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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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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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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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 catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.
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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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A time- and space-resolved deactivation study on the conversion of glycerol to aromatics over H-ZSM-5 was performed. For this purpose, glycerol was vaporized/pyrolyzed in a pyrolysis section followed by a catalytic aromatization step. Benchmark performance showed an induction period of ca. 20 min, followed by a rather constant BTX yield of ca. 25.4 ± 2.2C.% for 3–4 h time on stream (TOS). Subsequently, a rapid drop in BTX yield was observed due to catalyst deactivation. Severe coking leads to coverage of catalyst surface area and blockage of micropores, particularly at the entrance of the catalyst bed at short TOS, indicating the presence of an axial coke gradient in the fixed bed reactor. At longer TOS, coke was formed throughout the bed and negligible BTX yield was shown to be associated with the presence of coke at all bed positions. Besides coking, the acidity of the catalyst was also reduced, and dealumination occurred, both with a similar time–space evolution. The results were explained by a conversion-zone migration model, which includes a deactivation zone (with severely coked catalyst), a conversion zone (BTX formation), and an induction zone (a.o. (de-)alkylation reactions), and describes the time- and space-resolved evolution of coking and relevant changes in other catalyst characteristics.
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The scope of this thesis of Gerrit Bouwhuis, lecturer at Saxion Research Centre for Design and Technology in Enschede is the development of a new industrial applicable pre-treatment process for cotton based on catalysis. The pre-treatment generally consists of desizing, scouring and bleaching. These processes can be continuous or batch wise. Advances in the science of biocatalytic pre-treatment of cotton and catalytic bleaching formed the scientific basis for this work. The work of Agrawal on enzymes for bio-scouring and of Topalovic on catalytic bleaching led to the conclusion that reduced reaction temperatures for the pre-treatment processes of cotton are possible. A second reason for the present work is a persistent and strong pressure on the industry to implement ‘more sustainable’ and environmental friendlier processes. It was clear that for the industrial implementation of the newly developed process it would be necessary to ‘translate’ the academic knowledge based on the catalysts, into a process at conditions that are applicable in textile industry. Previous experiences learned that the transition from academic knowledge into industrial applicable processes often failed. This is caused by lack of experience of university researchers with industrial product and process development as well as a lack of awareness of industrial developers of academic research. This is especially evident for the so-called Small and Medium Enterprises (SME’s). To overcome this gap a first step was to organize collaboration between academic institutes and industries. The basis for the collaboration was the prospect of this work for benefits for all parties involved. A rational approach has been adopted by first gathering knowledge about the properties and morphology of cotton and the know how on the conventional pre-treatment process. To be able to understand the conventional processes it was necessary not only to explore the chemical and physical aspects but also to evaluate the process conditions and equipment that are used. This information has been the basis for the present lab research on combined bio-catalytic desizing and scouring as well as catalytic bleaching. For the measurement of the performance of the treatments and the process steps, the performance indicators have been evaluated and selected. Here the choice has been made to use industrially known and accepted performance indicators. For the new bio-catalytic pre-treatment an enzyme cocktail, consisting of amylase, cutinase and pectinase has been developed. The process conditions in the enzyme cocktail tests have been explored reflecting different pre-treatment equipment as they are used in practice and for their different operation conditions. The exploration showed that combined bio-catalytic desizing and scouring seemed attractive for industrial application, with major reduction of the reaction and the rinsing temperatures, leading to several advantages. The performance of this treatment, when compared with the existing industrial treatment showed that the quality of the treated fabric was comparable or better than the present industrial standard, while concentrations enzymes in the cocktail have not yet been fully optimized. To explore the application of a manganese catalyst in the bleaching step of the pre-treatment process the fabrics were treated with the enzyme cocktail prior to the bleaching. It has been decided not to use conventional pre-treatment processes because in that case the combined desizing and scouring step would not be integrated in the newly developed process. To explore catalytic bleaching it has been tried to mimic the existing industrial processes where possible. The use of the catalyst at 100°C, as occurs in a conventional steamer, leads to decomposition of the catalyst and thus no bleach activation occurs. This led to the conclusion that catalytic bleaching is not possible in present steamers nor at low temperatur
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The recycling of post consumer cotton textile waste is highly requested, due to the high environmental impact of cotton production. Often cotton is mixed in blends with polyethylene terephthalate (PET). For the generation of high value products from recycled cotton, it essential that PET is separated from the cotton first. In this contribution, the depolymerization of PET in cotton / PET blend is investigated for the separation of PET from cotton fibers. Ionic liquids and NaOH are used as catalysts for the depolymerization reaction in ethylene glycol (glycolysis). It will be shown that ionic liquids have no significant influence on the conversion of PET. However, 99% conversion is achieved in this process with 2 w/w % NaOH as catalyst. This enables the selective depolymerization of PET in presence of cotton and gives rise to an easy separation of cotton from cotton / PET blends.Paper for the 14th World Textile Conference, May 26th-28th2014, Bursa, Turkey.
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The catalytic coconversion of glycerol and toluene (93/7 wt %) over a technical H-ZSM-5/Al2O3 (60-40 wt %) catalyst was studied, aiming for enhanced production of biobased benzene, toluene, and xylenes (bio-BTX). When using glycerol/toluene cofeed with a mass ratio of 93/7 wt %, a peak BTX carbon yield of 29.7 ± 1.1 C.% (at time on stream (TOS) of 1.5-2.5 h), and an overall BTX carbon yield of 28.7 C.% (during TOS of 8.5 h) were obtained, which are considerably higher than those (19.1 ± 0.4 C.% and 11.0 C.%) for glycerol alone. Synergetic effects when cofeeding toluene on the peak and overall BTX carbon yields were observed and quantified, showing a relative increase of 3.1% and 30.0% for the peak and overall BTX carbon yield (based on the feedstock). These findings indicate that the strategy of cofeeding in situ produced toluene for the conversion of glycerol to aromatics has potential to increase BTX yields. In addition, BTX production on the catalyst (based on the fresh catalyst during the first run for TOS of 8.5 h and without regeneration) is significantly improved to 0.547 ton ton-1catalyst (excluding the 76% of toluene product that is 0.595 ton ton-1catalyst for the recycle in the cofeed) for glycerol/toluene cofeed, which was 0.426 ton ton-1catalyst for glycerol alone. In particular, this self-sufficient toluene product recycling strategy is advantageous for the production and selectivity (relative increase of 84.4% and 43.5% during TOS of 8.5 h) of biobased xylenes.
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