Catalytic pyrolysis of crude glycerol over a shaped H-ZSM-5 zeolite catalyst with (partial) recycling of the product oil was studied with the incentive to improve benzene, toluene, and xylene (BTX) yields. Recycling of the polycyclic aromatic hydrocarbon (PAH) fraction, after separation from BTX by distillation and co-feeding with the crude glycerol feed, was shown to have a positive effect on the BTX yield. Further improvements were achieved by hydrogenation of the PAH fraction using a Ru/C catalyst and hydrogen gas prior to co-pyrolysis, and BTX yields up to 16 wt% on feed were obtained. The concept was also shown to be beneficial to other biomass feeds such as e.g., Kraft lignin, cellulose, and Jatropha oil.
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Bio-aromatics (benzene, toluene, xylenes, BTX) were prepared by the catalytic pyrolysis of six different black liquors using both in situ and ex situ approaches. A wide range of catalysts was screened and conditions were optimized in microscale reactors. Up to 7 wt % of BTX, based on the organic fraction of the black liquors, was obtained for both the in situ and ex situ pyrolysis ( T = 500-600 °C) using a Ga-modified H-ZSM-5 catalyst. The in situ catalytic pyrolysis of black liquors from hardwood paper mills afforded slightly higher yields of aromatics/BTX than softwood black liquors, a trend that could be confirmed by the results obtained in the ex situ catalytic pyrolysis. An almost full deoxygenation of the lignin and carbohydrate fraction was achieved and both organic fractions were converted to a broad range of (substituted) aromatics. The zeolite catalyst used was remarkably stable and even after 100 experiments in batch mode with intermittent oxidative catalyst regeneration, the yields and selectivity toward BTX remained similar. The ex situ pyrolysis of black liquor has potential for large-scale implementation in a paper mill without disturbing the paper production process.
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The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al2O3 catalyst (ϕ 1.2–1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h–1). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g–1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition (ca. 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles (e.g., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged (e.g., >24 h), leading to a significantly enhanced total BTX production (e.g., 3000 mg g–1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N2 and Ar physisorption, XRD, HR-TEM-EDX, 27Al, and 29Si MAS ssNMR, NH3-TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced.
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Sustainable production of aromatics, especially benzene, toluene and xylenes (BTX), is essential considering their broad applications and the current global transition away from crude oil utilization. Aromatization of lower olefins, particularly ethene and propene, offers great potential if they are derived from more circular alternative carbon feedstocks such as biomass and waste plastics. This work aims to identify the preferred olefin feed, ethene or propene, for BTX production in a fixed-bed reactor. A commercial H-ZSM-5 (Si/Al = 23) catalyst was used as a reference catalyst, as well as a Ga-ZSM-5 catalyst, prepared by Ga ion-exchange of the H-ZSM-5 catalyst. At 773 K, 1 bar, 45 vol % olefin, 6.75 h−1, propene aromatization over the Ga-ZSM-5 catalyst exhibited higher BTX selectivity of 55 % and resulted in slower catalyst deactivation compared to ethene aromatization.
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Glycerol is an attractive bio-based platform chemical that can be converted to a variety of bio-based chemicals. We here report a catalytic co-conversion strategy where glycerol in combination with a second (bio-)feed (fatty acids, alcohols, alkanes) is used for the production of bio-based aromatics (BTX). Experiments were performed in a fixed bed reactor (10 g catalyst loading and WHSV of (co-)feed of 1 h-1) at 550 °C using a technical H-ZSM-5/Al2O3 catalyst. Synergistic effects of the co-feeding on the peak BTX carbon yield, product selectivity, total BTX productivity, catalyst life-time, and catalyst regenerability were observed and quantified. Best results were obtained for the co-conversion of glycerol and oleic acid (45/55 wt%), showing a peak BTX carbon yield of 26.7 C%. The distribution of C and H of the individual co-feeds in the BTX product was investigated using an integrated fast pyrolysis-GC-Orbitrap MS unit, showing that the aromatics are formed from both glycerol and the co-feed. The results of this study may be used to develop optimized co-feeding strategies for BTX formation. This journal is
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The use of H-ZSM-5 with various binders (Al2O3, SiO2, and kaolinite, 10 wt% on catalyst formulation) for the catalytic conversion of glycerol to bio-based aromatics (GTA) was investigated in a continuous bench-scale unit at a pyrolysis temperature of 450 °C, catalytic upgrading temperature of 500 °C, WHSV of pure glycerol of 1 h−1, and atmospheric pressure, and their performance was compared to H-ZSM-5 (SiO2/Al2O3 molar ratio of 28). The latter gave a peak BTX carbon yield of ca. 31.1C.%, a life-time of ca. 220 min, and a total BTX productivity of ca. 312 mg BTX g−1H-ZSM-5. The introduction of binders affects catalyst performance, which is the most profound and promising for the H-ZSM-5/Al2O3 catalyst. It shows a prolonged catalyst life-time of ca. 320 min and a higher total BTX productivity of ca. 518 mg BTX g−1H-ZSM-5, compared to the H-ZSM-5 without a binder. Catalyst characterization studies show that the addition of the binder does not have a major effect on the specific surface area, total pore volume, and total acidity. Other relevant properties were affected, though, such as micropore volume (SiO2), a reduced Brønsted acidity (Al2O3, and SiO2), and reduced crystallinity (SiO2). Coke formation causes severe catalyst deactivation, ultimately leading to an inactive catalyst for BTX formation. Catalyst characterization studies after an oxidative regeneration showed that the textural properties of the regenerated catalysts were close to those of the original catalysts. However, some dealumination of H-ZSM-5 occurs, resulting in decreased crystallinity and acidity, causing irreversible deactivation, which needs attention in future catalyst development studies.
