Maximizing carbon efficiency of petrochemical production from catalytic co-pyrolysis of biomass and plastics using gallium-containing MFI zeolites

Li, Jian; Yu, Yong; Li, Xiangyu; Wang, Wei; Yu, Gang; Deng, Shubo; Huang, Jun; Wang, Bin; Wang, Yujue

doi:10.1016/j.apcatb.2015.02.015

Cited by 101 publications

(83 citation statements)

References 55 publications

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“…The XRD patterns revealed that gallium modification caused a slight decrease in crystallinity (Figure and Table S1) due to the impregnation of gallium species, and from the XPS results of the Ga 3d spectra for modified HUSY zeolites (Figure ), we can conclude that most of the gallium species were introduced into the Y zeolite framework through the formation of Ga‐O(H)‐Al bonds (framework substitution at the zeolite surface) and Ga‐O(H)−Si bonds (framework substitution at the zeolite surface) . Moreover, the XPS spectra also indicated that the Ga 2 O 3 species was formed with the increase of gallium modification content (Figure ), thus decreasing the crystallinity.…”

Section: Discussionmentioning

confidence: 89%

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Zhou

Wei

et al. 2017

Chemistry A European J

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The effects of metal-modified acidic co-supports on the hydrodesulfurization (HDS) activity and isomerization selectivity of highly refractory organosulfur compounds such as 4,6-dimethyldibenzothiophene have been investigated. Y zeolite crystals with high Si/Al ratios and small crystallite sizes were successfully synthesized by a new hydrothermal synthesis approach. The synthesized Y zeolite crystals were ion-exchanged and stabilized. The prepared samples were then modified with different gallium contents using an impregnation method to adjust their acidity properties, and these modified samples were used as co-supports for NiMo sulfide HDS catalysts. The catalyst containing 10 wt.% zeolite Y modified by 2 wt.% gallium (NiMo/2GaY-ASA-A) exhibited the highest HDS activity, with 4,6-dimethyldibenzothiophene (4,6-DMDBT) conversion nearly double the rate of the catalyst without zeolite at 563 K, 4.0 MPa and liquid hourly space velocity (LHSV) of 40 h . NiMo/2GaY-ASA-A also exhibited superior isomerization ability, with 3,4'-DMBP, 4,4'DMBP, and 3,6-DMDBT as the main products, indicating that the isomerization pathway was the main reaction route over NiMo/2GaY-ASA-A. The superior catalytic performance is related to the synergistic effect of the proper amount of medium and strong Brønsted acid sites. The compounds 3,6-DMDBT and 3,7-DMDBT (isomers of 4,6-DMDBT) and 3,4,6-TMDBT and tetra-methyl-DBT (transmethyl products) were detected simultaneously in the HDS product of 4,6-DMDBT for the first time over NiMo/GaY-ASA-A catalysts. Finally, a new reaction network over NiMo/2GaY-ASA-A was proposed.

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Section: Discussionmentioning

confidence: 89%

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Zhou

Wei

et al. 2017

Chemistry A European J

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“…reported that ZSM‐5 impregnation with 3.8 wt% Ga increased p ‐xylene selectivity from 32% for ZSM‐5 to 58% for 3.8 wt% Ga/ZSM‐5 in co‐catalytic fast pyrolysis (co‐CFP) of 2‐methyfuran with propylene . Similar improvement also was observed in the study of co‐CFP of pine wood and LDPE with 5 wt% Ga/ZSM‐5 . Those authors suggested that the improvement of p ‐xylene selectivity was mainly attributed to the partial blockage of pore openings of ZSM‐5 zeolite by Ga‐oxides .…”

Section: Resultsmentioning

confidence: 95%

“…The main reaction pathways for the selective conversion of biomass into p ‐xylene in this work are summarized in Fig. , with respect to the products identified, the catalyst's characterizations and previous work . The transformation mainly included four main cascade reactions: the pyrolysis of lignocellulose biomass into oxygenated organic compounds; catalytic pyrolysis of oxygenates into aromatic monomers; the alkylation of light aromatics to xylenes; and finally the isomerization of m/o‐ xylenes to p ‐xylene.…”

Section: Resultsmentioning

confidence: 99%

“…The catalytic cracking of lignin into aromatics using a zeolite catalyst involves the formation of phenols and other oxygenates by thermal depolymerization of lignin through the cleavage of the CC and CO bonds in the lignin polymer, followed by the formation of the aromatics through catalytic cracking, deoxygenation, aromatization and oligomerization over zeolites . To increase aromatics yield and reduce coke yield, there are several reports on the production of aromatic chemicals by co‐catalytic pyrolysis of biomass and additives . For example, Zhang et al .…”

Section: Introductionmentioning

confidence: 99%

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Production of bio‐based p‐xylene via catalytic pyrolysis of biomass over metal oxide‐modified HZSM‐5 zeolites

Chang

Zhu

Jin

et al. 2018

J of Chemical Tech & Biotech

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BACKGROUND p‐Xylene is an important bulk chemical in the petrochemical industry, and the production of bio‐based p‐xylene is of great significance in both academic and industrial arenas. However, the biggest challenge for the production of p‐xylene from biomass is how to increase the yield and selectivity of p‐xylene. RESULTS The highest p‐xylene yield of 20.7 C‐mol% with a p‐xylene/xylenes ratio of 91.6% was obtained by the co‐catalytic pyrolysis of sawdust with 50 wt% methanol over the 20%La2O3/HZSM‐5(80) catalyst. Adding a La, Mg, Ce or Zn element into HZSM‐5 promoted the alkylation of benzene and toluene to form xylenes, and the isomerization of m/o‐xylenes to p‐xylene. CONCLUSION This work developed a one‐pot process in which lignocellulosic biomass (sawdust) was directionally converted into p‐xylene by coupling the catalytic pyrolysis of biomass into aromatic monomers, the alkylation of light aromatics to xylenes and the isomerization of m/o‐xylenes to p‐xylene over the metal oxide‐modified HZSM‐5 catalysts. The selectivity and yield of p‐xylene strongly depended on the acidity of the catalysts, reaction temperature and methanol additive during the catalytic pyrolysis of sawdust. © 2018 Society of Chemical Industry

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“…While CFP can rapidly convert biomass to aromatics, its carbon efficiency has yet to be improved to make the conversion process more economically competitive (Lazdovica et al, 2016;Li et al, 2013Li et al, , 2015Widayatno et al, 2015). It is well-known that natural lignocellulosic biomass consists of three major components, i.e., cellulose (40-50 wt.%), hemicellulose (25-35 wt.%), and lignin (15-20 wt.%) (Alonso et al, 2010;Huber et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

Maximizing carbon efficiency of petrochemical production from catalytic co-pyrolysis of biomass and plastics using gallium-containing MFI zeolites

Cited by 101 publications

References 55 publications

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Gallium Modified HUSY Zeolite as an Effective Co‐support for NiMo Hydrodesulfurization Catalyst and the Catalyst's High Isomerization Selectivity

Production of bio‐based p‐xylene via catalytic pyrolysis of biomass over metal oxide‐modified HZSM‐5 zeolites

Enhancement of biomass conversion in catalytic fast pyrolysis by microwave-assisted formic acid pretreatment

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