Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review

Liu, Bin; Gao, Feng

doi:10.3390/catal8020044

Cited by 29 publications

(25 citation statements)

References 125 publications

(192 reference statements)

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“…However, to the best of our knowledge, there is still a lack of mechanistic modeling on the detailed picture of how H 2 transfers from alcohols/acids to bioderived polyols, carboxylic acids, and aldehydes on two different sites. Computational studies on critical steps for C−H and C−O bond cleavage of polyols and carboxylic acids indicate that preventing substrate decomposition might be key to improving hydrogenation selectivity . Dehydrogenation, on the other hand, seems to be kinetically more favorable than the hydrogenation.…”

Section: Classification Of Cth Processesmentioning

confidence: 99%

Catalytic Transfer Hydrogenation of Biomass‐Derived Substrates to Value‐Added Chemicals on Dual‐Function Catalysts: Opportunities and Challenges

et al. 2018

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Aqueous‐phase hydrodeoxygenation (APH) of bioderived feedstocks into useful chemical building blocks is one the most important processes for biomass conversion. However, several technological challenges, such as elevated reaction temperature (220–280 °C), high H2 pressure (4–10 MPa), uncontrollable side reactions, and intensive capital investment, have resulted in a bottleneck for the further development of existing APH processes. Catalytic transfer hydrogenation (CTH) under much milder conditions with non‐fossil‐based H2 has attracted extensive interest as a result of several advantageous features, including high atom efficiency (≈100 %), low energy intensity, and green H2 obtained from renewable sources. Typically, CTH can be categorized as internal H2 transfer (sacrificing small amounts of feedstocks for H2 generation) and external H2 transfer from H2 donors (e.g., alcohols, formic acid). Although the last decade has witnessed a few successful applications of conventional APH technologies, CTH is still relatively new for biomass conversion. Very limited attempts have been made in both academia and industry. Understanding the fundamentals for precise control of catalyst structures is key for tunable dual functionality to combine simultaneous H2 generation and hydrogenation. Therefore, this Review focuses on the rational design of dual‐functionalized catalysts for synchronous H2 generation and hydrogenation of bio‐feedstocks into value‐added chemicals through CTH technologies. Most recent studies, published from 2015 to 2018, on the transformation of selected model compounds, including glycerol, xylitol, sorbitol, levulinic acid, hydroxymethylfurfural, furfural, cresol, phenol, and guaiacol, are critically reviewed herein. The relationship between the nanostructures of heterogeneous catalysts and the catalytic activity and selectivity for C−O, C−H, C−C, and O−H bond cleavage are discussed to provide insights into future designs for the atom‐economical conversion of biomass into fuels and chemicals.

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Section: Classification Of Cth Processesmentioning

confidence: 99%

Catalytic Transfer Hydrogenation of Biomass‐Derived Substrates to Value‐Added Chemicals on Dual‐Function Catalysts: Opportunities and Challenges

et al. 2018

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“…For instance, vegetable oils, whose fatty acid profile considerably varies, depending on the raw material, lead to a wide range of transesterification yields and thus subsequent crude glycerol purities [38]; • Chemical transformation: Both in the case of crude or pure glycerol (especially for the latter), multiple chemical routes have been investigated to produce more valuable products. Among them, the most common or described chemical routes should be pointed out, such as glycerol carboxylation, hydrogenolysis, oxidation, acetylation, and reforming, among others, which will be thoroughly explained in the following sections [1,29]. It is important to note that there are studies focused on the sustainability of biodiesel production.…”

Section: Treatment or Management Of Crude Glycerolmentioning

confidence: 99%

“…The reaction is commonly described in the literature under basic conditions, mainly due to the fact that alkaline media accelerates the reaction, improves the selectivity to C3 products, and prevents deactivation [183]. Recent advances in the employment of noble metals as active phases, especially Au and Pt, are focused on selective oxidation base-free and room condition reactions [29,[184][185][186][187]. In this line, support properties may be key to achieving this objective through metal particle sintering prevention [188], as well as the establishment of metal synergies with superficial acid-base centers [189].…”

