A time- and space-resolved catalyst deactivation study on the conversion of glycerol to aromatics using H-ZSM-5

He, Shan; Goldhoorn, Hero Reinder; Tegudeer, Zhuorigebatu; Chandel, Anshu; Heeres, André; Stuart, Marc C. A.; Heeres, Hero Jan

doi:10.1016/j.cej.2022.134620

Cited by 22 publications

(12 citation statements)

References 44 publications

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“…Eventually, the carbon formed blocks the micropores and the acid sites resulting in the catalyst deactivation. In the deactivation phase, the BTX and BTEX yields drop drastically, however, unconverted glycerol, acetol, acetaldehyde, and acrolein remained in the product [ 15 ]. Table 1 shows the reported catalysts for glycerol conversion to aromatics and reaction conditions with selectivity towards BTX.…”

Section: Effect Of Time On Streammentioning

confidence: 99%

“…The longer time on stream, the more coke accumulation. The mechanism proposed for this scenario posits that initially, coke is formed at the microporous channel of the H-ZSM-5 catalyst, followed by accumulation on the external surface of the zeolite as the time on stream increases [15]. The primary cause of the coke formation is the strong acid sites of the H-ZSM-5 catalysts, which have been improved by the design of shape-selective catalysts [35], metals, additive addition [33], and dealumination [43].…”

Section: Prospects Of Catalytic Glycerol To Bio-aromaticsmentioning

confidence: 99%

“…However, glycerol is a platform molecule with three hydroxyl groups which can be transformed into fuels and fine chemicals. Many reaction pathways such as acetylation [12], carboxylation [13], etherification [14], oxidation, dehydration, gasification, aromatization [15,16], etc. have been adopted to valorize glycerol.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Conversion of Glycerol to Bio-Based Aromatics

Okoye¹,

Duque-Brito²,

Lobata-Peralta³

et al. 2023

Ethanol and Glycerol Chemistry - Production, Modelling, Applications, and Technological Aspects

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Green application of biodiesel-derived glycerol will boost biodiesel production in terms of sustainability and economics. The glycerol to liquid fuels is a promising route that provides an additional energy source, which contributes significantly to energy transition besides biodiesel. This pathway could generate alkyl-aromatic hydrocarbons with a yield of ∼60%, oxygenates, and gases. MFI Zeolites (H-ZSM-5) catalysts are mainly used to propagate the aromatization pathway. This chapter presents the pathways, challenges, catalytic design, influences of catalyst acidity, metal addition, reaction condition, and catalysts deactivation on glycerol conversion to hydrocarbon fuels and aromatics. Studies revealed that time on stream, temperature, and weight hourly space velocity (range of 0.1–1 h−1) influences the benzene, toluene, and xylene BTX and benzene, toluene, ethylbenzene, and xylene BTEX yield. Acidity of the H-ZSM-5 could be tailored by metals, additives, and binders. Bronsted acidity promotes coke formation which results in reversible deactivation of the H-ZSM-5 catalyst. It is hoped that this study will promote intensified research on the use of glycerol for purposes of fuel generating and valuable products.

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Section: Effect Of Time On Streammentioning

confidence: 99%

Section: Prospects Of Catalytic Glycerol To Bio-aromaticsmentioning

confidence: 99%

See 1 more Smart Citation

Catalytic Conversion of Glycerol to Bio-Based Aromatics

Okoye¹,

Duque-Brito²,

Lobata-Peralta³

et al. 2023

Ethanol and Glycerol Chemistry - Production, Modelling, Applications, and Technological Aspects

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“…The nature of the coke formed is related to the working temperature, which the soft coke is generated at temperatures up to 400 °C, while the hard coke is formed at temperatures above 500 °C. [72] Scheme 2 shows the possible routes for coke formation under the catalyst surface. The compounds were identified by GC-MS and these compounds are the most superficial extracted by solvent.…”

Section: Chemcatchemmentioning

confidence: 99%

Glycerol Conversion into Allyl Alcohol Using a Coke‐tolerant ZnAl₂O₄‐β Zeolite Catalyst: Effect of Structural, Textural, and Acidic Properties on Catalytic Stability

