Ultrasonic-assisted catalytic transfer hydrogenation for upgrading pyrolysis-oil

Struhs, Ethan; Hansen, Samuel; Mirkouei, Amin; Ramirez-Corredores, Maria Magdalena; Sharma, Kavita; Spiers, Robert; Kalivas, John H.

doi:10.1016/j.ultsonch.2021.105502

Cited by 14 publications

(7 citation statements)

References 35 publications

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“…Ammonium formate decomposed into formic acid and ammonia in the Pd/MWCNTs system. [ 37 ] With increasing formic acid concentration, HO• could be effectively removed, [ 38 ] that is, formic acid reacted with HO• to generate HCOO•. As free radicals reacted with solute molecules at the bubble–liquid interface, [ 36 ] HCOO• and water were hydrogenated with soybean oil as hydrogen donors under the catalysis of Pd/MWCNTs.…”

Section: Results and Analysismentioning

confidence: 99%

“…The reaction equation of water to produce free radicals is as follows [36] H 2 O → H • + • OH (8) Ammonium formate decomposed into formic acid and ammonia in the Pd/MWCNTs system. [37] With increasing formic acid concentration, HO• could be effectively removed, [38] that is, formic acid reacted with HO• to generate HCOO•. As free radicals reacted with solute molecules at the bubble-liquid interface, [36] The results showed that ultrasound can accelerate the reaction rate through the formation of highly active free radicals and the reaction between free radicals and solute molecules.…”

Section: Study On Mechanism Of Cth Catalyzed By Ultrasound-assisted P...mentioning

confidence: 99%

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Application of Pd/MWCNTs Catalyst in Ultrasound‐Assisted Catalytic Transfer of Hydrogenated Soybean Oil

Guo

et al. 2022

Euro J Lipid Sci & Tech

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To provide a new, safe, and efficient way to produce hydrogenated oils, a loaded Pd/MWCNTs catalyst is studied and applied to the catalytic transfer of soybean oil under ultrasound conditions. Pd is loaded onto multiwalled carbon nanotubes (MWCNTs) by impregnation, and the Pd loading is ≈0.8%. Through X‐ray diffraction analysis, it is found that the characteristic emission peaks of Pd appear at the 2θ = 40.3°, 46.7°, and 68.2° locations. Moreover, transmission electron microscopy reveals that the catalyst is uniformly dispersed and less agglomerated. X‐ray photoelectron spectroscopy spectra show that Pd is successfully loaded onto MWCNTs. Pd/MWCNTs catalyst is then applied to the catalytic transfer of hydrogenated soybean oil. The results show that when ultrasonic power is 100 W, catalyst concentration is 2.0% w/w, hydrogenation temperature is 80 °C, donor concentration is 0.32 mol/50 mL H2O, the maximum hydrogenation conversion is 31.97%, and the content of trans‐fatty acid is only 1.52%. Pd/MWCNTs catalyst can be recycled for four times in catalytic hydrogenation of soybean oil, and the activity of the catalyst decreases to 78.5% at the fourth time. Practical Application (PA): In this study, Pd is well loaded on multiwalled carbon nanotubes (MWCNTs) by means of ultrasound. The ultrasonic assisted Pd/MWCNTs catalyst catalyzes the transfer hydrogenation of soybean oil. The hydrogenation conversion rate of soybean oil is significantly improved by this method, and the content of trans fatty acid in hydrogenated soybean oil is low. The Pd/MWCNTs can be recycled for four times as a catalyst.

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Section: Results and Analysismentioning

confidence: 99%

Section: Study On Mechanism Of Cth Catalyzed By Ultrasound-assisted P...mentioning

confidence: 99%

Application of Pd/MWCNTs Catalyst in Ultrasound‐Assisted Catalytic Transfer of Hydrogenated Soybean Oil

Guo

et al. 2022

Euro J Lipid Sci & Tech

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“…The existence of ammonium formate signal in some samples suggests that not all H-donor molecules decayed under the circumstances used. This is especially relevant for samples with a high concentration of H-donor (Struhs et al, 2021). Since the pyrolysis process was used for bio-oil production the 1 H and 13 C NMR study has been deployed for the evaluation of H-C functional groups.…”