Section: Glycerol Selective Oxidationmentioning

confidence: 99%

“…Therefore, many processes (as will be explained in the following sections) can make glycerol a valuable by-product, by obtaining a purer product (using it for energy purposes) or by chemical reactions (to obtain new compounds). Research on glycerol transformation is very intensive, as evidenced by the large number of publications in the field (Figure 1), including 2835 publications from 2018 to 2020, using the Scopus database and "glycerol or glycerine" and "catalysis" as search words, and 15 reviews since 2018 [22][23][24] for special issues (for instance, New Glycerol Upgrading Processes, in the Catalyst journal [25]), books [26,27], book chapters [28], local density theories [29], and even large European projects like "Production of cyclic carbonates from CO 2 using renewable feedstocks" [30] and "Glycerol Biorefinery Approach for the Production of High Quality Products of Industrial Value" [31].…”

Section: Introductionmentioning

confidence: 99%

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Recent Advances in Glycerol Catalytic Valorization: A Review

et al. 2020

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Once a biorefinery is ready to operate, the main processed materials need to be completely evaluated in terms of many different factors, including disposal regulations, technological limitations of installation, the market, and other societal considerations. In biorefinery, glycerol is the main by-product, representing around 10% of biodiesel production. In the last few decades, the large-scale production of biodiesel and glycerol has promoted research on a wide range of strategies in an attempt to valorize this by-product, with its transformation into added value chemicals being the strategy that exhibits the most promising route. Among them, C3 compounds obtained from routes such as hydrogenation, oxidation, esterification, etc. represent an alternative to petroleum-based routes for chemicals such as acrolein, propanediols, or carboxylic acids of interest for the polymer industry. Another widely studied and developed strategy includes processes such as reforming or pyrolysis for energy, clean fuels, and materials such as activated carbon. This review covers recent advances in catalysts used in the most promising strategies considering both chemicals and energy or fuel obtention. Due to the large variety in biorefinery industries, several potential emergent valorization routes are briefly summarized.

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“…Some of these products serve as intermediates in many reactions, while others are used as the end-product. Their applications cut across polymers, cosmetics, food, pharmaceuticals, tobacco, paints, fine chemical industries, and fuel additives [ 5 , 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

Optimization and Characterization of Mesoporous Sulfonated Carbon Catalyst and Its Application in Modeling and Optimization of Acetin Production

et al. 2020

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In this study, an optimized mesoporous sulfonated carbon (OMSC) catalyst derived from palm kernel shell biomass was developed using template carbonization and subsequent sulfonation under different temperatures and time conditions. The OMSC catalyst was characterized using acid-base titration, elemental analysis, XRD, Raman, FTIR, XPS, TPD-NH3, TGA-DTA, SEM, and N2 adsorption–desorption analysis to reveal its properties. Results proved that the OMSC catalyst is mesoporous and amorphous in structure with improved textural, acidic, and thermal properties. Both FTIR and XPS confirmed the presence of -SO3H, -OH, and -COOH functional groups on the surface of the catalyst. The OMSC catalyst was found to be efficient in catalyzing glycerol conversion to acetin via an acetylation reaction with acetic acid within a short period of 3 h. Response surface methodology (RSM), based on a two-level, three-factor, face-centered central composite design, was used to optimize the reaction conditions. The results showed that the optimized temperature, glycerol-to-acetic acid mole ratio, and catalyst load were 126 °C, 1:10.4, and 0.45 g, respectively. Under these optimum conditions, 97% glycerol conversion (GC) and selectivities of 4.9, 27.8, and 66.5% monoacetin (MA), diacetin (DA), and triacetin (TA), respectively, were achieved and found to be close to the predicted values. Statistical analysis showed that the regression model, as well as the model terms, were significant with the predicted R2 in reasonable agreement with the adjusted R2 (<0.2). The OMSC catalyst maintained excellent performance in GC for the five reaction cycles. The selectivity to TA, the most valuable product, was not stable until the fourth cycle, attributable to the leaching of the acid sites.

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Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review

Cited by 29 publications

References 125 publications

Catalytic Transfer Hydrogenation of Biomass‐Derived Substrates to Value‐Added Chemicals on Dual‐Function Catalysts: Opportunities and Challenges

Catalytic Transfer Hydrogenation of Biomass‐Derived Substrates to Value‐Added Chemicals on Dual‐Function Catalysts: Opportunities and Challenges

Recent Advances in Glycerol Catalytic Valorization: A Review

Optimization and Characterization of Mesoporous Sulfonated Carbon Catalyst and Its Application in Modeling and Optimization of Acetin Production

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