In-situ catalytic upgrading of biomass pyrolysis vapor: Co-feeding with methanol in a multi-zone fixed bed reactor

The in-situ catalytic upgrading of the biomass pyrolysis vapor and its mixture with methanol were conducted in a fixed bed multi-zone reactor. The steps were comprised; thermally converting the biomass in the pyrolysis reactor, passing its vapor in contact with the HZSM-5 zeolite catalyst in the presence of methanol vapor, and transformation of the resulting upgraded pyrolysis vapor into the liquid product. The biomass pyrolysis and catalytic pyrolysis vapor upgrading were performed at 500 degrees C. The highly valuable chemicals production was a function of the hydrogen to carbon effective ratio (H/C-eff) of the feed. This ratio was regulated by changing the relative amount of biomass and methanol. More aromatic hydrocarbons (50.02 wt.) and less coke deposition on the catalyst (1.3 wt.) were yielded from the biomass, when methanol was co-fed to the catalytic pyrolysis process (H/C-eff = 1.35). In this contribution, the deposited coke on the catalyst was profoundly investigated. The coke, with high contents of oxo-aromatics and aromatic compounds, was generated by polymerization of biomass lignin derived components activated by catalyst acid sites. (C) 2015 Elsevier Ltd. All rights reserved

W-Nb-O oxides with tunable acid properties as efficient catalysts for the transformation of biomass-derived oxygenates in aqueous systems

[EN] W-Nb-O oxide bronzes, prepared hydrothermally, have been characterized and studied as catalysts for both the gas-phase dehydration of glycerol and the liquid-phase selective condensation of light oxygenates derived from primary treatments of biomass (a mixture containing acetic acid, ethanol, propanal, hydroxyacetone and water). By controlling the nominal composition of the catalysts, it is possible to tune their textural and acid properties (concentration and nature of acid sites) to selectively produce acrolein from glycerol or C-5-C-10 hydrocarbons (with low O contents and with high yields) from light oxygenates. Interestingly, these catalysts are stable when working in gas phase reactions and they are re-usable, with high resistance to leaching, when working in aqueous media.Financial support by the Spanish Government (CTQ-2015-68951-C3-1, CTQ-2015-67592, MAT2016-78362-C4-4-R and SEV-2016-0683) and Generalitat Valenciana (GVA, PROMETEO/2018/006) is gratefully acknowledged. A. F.-A. and D. D. thank the "La Caixa-Severo Ochoa" Foundation and Severo Ochoa Excellence Program (SVP-2016-0683), respectively, for their fellowships. The authors thank the ICTS Centro Nacional de Microscopia Electronica (UCM) for instrumental facilities.Delgado-Muñoz, D.; Fernández-Arroyo, A.; Domine, ME.; García-González, E.; López Nieto, JM. (2019). W-Nb-O oxides with tunable acid properties as efficient catalysts for the transformation of biomass-derived oxygenates in aqueous systems. Catalysis Science & Technology. 9(12):3126-3136. https://doi.org/10.1039/c9cy00367cS31263136912Huber, G. W., Iborra, S., & Corma, A. (2006). Synthesis of Transportation Fuels from Biomass:  Chemistry, Catalysts, and Engineering. Chemical Reviews, 106(9), 4044-4098. doi:10.1021/cr068360dCorma, A., Iborra, S., & Velty, A. (2007). Chemical Routes for the Transformation of Biomass into Chemicals. Chemical Reviews, 107(6), 2411-2502. doi:10.1021/cr050989dTuck, C. O., Perez, E., Horvath, I. T., Sheldon, R. 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Effects of pretreatments of Napier Grass with deionized water, sulfuric acid and sodium hydroxide on pyrolysis oil characteristics

The depletion of fossil fuel reserves has led to increasing interest in liquid bio-fuel from renewable biomass. Biomass is a complex organic material consisting of different degrees of cellulose, hemicellulose, lignin, extractives and minerals. Some of the mineral elements tend to retard conversions, yield and selectivity during pyrolysis processing. This study is focused on the extraction of mineral retardants from Napier grass using deionized water, dilute sodium hydroxide and sulfuric acid and subsequent pyrolysis in a fixed bed reactor. The raw biomass was characterized before and after each pretreatment following standard procedure. Pyrolysis study was conducted in a fixed bed reactor at 600 o�C, 30 �C/min and 30 mL/min N2 flow. Pyrolysis oil (bio-oil) collected was analyzed using standard analytic techniques. The bio-oil yield and characteristics from each pretreated sample were compared with oil from the non-pretreated sample. Bio-oil yield from the raw sample was 32.06 wt% compared to 38.71, 33.28 and 29.27 wt% oil yield recorded from the sample pretreated with sulfuric acid, deionized water and sodium hydroxide respectively. GC–MS analysis of the oil samples revealed that the oil from all the pretreated biomass had more value added chemicals and less ketones and aldehydes. Pretreatment with neutral solvent generated valuable leachate, showed significant impact on the ash extraction, pyrolysis oil yield, and its composition and therefore can be regarded as more appropriate for thermochemical conversion of Napier grass

