Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Some experimental studies have demonstrated the positive influence of the concentration of Brønsted acid sites on the acrolein yield, as well as the relationship of Lewis sites on the production of acetol. These authors contributed equally to the work. Their HA values are between −8 and −3 and result in acrolein selectivities up to 70%; however, these catalysts show low stability and rapid deactivation. )}�tw�JGK��n)�Z�S���.�Lio��������r��C��G�|x箊���ꨶd� �d��b���NO]��]6T/�`L�I�X9�:гzVz0�!�̑�Cˤ�� P�P Z�!۲��อW�7�/�\����DV2� �3؍b�~M�M�l�g3���Hy�����w����}3�'_���*�3�z��r&�Bڌ�a=Xv�$̊U�J�-1s�����J�p�8^����{��[*�5}��r�?K�hY�)��n(����'�=� ���Ǐ�Ἳ��^���2?�S'\�3]��ő��l֪� The main process variables in the gas phase are the reaction temperature, the concentration of glycerol in water, and the space velocity in fixed-bed reactors. Similar results have been reported for the reaction in the presence of NH4-La-modified H-β zeolite, hierarchical mesoporous H-ZSM-5 zeolites, and phosphotungstic acid supported on Cs-modified SBA-15 [30, 32, 33, 34]. The purpose of this study is to synthesize acrolein from glycerol using FePO 4 catalyst in liquid phase dehydration. Among the tested zeolites, H-ZSM-5 (150), H-β (25), and H-ferrierite (55) showed high catalytic activities with conversions of 93.7, 95.2, and 70.9%, respectively, and acrolein yields around 53.8, 44.7 and 54.6% in the same order, at 614 K. In other studies, Corma et al. Article (Special Column on Novel Catalysts for Energy and Environmental Issues), Conversion of glycerol to acrolein by mesoporous sulfated zirconia-silica catalyst. The glycerol-dehydration reaction was continued for a few hours, and glycerol conversion (Equation 1) and acrolein selectivity (Equation 2) were used to evaluate the catalyst performance. An open‐macropore‐structured and Brønsted‐acidic catalyst (Marigold‐like silica functionalized with sulfonic acid groups, MS‐FS) was synthesized for the stable and selective production of acrolein from glycerol. MUICaT-5 catalyst gave 86% of glycerol conversion and 60% of acrolein selectivity. Rational Design of a Bifunctional Catalyst for the Oxydehydration of Glycerol: A Combined Theoretical and Experimental Study, cssc_201402057_sm_miscellaneous_information.pdf. Unlimited viewing of the article PDF and any associated supplements and figures. Working off-campus? The aim of the present investigations is the heterogeneously catalysed conversion of glycerol to acrolein by dehydration. The main reason for fast deactivation is coke deposition on the catalyst surface. Group 3 includes catalysts such as alumina impregnated with phosphoric acid, heteropolyacids supported on alumina, niobium oxide calcined at 773 K, HZSM zeolite, and pure alumina. [18] evaluated the activity of a ZSM-5-based catalyst on the conversion of glycerol/water mixtures to acrolein in a fluidized-bed reactor. /Filter/FlateDecode These solids show acrolein selectivities not greater than 30% but remain stable for 10 h on stream. Highly Efficient Process for the Conversion of Glycerol to Acrylic Acid via Gas Phase Catalytic Oxidation of an Allyl Alcohol Intermediate. Effect of the reaction temperature on the glycerol conversion and acrolein selectivity with time-on-stream. The reactor temperature determines the products present in the glycerine dehydration reaction mixture, and according to thermodynamics, the acrolein production would be predominant from 480 K reaching its maximum at 600 K [7]. Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. Data from [28]. An improvement of the acrolein selectivity was also observed with the rise of temperature at initial activities, maintaining the trends along the TOS and resulting in a higher acrolein yield at 593 K even after 10 h. Similar behavior has been reported for the glycerol dehydration performed over several catalysts such as H-ZSM-5 (150), H-β (25) and H-ferrierite (55), La-NH4-modified H-β (13) zeolite, and aluminosilicophosphate nanospheres (ASPN-40) [23, 24, 30, 31]. Continuous two-step catalytic conversion of glycerol to pyridine bases in high yield. The production of acrolein from glycerine in the presence of hierarchical H-ZSM-5 zeolites has proven to be feasible. The Reaction Pathway of Cellulose Pyrolysis to a Multifunctional Chiral Building