Solid phosphoric acid catalysts based on mesoporous silica for levoglucosenone production <i>via</i> cellulose fast pyrolysis

Santander, José Anibal; Álvarez, Mariana; Gutierrez, Victoria; Volpe, María Alicia

doi:10.1002/jctb.5795

Cited by 18 publications

(11 citation statements)

References 49 publications

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“…The resulting P-zeosils are related compositionally to amorphous H 3 PO 4 -modified silicas, known as “solid phosphoric acids” (SPAs). Since the 1930s, the SPAs have been used commercially in large-scale catalytic processes such as propene oligomerization and benzene alkylation. − Recently, an SPA was also reported to steer the fast pyrolysis of cellulose toward levoglucosenone. , The active sites in SPAs are thought to be free phosphoric acid oligomers, whose proximity to the silica surface shifts the oligomerization equilibria and alters the catalytic activity. Introducing phosphorus also changes the acidity of crystalline aluminosilicates, − and is widely used to improve zeolite stability under hydrothermal reaction conditions .…”

Section: Introductionmentioning

confidence: 99%

“…4−6 Recently, an SPA was also reported to steer the fast pyrolysis of cellulose toward levoglucosenone. 7,8 The active sites in SPAs are thought to be free phosphoric acid oligomers, whose proximity to the silica surface shifts the oligomerization equilibria and alters the catalytic activity. Introducing phosphorus also changes the acidity of crystalline aluminosilicates, 9−12 and is widely used to improve zeolite stability under hydrothermal reaction conditions.…”

Section: ■ Introductionmentioning

confidence: 99%

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P-Site Structural Diversity and Evolution in a Zeosil Catalyst

Jain

Tabassum

et al. 2021

J. Am. Chem. Soc.

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Phosphorus-modified siliceous zeolites, or P-zeosils, catalyze the selective dehydration of biomass derivatives to platform chemicals such as p-xylene and 1,3-butadiene. Water generated during these reactions is a critical factor in catalytic activity, but the effects of hydrolysis on the structure, acidity, and distribution of the active sites are largely unknown. In this study, the Psites in an all-silica self-pillared pentasil (P-SPP) with a low P-loading (Si/P = 27) were identified by solid-state 31 P NMR using frequency-selective detection. This technique resolves overlapping signals for P-sites that are covalently bound to the solid phase, as well as oligomers confined in the zeolite but not attached to the zeolite. Dynamic Nuclear Polarization provides the sensitivity necessary to conduct 29 Si-filtered 31 P detection and 31 P− 31 P correlation experiments. The aforementioned techniques allow us to distinguish sites with P−O−Si linkages from those with P−O− P linkages. The spectra reveal a previously unappreciated diversity of P-sites, including evidence for surface-bound oligomers. In the dry P-zeosil, essentially all P-sites are anchored to the solid phase, including mononuclear sites and dinuclear sites containing the [Si−O−P−O−P−O−Si] motif. The fully-condensed sites evolve rapidly when exposed to humidity, even at room temperature. Partially hydrolyzed species have a wide range of acidities, inferred from their calculated LUMO energies. Initial cleavage of some P− O−Si linkages results in an evolving mixture of surface-bound mono-and oligonuclear P-sites with increased acidity. Subsequent P− O−P cleavage leads to a decrease in acidity as the P-sites are eventually converted to H 3 PO 4 . The ability to identify acidic sites in Pzeosils and to describe their structure and stability will play an important role in controlling the activity of microporous catalysts by regulating their water content.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

P-Site Structural Diversity and Evolution in a Zeosil Catalyst

Jain

Tabassum

et al. 2021

J. Am. Chem. Soc.

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“…An optimal concentration of sulfuric acid can also be used in lieu of phosphoric acid to improve the yield of levoglucosenone . Solid phosphoric acid, solid acid catalysts, sulfated zirconia, sulfated titania, and other metal oxides are some candidates that can be used for boosting the yield of levoglucosenone through catalytic fast pyrolysis . Further, ionic liquids, and polar aprotic solvents facilitate higher conversion of cellulose to levoglucosenone at optimal temperature, reaction time, and catalyst‐to‐feedstock ratio …”

Section: Platform Chemicals From Cellulose: Potential Targets Of Pyromentioning

confidence: 99%

“…40 Solid phosphoric acid, solid acid catalysts, sulfated zirconia, sulfated titania, and other metal oxides are some candidates that can be used for boosting the yield of levoglucosenone through catalytic fast pyrolysis. 123,44,87,[124][125][126] Further, ionic liquids, and polar aprotic solvents facilitate higher conversion of cellulose to levoglucosenone at optimal temperature, reaction time, and catalyst-to-feedstock ratio. 41,42,57,127 Hydrogenated levoglucosenone (dihydrolevoglucosenone, Cyrene™) is a novel bio-based solvent that has the potential to replace N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and sulfolane.…”