Biomass pyrolysis and catalytic upgrading of pyrolysis vapors for the production of fuels and chemicals / Masoud Asadieraghi

The accurate determination of the biomass thermal properties is particularly important while studying biomass pyrolysis processes. The various palm oil biomass samples (palm kernel shell (PKS), empty fruit bunches (EFB) and palm mesocarp fibre (PMF)) thermochemical behavior was investigated during pyrolysis. To eliminate the negative impacts of inorganic constituents during biomass thermochemical processes, leaching method by different diluted acid solutions was chosen. The different palm oil biomass samples were pretreated by various diluted acid solutions (H2SO4, HClO4, HF, HNO3, HCl). Acids with the highest degrees of demineralization were selected to investigate the dematerialization impacts on the biomass thermal characteristics and physiochemical structure. Thermogravimetric analysis coupled with mass spectroscopy (TGA-MS) and Fourier transform infrared spectroscopy (TGA-FTIR) were employed to examine the biomass thermal degradation. TGA and DTG (Derivative thermogravimetry) indicated that the maximum degradation temperatures increased after acid pretreatment due to the minerals catalytic effects. Pyrolysis bio-oil from biomass comprised varieties of undesirable oxygenates and heavy compounds have to be treated. In-situ upgrading of bio-oil pyrolysis vapor is a promising approach demonstrating numerous benefits. Due to the highly complex nature of bio-oil, understanding the reaction pathways is highly desirable for catalyst and process screening. Therefore, the study of model compounds is the first step in simplifying the problem complexity to develop the fundamental processes and catalysts knowledge required to design bio-oil upgrading strategies. Three most important classes of catalysts including zeolites, mesoporous catalysts and metal based catalysts are mostly utilized for vapor phase bio-oil upgrading. The in-situ catalytic upgrading of PKS fast pyrolysis vapors was performed over each individual meso-H-ZSM-5, Ga/meso-HZSM-5 and Cu/SiO2 catalyst or a cascade system of iv them in a multi-zone fixed bed reactor. The catalysts were characterized using SEM, XRF, XRD, N2 adsorption and NH3-TPD methods. Furthermore, the produced bio-oils were analyzed using GC–MS, FTIR, CHNS/O elemental analyzer and Karl Fischer titration. Among different catalysts, meso-H-ZSM-5 zeolite demonstrated a very good activity in aromatization and deoxygenation during upgrading. The gallium incorporation into the meso-HZSM-5 zeolite increased the bio-oil yield and aromatics selectivity. A cascade system of catalysts comprising meso-HZSM-5, Ga (1.0 wt. %) /meso-HZSM-5 and Cu (5.0 wt. %) /SiO2 indicated the best performance on aromatics formation (15.05 wt. %) and bio-oil deoxygenation through small oxygenates, lignin derived phenolics and sugar derived compound conversion, respectively. Furthermore, catalytic upgrading of the PKS biomass pyrolysis vapor and its mixture with methanol were conducted in aforementioned fixed bed multi-zone reactor using HZSM-5 zeolite catalyst. The highly valuable chemicals production was a function of the hydrogen to carbon effective ratio (H/Ceff.) of the feed. This ratio was regulated by changing the relative amount of biomass and methanol. More aromatics (50.02 wt. %) and less coke deposition on the catalyst (1.3 wt. %) were yielded from the biomass, when methanol was co-fed to the catalytic pyrolysis process (H/Ceff. = 1.35). In this contribution, the deposited coke on the catalyst was profoundly investigated. The coke, with high contents of oxo-aromatics and aromatic compounds, was generated by polymerization of biomass lignin derived components

A Parametric Study of the Drying Process of Polypropylene Particles in a Pilot-Scale Fluidized Bed Dryer using Computational Fluid Dynamics

Fluidized Bed Dryer (FBD) is one of the efficient methods for drying moist particulate products. At the same time, the design and optimization of a full industrial scale FDB requires extensive studies. Using a pilot-scale dryer can be deemed as an efficient tool to obtain essential information on the drying phenomenon. Although these kinds of experimental analyses can provide valuable insight, there are still some operational limitations, including high-pressure or high-temperature conditions, which make the use of a computational procedure highly desirable. In this study, Computational Fluid Dynamics (CFD) approach has been employed to investigate a dryer. The results of numerical simulations were verified using the experimental data obtained from a pilot-scale dryer. The present investigation aims to study the effects of different operating conditions. It was observed that the impacts of gas inlet temperature were negligible, as the dryer was equipped with a thermal jacket, while the gas injection velocity had significant effects on the dryer’s performance. Moreover, the efficiencies of the conical and horizontal gas distributors were compared and it was concluded that the conical configuration results in better performance. The numerical and experimental investigation from this study can facilitate the design and scale-up of an industrial dryer plant