanosheets (Li et al, 2017), hexagonal nanorods (h-WO 3 ), and monoclinic nanosheets (m-WO 3 ) (Li et al, 2018b). Detailed structural studies showed the crucial importance of surface LAS formed upon adsorption of water on the surface of WO 3 for cellulose conversion to EG.…”

Section: Cellulose Hydrogenolysismentioning

confidence: 99%

“…On one hand, it was demonstrated that the reactions of the glucose retro-aldol condensation to glycolaldehyde and its hydrogenation to EG occur independently on different catalytic sites, thus, their intimate contact is not needed (Wiesfeld et al, 2019). On the other hand, the interaction of WO 3 and metallic nanoparticles occurring at the electronic level leads to increase of the number of W 5+ active sites (Li et al, 2017, 2018b; Chu and Zhao, 2018), which selectively break the C2-C3 bond in glucose (Chai et al, 2017). These data demonstrate the necessity of close contact between acidic and metallic sites.…”

Section: Cellulose Hydrogenolysismentioning

confidence: 99%

“…Cellulose is a natural polymer consisting of glucose repeating units and is the most promising alternative for syntheses of value-added chemicals to replace non-renewable resources such as gas and oil (Li et al, 2015b, 2018a). Currently, there are numerous methods for direct catalytic conversion of cellulose to a number of valuable chemicals such as glucose (Shrotri et al, 2016, 2018), hexitols (Li et al, 2015a; Zada et al, 2017; Shrotri et al, 2018), glycols (Li et al, 2015a; Zheng et al, 2017), 5-hydroxymethylfurfural (Li et al, 2018b), methane (Wang et al, 2018), hydrogen (Wen et al, 2010), hexane and hexanols (Liu et al, 2014, 2015; Op De Beeck et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

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Cellulose Conversion Into Hexitols and Glycols in Water: Recent Advances in Catalyst Development

et al. 2019

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Conversion of biomass cellulose to value-added chemicals and fuels is one of the most important advances of green chemistry stimulated by needs of industry. Here we discuss modern trends in the development of catalysts for two processes of cellulose conversion: (i) hydrolytic hydrogenation with the formation of hexitols and (ii) hydrogenolysis, leading to glycols. The promising strategies include the use of subcritical water which facilitates hydrolysis, bifunctional catalysts which catalyze not only hydrogenation, but also hydrolysis, retro-aldol condensation, and isomerization, and pretreatment (milling) of cellulose together with catalysts to allow an intimate contact between the reaction components. An important development is the replacement of noble metals in the catalysts with earth-abundant metals, bringing down the catalyst costs, and improving the environmental impact.

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Do not forget the classical catalyst poisons: The case of biomass to glycols via catalytic hydrogenolysis

Molder

Kersten

Lange

et al. 2022

Biofuels Bioprod Bioref

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The conversion of herbaceous biomass to glycols via tungstate catalyzed hydrogenolysis is challenging owing to its high content of extractives, inorganics and S/N, compared with woody biomass. We tested the hydrogenolysis performance of hay in batch autoclave experiments in the presence of soluble sodium polytungstate and Raney Ni at 245°C, both in excess of catalyst as well as under catalyst‐starving conditions. By this method, we found that additional tungstate and Raney Ni poisons, or at least their much higher concentrations, are present in the hay feedstock compared with woody biomass. It turns out that N‐ and in particular S‐containing components present in hay are the root cause for deactivation of the hydrogenation catalyst. From the experimental data we have derived feedstock criteria for N and S that should be targeted in terms of catalyst consumption for operation in an industrially relevant window. These challenging criteria urge the development of effective pretreatments for S/N removal or the employment of S/N‐tolerant catalysts in the field of catalytic biomass conversion. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Effect of the surface acid sites of tungsten trioxide for highly selective hydrogenation of cellulose to ethylene glycol

Cited by 28 publications

References 49 publications

Enhanced Ni/W/Ti Catalyst Stability from Ti–O–W Linkage for Effective Conversion of Cellulose into Ethylene Glycol

Enhanced Ni/W/Ti Catalyst Stability from Ti–O–W Linkage for Effective Conversion of Cellulose into Ethylene Glycol

Cellulose Conversion Into Hexitols and Glycols in Water: Recent Advances in Catalyst Development

Do not forget the classical catalyst poisons: The case of biomass to glycols via catalytic hydrogenolysis

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