Section: Levoglucosenonementioning

confidence: 99%

Cellulose fast pyrolysis for platform chemicals: assessment of potential targets and suitable reactor technology

Parihar

Bhattacharya

2019

Biofuels Bioprod Bioref

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The cellulosic component of lignocellulosic biomass can be converted to commercially valuable platform chemicals through pyrolysis provided it is effectively controlled and optimized. This review first discusses the underpinning kinetics and mechanism of cellulose pyrolysis to identify target platform chemicals. Platform chemicals like 5‐hydroxymethyl furfural, 5‐chloromethyl furfural, and levoglucosenone, which are potentially amenable to the pyrolytic conversion of cellulose, are then elucidated. There are laboratory and large‐scale reactor technologies available for converting biomass to bio‐oil but they have not been comprehensively investigated for producing platform chemicals through pyrolysis. This review critically evaluates different reactor types available for developing the catalytic pyrolysis process for converting cellulosic component of biomass to platform chemicals. The fluidized bed reactor stands out as the most suitable reactor technology for the catalytic pyrolysis of cellulose to platform chemicals owing to attributes like short residence time, high heating rate, uniform mixing, efficient heat transfer, and scalability of operations. This article provides perspective on the implementation of this technology for the pyrolysis of the cellulosic component of biomass to platform chemicals. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd

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“…Cellulose contains numerous intramolecular and intermolecular hydrogen bonds in the structure, which severely hinders cellulose hydrolysis . Thus, many types of catalyst, including liquid acid, enzyme, solid acid, porous carbon, metal‐organic frameworks, H‐zeolite, and silica/carbon nanocomposites, have been employed to hydrolyze cellulose. Compared with the heterogeneous solid acid catalyst, the homogeneous catalyst has several shortcomings, such as equipment corrosion, the extra acid waste, environmental pollution, and complex and difficult separation process despite its high hydrolysis efficiency.…”

Section: Introductionmentioning

confidence: 99%

Catalytic hydrolysis of cellulose to total reducing sugars with superior recyclable magnetic multifunctional MCMB‐based solid acid as a catalyst

Shi

Zhang

et al. 2019

J of Chemical Tech & Biotech

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BACKGROUND: Effective cellulose hydrolysis has a huge potential for producing high value-added biomass-based platform chemicals, such as glucose, hydroxymethylfurfural, levulinic acid, and total reducing sugars (TRS). Particularly, a magnetic multifunctional solid acid catalyst (Fe 3 O 4 /Cl-MCMB-SO 3 H) was synthesized by loading the active groups on the magnetic mesocarbon microbead (MCMB) derived from the co-calcination of coal tar pitch and ferroferric oxide, which was applied as a catalyst in the conversion of cellulose into TRS. RESULTS: Given the superior properties of MCMB, a novel magnetic MCMB-based solid acid with cellulose-binding domain (-Cl group) and catalytic domain (-SO 3 H group) was successfully prepared. Results indicated that this catalyst exhibited superior catalytic activity, recyclability and regenerability, and easy separation from the reactant. The acidic densities of -SO 3 H and -Cl in Fe 3 O 4 /Cl-MCMB-SO 3 H reached 1.77 and 1.32 mmol/g, respectively. The 68.6% TRS yield can be obtained from cellulose at 140 ∘ C for 3 h in distilled water by using Fe 3 O 4 /Cl-MCMB-SO 3 H as the catalyst.The TRS yield still reached 61.1% after the catalyst was used six times. Importantly, through catalyst regeneration, the -SO 3 H density and TRS yield still reached 1.69 mmol/g and 67.3%, indicating that the catalyst exhibited excellent regenerability. CONCLUSION: Such multifunctional magnetic catalyst would be a promising catalyst in the conversion of cellulose into biofuels, which was attributed to the efficient catalytic performance, magnetism, and excellent recyclability and regenerability.

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Solid phosphoric acid catalysts based on mesoporous silica for levoglucosenone production via cellulose fast pyrolysis

Cited by 18 publications

References 49 publications

P-Site Structural Diversity and Evolution in a Zeosil Catalyst

P-Site Structural Diversity and Evolution in a Zeosil Catalyst

Cellulose fast pyrolysis for platform chemicals: assessment of potential targets and suitable reactor technology

Catalytic hydrolysis of cellulose to total reducing sugars with superior recyclable magnetic multifunctional MCMB‐based solid acid as a catalyst

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