Section: Bio-oil Characterizationmentioning

confidence: 99%

Catalytic microwave preheated co-pyrolysis of lignocellulosic biomasses: A study on biofuel production and its characterization

Jacqueline

Muthuraman

Karthick

et al. 2022

Bioresource Technology

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“…In order to be able to process fast pyrolysis bio-oil in conventional hydrotreating reactors, different approaches have been attempted, including mild hydrotreating for stabilization of the fast pyrolysis bio-oil, formulation using surfactants and low molecular weight alcohols, esterification and dewatering using alcohols, ultrasonic-assisted catalytic transfer hydrogenation, coprocessing in continuously stirred tank reactors using slurry hydrocracking catalysts and hydrogen, , or utilizing adsorbents for removal of reactive carbonyl groups . The common theme in all these approaches is to stabilize or remove/convert the reactive molecules present in fast pyrolysis bio-oil.…”

Section: Introductionmentioning

confidence: 99%

Derivatizing of Fast Pyrolysis Bio-Oil and Coprocessing in Fixed Bed Hydrotreater

et al. 2022

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In several countries forest-based biofuels are being developed and to some extent also deployed. Fast pyrolysis bio-oil produced from, for example, sawdust, has now been coprocessed in fluid catalytic cracking refinery units in a number of commercial trials. However, this application is limited to about 10% of the total feed, and coprocessing in conventional fixed bed hydrotreaters is necessary to reach the high potential with this feedstock. Feeding and upgrading of fast pyrolysis bio-oil in a fixed bed reactor configuration is still problematic due to the inherent bio-oil properties. Stabilization of reactive compounds in fast pyrolysis bio-oil and mild hydrotreatment in a separate refining unit prior to refinery integration has therefore been developed the past decade. Another approach, presented here, involves complete dewatering of fast pyrolysis bio-oil by azeotropic distillation using mesityl oxide as the solvent, followed by conversion of the abundant hydroxyl compounds via mixed anhydride esterification methodology using an external source of mixed carboxylic acids of different chain lengths originating from renewable tall oil fatty acids, providing a lipophilic feed component. Dewatering and derivatizing were carried out in reactors up to 50 dm3 with a mass ratio of fast pyrolysis bio-oil to tall oil fatty acid of 10:13. The produced lipophilic oils were miscible with a petroleum light gas oil fraction and exhibited superior stability even after accelerated aging at elevated temperature (80 °C). The derivatized oils were thus mixed with light gas oil, with a proportion of 30 wt % derivatized oil in final blends and hydrotreated continuously in pilot fixed bed reactors for 14 days at 4 operating conditions without plugging or excessive exotherms. The test conditions were varied; the reactor pressure was either 55 or 80 bar, temperature 380 or 400 °C, and liquid hourly space velocity either 1 or 2 h–1 during the hydrotreatment. Successful hydrodeoxygenation and desulfurization were accomplished, whereas an increasing nitrogen concentration could be observed in the liquid products with the particular catalyst and reaction conditions employed. The observed hydrogen consumption (15–20 g/kg feed) was compared with the stoichiometric consumption for direct deoxygenation and with typical consumptions for industrial hydrotreated vegetable oil processing. The measured biogenic carbon content in hydrotreated liquid products (26.7%) agreed extremely well with the calculated biogenic carbon content in the hydrotreating feed (26.6%) that consisted of the blend of derivatized oil and petroleum light gas oil. The overall results are very promising since simple unit operations can be used to produce derivatized fast pyrolysis bio-oils that do not need additional standalone hydrotreating units but can be coprocessed in existing ones.

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Ultrasonic-assisted catalytic transfer hydrogenation for upgrading pyrolysis-oil

Cited by 14 publications

References 35 publications

Application of Pd/MWCNTs Catalyst in Ultrasound‐Assisted Catalytic Transfer of Hydrogenated Soybean Oil

Application of Pd/MWCNTs Catalyst in Ultrasound‐Assisted Catalytic Transfer of Hydrogenated Soybean Oil

Catalytic microwave preheated co-pyrolysis of lignocellulosic biomasses: A study on biofuel production and its characterization

Derivatizing of Fast Pyrolysis Bio-Oil and Coprocessing in Fixed Bed Hydrotreater

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