Upgrading of the Acid-Rich Fraction of Bio-oil by Catalytic Hydrogenation-Esterification

Chen, Junhao; Cai, Qinjie; Liang, Lu; Leng, Furong; Wang, Shurong

doi:10.1021/acssuschemeng.6b02366

Cited by 41 publications

(24 citation statements)

References 63 publications

(124 reference statements)

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“…2017 Chen et al 2017 . The most common practice is to add a catalyst during the pyrolysis process to selectively control the distribution of pyrolysis products and further increase the yield of the desired target product, thereby improving the bio-oil quality.…”

Section: Introductionmentioning

confidence: 99%

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

Cheng

Jiang

Xia

et al. 2021

Preprint

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Cellulose is one of the main components of terrestrial biomass. In this study, a zeolite catalyst (ZSM-5) was used to catalyze the pyrolysis of cellulose. The components produced during pyrolysis were tested by Py-GC/MS, and the pyrolysis mechanism was analyzed by density functional theory (DFT). The results showed that furans and sugars were the primary pyrolysis products. After catalytic pyrolysis, the furfural content was significantly lower than that of non-catalytic pyrolysis. However, the yield of aromatic hydrocarbons increased significantly, especially benzene, which increased from almost zero to 13.04%. DFT further explored the specific reaction pathway of catalytic pyrolysis. It was found that under the catalysis of ZSM-5, the catalyst directly participated in most cellulose pyrolysis reactions. Also, the electrophilicity of acid sites in the reaction system played an important role. Therefore, the catalysis of the molecular sieve can significantly reduce the energy barrier of each path. In generating aromatic hydrocarbons, the decarbonylation reaction and dehydration reaction of furfural can be completely catalyzed, thereby increasing the reaction rate of generating aromatic hydrocarbons. Some deoxygenation steps occurred during the reaction, which made the catalytic pyrolysis reaction easier to develop, and improved the bio-oil quality.

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Section: Introductionmentioning

confidence: 99%

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

Cheng

Jiang

Xia

et al. 2021

Preprint

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“…Simultaneously, both oxygen (removed as H 2 O in esterification) content and acidity are decreased, without requiring any additives such alcohols and with lower hydrogen consumption. 24,44…”

Section: Resultsmentioning

confidence: 99%

“…23 More recently, hydrotreating of methanol solutions containing furfural, hydroxyacetone, guaiacol, and acetic acid over Cu/SBA-15 has shown to lead to the formation of diverse saturated esters and alcohols. 24…”

Section: Introductionmentioning

confidence: 99%

Hydrotreating of Guaiacol and Acetic Acid Blends over Ni₂P/ZSM-5 Catalysts: Elucidating Molecular Interactions during Bio-Oil Upgrading

et al. 2019

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Catalytic hydrodeoxygenation (HDO) is an effective technology for upgrading pyrolysis bio-oils. Although, in the past years, this process has been extensively studied, the relevance of the cross-reactivity between the numerous chemical components of bio-oil has been scarcely explored. However, molecular coupling can be beneficial for improving the bio-oil characteristics. With the aim of gaining a better understanding of these interactions, this work investigates the catalytic hydrodeoxygenation of mixtures of two typical components of pyrolysis bio-oils: guaiacol and acetic acid. The catalytic tests were carried out employing a bifunctional catalyst based on nickel phosphide (Ni2P) deposited over a commercial nanocrystalline ZSM-5 zeolite. The influence of both hydrogen availability and temperature on the activity and product distribution, was evaluated by carrying out reactions under different H2 pressures (40–10 bar) and temperatures (between 260 and 300 °C). Using blends of both substrates, a partial inhibition of guaiacol HDO occurred because of the competence of acetic acid for the catalytic active sites. Nevertheless, positive interactions were also observed, mainly esterification and acylation reactions, which could enhance the bio-oil stability by reducing acidity, lowering the oxygen content, and increasing the chain length of the components. In this respect, formation of acetophenones, which can be further hydrogenated to yield ethyl phenols, is of particular interest for biorefinery applications. Increasing the temperature results in an increment of conversion but a decrease in the yield of fully deoxygenated molecules due to the production of higher proportion of catechol and related products. Additional experiments performed in the absence of hydrogen revealed that esterification reactions are homogeneously self-catalyzed by acetic acid, while acylation processes are mainly catalyzed by the acidic sites of the zeolitic support.