Block: The Role of Water Unveiled by a DFT Computational Investigation. We use cookies to help provide and enhance our service and tailor content and ads. Data from [24]. [33] showed that desilicated samples of H-ZSM-5 zeolite resulted in an improvement of the glycerol conversion (100%) and the acrolein yield (66–74%) regarding the parent zeolite (Si/Al = 40) which reached 95% of conversion and an acrolein yield of 53% at 548 K. The desilicated zeolites maintained the glycerol conversion around 70% up to 7 h of TOS, while the acrolein yield decreased to 20% at the same time. The glycerol conversion increases with acid center concentration under the 15 specified reaction condition. When working with continuous reactors, the space velocity is useful to relate the feed rate to the amount of catalyst. Supported heteropolyacids, mainly phosphotungstic (H3PW12O40) and silicotungstic acid (H4SiW12O40), and their alkali-substituted salts present high activity to convert glycerine into acrolein. Use the link below to share a full-text version of this article with your friends and colleagues. It is proposed that the milder acidity due to dilution of zirconium species by silica and large pore size for faster diffusion contributed towards the better catalytic performance. Zeolites modified by ion-exchange have also been tested in the glycerol dehydration. A high acrolein yield of 73 % was achieved and maintained for 50 h in the presence of the MS‐FS catalyst. Effect of the water content in the feedstock on the glycerol conversion and the acrolein yield with time-on-stream. Consequently, the catalyst stability with the time-on-stream (TOS) is adversely affected when increasing glycerol content in the feed. Dehydration of glycerol was carried out at 523 K , where the temperature was lower than that of previous reports (ca. Table 4 summarizes some relevant catalysts used in the gas-phase conversion of glycerine to acrolein, as well as the reaction conditions and their catalytic performance. . [23, 24] as catalysts for the glycerine dehydration in a fixed-bed reactor, taking into account several parameters such as the composition of the catalyst (SiO2/Al2O3 molar ratio), the reaction temperature, and the amount of water in the feed. Kim et al. 4–6. Learn about our remote access options, World Class University (WCU) program of chemical Convergence for Energy & Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul 151‐741 (Republic of Korea), Fax: (+82) 2‐885‐6670. 2 Care should be taken concerning the choice of the reference conditions, since the three ways of expressing space velocity find extensive use. By Vinicius Rossa, Gisel Chenard Díaz, Germildo Juvenal Muchave, Donato Alexandre Gomes Aranda and Sibele Berenice Castellã Pergher, By Erika Chrisman, Viviane Lima and Príscila Menechini. If you do not receive an email within 10 minutes, your email address may not be registered, HeadquartersIntechOpen Limited5 Princes Gate Court,London, SW7 2QJ,UNITED KINGDOM. Continuous Flow Organic Chemistry: Successes and Pitfalls at the Interface with Current Societal Challenges. Refined acrolein is needed as starting material for the synthesis of fine and intermediate chemicals such as methionine, fragrances as well as dyes. Published by Elsevier B.V. All rights reserved. Data from [26]. The conversion of glycerol declined from 99.8 to 94%, while the acrolein yield decreased from 91.8 to 67.7% with the increment in glycerol concentration from 10 to 40%. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. [34] used a mesoporous molecular sieve modified (SBA-15) with cesium as support for H3PW12O40 and used the resulting solid (H3PW12O40/Cs-SBA-15) as catalyst for the glycerol dehydration. This work was supported by Grant-in-Aid for Research Activity Start-up (KAKENHI, 21860004) and for Young Scientists (KAKENHI, 26709060) from Japan Society for the Promotion of Science (JSPS). The catalyst calcined at 673 K achieved 98.9% of glycerol conversion and an acrolein yield of 74.4% at 558 K. The acrolein yield and the deactivation were found to be higher and slower, respectively, than those of WO3/ZrO2 and H-ZSM-5 which are typical acid catalysts [38]. X g l y c e r o l = n r e a c t e d n f e e d × 100 % = n f e e d − n q u a n t i f i e d n f e e d × 100 %
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