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The present invention relates to a novel process for the preparation of low molecular weight aromatic compounds such as benzene, toluene, and xylenes (BTX) from plastics. Provided is a thermo-catalytic pyrolysis process for the preparation of aromatic compounds from a feed stream comprising plastic, comprising the steps of: a) subjecting a feed stream comprising a plastic to a pyrolysis treatment at a pyrolysis temperature in the range of 600-1000°C to produce pyrolysis vapors; b) optionally cooling the pyrolysis vapors to a temperature that is below the pyrolysis temperature; c) contacting the vaporous phase with an aromatization catalyst at an aromatization temperature in the range of 450 - 700 °C, which aromatization temperature is at least 50°C lower than the pyrolysis temperature, in a catalytic conversion step to yield a conversion product comprising aromatic compounds; and d) optionally recovering the aromatic compounds from the conversion product.
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A process for the prepn. of arom. compds. from a feed stream contg. biomass or mixts. of biomass, the process comprising: a) subjecting a feed stream contg. biomass or mixts. of biomass to a process to afford a conversion product comprising arom. compds.; b) recovering the arom. compds. from said conversion product; c) sepg. a higher mol. wt. fraction comprising polyarom. hydrocarbons (PAH) from a lower mol. wt. fraction comprising benzene, toluene and xylene (BTX) by distn.; d) reducing at least part of said higher mol. wt. fraction to obtain a reduced fraction comprising polycyclic aliphatics (PCA); and e) subjecting the higher mol. wt. fraction obtained in step c), the reduced fraction obtained in step d), or a mixt. thereof, to a process to obtain lower mol. wt. aroms. (BTX). [on SciFinder(R)]
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The catalytic conversion of glycerol to aromatics (GTA, e.g., benzene, toluene, and xylenes, BTX) over a shaped H-ZSM-5/Al2O3 (60/40 wt%) catalyst was investigated in a continuous fixed-bed reactor to study the addition of the Al2O3 binder in the catalyst formulation on catalyst performance. The experiments were performed under N2 at 550 °C, a WHSV of glycerol (pure) of 1 h−1, and atmospheric pressure. The spent H-ZSM-5/Al2O3 catalysts were reused after an oxidative regeneration at 680 °C and in total 5 reaction-regeneration cycles were performed. Catalyst characterization studies show that the addition of the Al2O3 binder does not affect the surface area and crystallinity of the formulation, but increases the total pore volume (mesopores in particular) and total acidity (Lewis acidity in particular). The H-ZSM-5/Al2O3 (60/40 wt%) catalyst shows a considerably prolonged catalyst life-time (8.5 vs. 6.5 h for H-ZSM-5), resulting in a significant increase in the total BTX productivity (710 vs. 556 mg g−1 H-ZSM-5). Besides, the addition of the Al2O3 binder retards irreversible deactivation. For instance, after 3 regenerations, catalyst performance is comparable to the fresh one. However, after 4 regenerations, some irreversible catalyst deactivation occurs, associated with a reduction in total pore volume, crystallinity, and acidity (Brønsted acidity in particular), and meso-porosity of the Al2O3 binder. This study shows that both the stability and reusability of H-ZSM-5-based catalysts for GTA are remarkably enhanced when using a suitable binder.
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Pyrolysis liquids from lignocellulosic biomass have the potential to be used as a feed for aromatics such as benzene, toluene, and xylenes (BTX) using catalytic upgrading with zeolites. We here report an experimental study on the conversion of various pyrolysis oil fractions to determine the most suitable one for BTX synthesis. For this purpose, the pyrolysis liquid was fractionated using several extraction/distillation steps to give four fractions with different chemical compositions. The fractions were analyzed in detail using nuclear magnetic resonance spectroscopy, elemental analysis, gas chromatography-mass spectroscopy, thermogravimetric analysis, Karl-Fischer titration, and gel permeation chromatography. Catalytic pyrolysis experiments were carried out using a tandem microreactor with H-ZSM-5 (23) as the catalyst. The highest BTX yield of 24% (on a carbon and dry basis) was obtained using the fractions enriched in phenolics, whereas all others gave far lower yields (4.4-9%, on a carbon and dry basis). Correlations were established between the chemical composition of the feed fraction and the BTX yield. These findings support the concept of a pyrolysis biorefinery, where the pyrolysis liquid is separated into well-defined fractions before further dedicated catalytic conversions to biobased chemicals and biofuels using tailored catalysts.
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