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“…Studies showed that reaction pressure could affect both hydrogenation and cracking processes: the elevation of hydrogen pressure could improve the hydrogenation efficiency of bio-oil components (Mortensen et al 2011); pressurized cracking favored the formation of liquid hydrocarbons, but this influence became insignificant when the pressure was above 2 MPa (Wang et al 2013b). 4 MPa was selected in this work because the author's previous study using this pressure successfully achieved the hydrogenation of aldehyde group , which is also a typical unsaturated functional group in bio-oil, and similar pressures were also used in the mild hydrogenation of bio-oil components (Vispute et al 2010;Chen et al 2016). The weights of hydrogenation and the cracking catalysts were both 2 g. The weight hourly space velocity of liquid feedstock was 2 h -1 , in terms of the weight of the hydrogenation catalyst.…”

Section: Catalytic Reactionmentioning

confidence: 99%

Aromatic Hydrocarbon Generation from a Simulated Bio-oil Fraction by Dual-stage Hydrogenation-cracking: Hydrogen Supply and Transfer Behaviors

Cai¹,

Xu²,

Zhang³

et al. 2017

BioResources

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The improvement of the hydrogen-poor composition of bio-oil is important for its cracking to produce aromatic hydrocarbons. In this work, a mild hydrogenation pre-treatment and methanol cocracking were combined to implement proper hydrogen supplementation for cracking. Acetic acid (HAc), hydroxypropanone (HPO), and cyclopentanone (CPO) were selected as model compounds and mixed to prepare a simulated distilled fraction (SDF) of bio-oil. The hydrogen supply and transfer behaviours in hydrogenation-cracking were investigated. For the conversion of individual components: HAc was difficult to be hydrogenated, and therefore in the cracking stage, the conversion and oil phase yield were low; ketones were successfully hydrogenated to alcohols, and thus high aromatic hydrocarbon yields were achieved. Hydrogenation-cracking of SDF showed that the inferior performance of HAc was improved by an internal hydrogen transfer, namely the alcohols produced from ketones supplied hydrogen for HAc conversion. However, because of the high HAc content in SDF, this hydrogen supplement was not sufficient. Therefore, methanol (MeOH) was used as the coreactant for secondary hydrogen supply. The integral efficient conversion of SDF and MeOH to aromatic hydrocarbons was achieved when the MeOH blending ratio was 30%. Finally, a reaction mechanism of hydrogenationcocracking was proposed.

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Upgrading of the Acid-Rich Fraction of Bio-oil by Catalytic Hydrogenation-Esterification

Cited by 41 publications

References 63 publications

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

Hydrotreating of Guaiacol and Acetic Acid Blends over Ni₂P/ZSM-5 Catalysts: Elucidating Molecular Interactions during Bio-Oil Upgrading

Aromatic Hydrocarbon Generation from a Simulated Bio-oil Fraction by Dual-stage Hydrogenation-cracking: Hydrogen Supply and Transfer Behaviors

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Upgrading of the Acid-Rich Fraction of Bio-oil by Catalytic Hydrogenation-Esterification

Cited by 41 publications

References 63 publications

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

WITHDRAWN: The Catalytic Pyrolysis Mechanism of Cellulose On ZSM-5: Based On Py-GC/MS And Density Functional Theory

Hydrotreating of Guaiacol and Acetic Acid Blends over Ni2P/ZSM-5 Catalysts: Elucidating Molecular Interactions during Bio-Oil Upgrading

Aromatic Hydrocarbon Generation from a Simulated Bio-oil Fraction by Dual-stage Hydrogenation-cracking: Hydrogen Supply and Transfer Behaviors

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Hydrotreating of Guaiacol and Acetic Acid Blends over Ni₂P/ZSM-5 Catalysts: Elucidating Molecular Interactions during Bio-Oil Upgrading