et al. 2023

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Catalysts with different ZnAl 2 O 4 contents impregnated in beta zeolite were synthesized and their catalytic activity in glycerol dehydration to allyl alcohol was investigated. The materials were characterized by XRD, XRF, FTIR, DRIFTS-pyridine, NH 3 -TPD, and N 2 physisorption. In addition, the surface electrostatic potential maps were generated by a molecular mechanics approach. The XRD patterns indicated a high dispersion of the ZnAl 2 O 4 , evidenced by the absence of reflections in the diffractograms, except for the sample containing the highest spinel content. The FTIR spectra indicated the presence of zinc aluminate spinel in the zeolite matrix. The DRIFTS-pyridine and NH 3 -TPD analyses indicated that the incorporation of ZnAl 2 O 4 modifies the acidic properties of the zeolite concerning the number, type, and distribution of acid sites. The N 2 physisorption tests showed the maintenance of the micro and mesoporous properties of H-BEA after modification, despite the reduction of the specific area and pore volume values. The samples impregnated with the ZnAl 2 O 4 phase showed larger mesopores sizes, which may favor its catalytic performance. The catalytic tests indicated the allyl alcohol production for the impregnated materials, which the best results were obtained by the sample containing 2 % of ZnAl 2 O 4 , with 90.65 % glycerol conversion and 37 % allyl alcohol selectivity due to appropriate tuning of the acidic and textural properties, as well as the presence of basic sites evidenced by CO 2 -TPD analysis and electrostatic potential maps. The presence of acid-base sites is essential to conduct hydrogen transfer, according to the proposed mechanism, generating allyl alcohol. Finally, the results with a longer reaction period showed greater stability for the sample impregnated with low spinel content, whose coke deposition was smaller, which may be related to the larger size of secondary mesopores.

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“…Coprocessing of glycerol with alcohol (methanol) can increase the H/C eff ratio, which not only resolves the density issue of glycerol but also increases the alkyl-aromatics yield with an improved catalyst lifetime . Nonselective reactions occurring on the surface-located active sites of ZSM-5 encourage undesired side-reactions of xylene disproportionation to produce toluene and trimethylbenzenes at the cost of p -X. − The aim of present is to develop a GTA ‑ p X (glycerol-to-aromatics priority to p -X) catalytic process suitable for the selective production of p -X-rich alkyl-aromatics from bioderived crude glycerol. Three important strategies, i.e., (i) narrowing of the pore opening of micropores with sufficient 3D pore structures, (ii) reduced Brønsted acidity, and (iii) promoted Lewis acidity, have been adopted in the present study through the functionalized ZSM-5 catalyst to facilitate effective carbon conversion of glycerol toward the formation of aromatics with special focus on p -X selectivity.…”

Section: Introductionmentioning

confidence: 99%

Renewable p-Xylene Production by Catalytic Conversion of Crude Bioglycerol (GTA^-pX Process)

Singh

Arumugam

Kumar

et al. 2023

Ind. Eng. Chem. Res.

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The studies report an efficient vapor-phase continuous-flow process that operates on a ZSM-5 micro−mesoporous composite catalyst system (facilitated by molecular-level interaction of tetraethyl orthosilicate (TEOS) and Zn species) for the production of sustainable para-xylene (p-X)-enriched alkyl-aromatics from crude bioglycerol. The process achieved 100% conversion of glycerol by coprocessing with methanol to produce industrially important liquid stock possessing ∼85% alkyl-aromatics, especially xylene isomers, which is the highest ever reported to the best of our knowledge. The xylene isomers consisting of ∼57% p-X are attractive for renewable petrochemical and polymer (poly(ethylene terephthalate)) production applications. The liquid stock consisting of xylene-rich alkyl-aromatics with minimum benzene content and possessing a high octane rating (research octane rating (RON) = 104) also has potential for gasoline blending applications.

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A time- and space-resolved catalyst deactivation study on the conversion of glycerol to aromatics using H-ZSM-5

Cited by 22 publications

References 44 publications

Catalytic Conversion of Glycerol to Bio-Based Aromatics

Catalytic Conversion of Glycerol to Bio-Based Aromatics

Glycerol Conversion into Allyl Alcohol Using a Coke‐tolerant ZnAl₂O₄‐β Zeolite Catalyst: Effect of Structural, Textural, and Acidic Properties on Catalytic Stability

Renewable p-Xylene Production by Catalytic Conversion of Crude Bioglycerol (GTA^-pX Process)

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A time- and space-resolved catalyst deactivation study on the conversion of glycerol to aromatics using H-ZSM-5

Cited by 22 publications

References 44 publications

Catalytic Conversion of Glycerol to Bio-Based Aromatics

Catalytic Conversion of Glycerol to Bio-Based Aromatics

Glycerol Conversion into Allyl Alcohol Using a Coke‐tolerant ZnAl2O4‐β Zeolite Catalyst: Effect of Structural, Textural, and Acidic Properties on Catalytic Stability

Renewable p-Xylene Production by Catalytic Conversion of Crude Bioglycerol (GTA-pX Process)

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Product

Resources

About

Glycerol Conversion into Allyl Alcohol Using a Coke‐tolerant ZnAl₂O₄‐β Zeolite Catalyst: Effect of Structural, Textural, and Acidic Properties on Catalytic Stability

Renewable p-Xylene Production by Catalytic Conversion of Crude Bioglycerol (GTA^-pX Process)