102-62-5Relevant academic research and scientific papers
Activity and stability of polyaniline-sulfate-based solid acid catalysts for the transesterification of triglycerides and esterification of fatty acids with methanol
Zi?ba,Drelinkiewicz,Konyushenko,Stejskal
, p. 169 - 181 (2010)
A polymeric catalyst, polyaniline-sulfate, was studied in the transesterification of triglycerides (triacetin, castor oil) and esterification of fatty acid, ricinoleic acid with methanol at mild conditions (temperature of 50-60 °C). Polymer powder (PANI-S) and three samples of various contents of polymer deposited on carbon support were examined. The samples of catalysts, before and after catalytic tests were characterized by BET, FT-IR, XRD and SEM techniques. The acid capacity was also determined. All the samples were found to be active solid acid catalysts in both tested reactions. Catalytic performance of polyaniline-sulfate-based catalysts for methanolysis of triacetin (glycerol triacetate) the shortest triglyceride molecule differed from that for vegetable oil, castor oil, consisting of long chain triglycerides of ricinoleic acid. In transesterification of triacetin PANI-S powder was more active than carbon-supported catalysts. In methanolysis of vegetable oil the outermost surface of catalysts was mainly involved and much higher activity was exhibited by carbon-supported catalysts with deposited polymer, especially with low content of polymer (13.1 wt.%). The activity of polyaniline-sulfate-based catalysts was almost stable during recycling use in tested reactions. After five successive catalytic runs, their activities were found to be ca. 80-95% relative to the activities of fresh catalysts.
Catalytic acetylation of glycerol with acetic anhydride
Silva, Leonardo N.,Gon?alves, Valter L.C.,Mota, Claudio J.A.
, p. 1036 - 1039 (2010)
We studied the acetylation of glycerol with acetic anhydride using different solid acid catalysts. The results indicated that at 60 °C, zeolite Beta and K-10 Montmorillonite showed 100% selectivity to triacetin within 20 min, with a molar ratio of 4:1. Amberlyst-15 acid resin yielded 100% triacetin after 80 min, whereas niobium phosphate gave diacetin and triacetin in 53% and 47% selectivity, respectively. All catalysts were more selective to triacetin than the uncatalyzed reaction. By contrast, zeolite Beta gave poor yield of triacetin when acetic acid was used as acetylating agent. The different behavior was explained in terms of the stabilization of the acylium ion intermediate.
Sulfonic acid functionalized deoxycellulose catalysts for glycerol acetylation to fuel additives
Kim, Inbae,Kim, Jaesung,Lee, Doohwan
, p. 31 - 37 (2014)
Various forms of sulfonic acid (SO3H) functionalized cellulose-based heterogeneous catalysts were prepared, and their properties on glycerol acetylation reactions to mono-, di-, and triacetin products were investigated. Superior catalytic activity and stability for the reactions was observed on SO3H-NDOC catalyst that is obtained by (i) crosslinking of the cellulose units with epichlorohydrin into a three-dimensionally-networked deoxycellulose-matrix and (ii) sulfonic acid functionalization on the crosslinked deoxycellulose support via CS atomic linkages (CSO3H). It was found that sulfonic acid functionalization via an ether type OS atomic linkage (COSO3H) or the direct utilization of the pristine cellulose support without a fortification by crosslinking led to significant deactivation of the catalysts by substantial acidity loss. The intrinsic glycerol conversion turnover rate on SO3H-NDOC was comparable to that of commercial Amberlyst-15 solid resin, demonstrating the effectiveness of this renewable cellulose-derived heterogeneous catalyst for glycerol acetylation to fuel additives.
Fe4(SiW12O40)3-catalyzed glycerol acetylation: Synthesis of bioadditives by using highly active Lewis acid catalyst
Da Silva, Márcio José,Liberto, Natalia Aparecida,De Andrade Leles, Lorena Cristina,Pereira, Ulisses Alves
, p. 69 - 83 (2016)
In order to investigate the effect of Lewis acidic metals on the acid properties of Keggin heteropolyacids catalysts, a set of metal-exchanged HPAs (i.e. M3/nPW12O40, M3/nPMo12O40 and M4/nSiW12O40 (M?=?Cu, Co and Mn, n?=?2; M?=?Fe, n?=?3) were synthesized and their activity on glycerol esterification with acetic acid was evaluated. This procedure avoids the use of corrosive Br?nsted acid catalysts. Regardless of the heteropoly anion, the activity of catalysts in terms of metal cations followed the sequence: Fe3+>?Cu2+>?Mn2+>?Co2+. It has been found that among the HPAs, only H4SiW12O40 has the acidic protons that can be successfully exchanged with Fe3+ cations, resulting in Fe4(SiW12O40)3 salt, the most active and selective catalyst. The highest conversion (ca.99.9%) was achieved in Fe4(SiW12O40)3-catalyzed esterification reactions, along with the highest selectivity for di and triacetyl glycerol (ca.55 and 42%, respectively). Effects of temperature, stoichiometry of reactants, concentration and nature of catalysts were assessed. A kinetic study of Fe4(SiW12O40)3 or H4SiW12O40-catalyzed reactions was conducted and the activation energy determined.
Pheromone synthesis. Part 255: Synthesis and GC-MS analysis of pheromonal triacylglycerols of male Drosophila fruit flies
Mori, Kenji
, p. 5752 - 5762 (2014)
Pheromonal triacylglycerols and their analogs, 1A, 1B, 2A, 2B, 3A, 3B, and 3C, of male Drosophila fruit flies were synthesized and analyzed by GC-MS. Their GC retention times were found to be a reliable measure to analyze and identify these triacylglycerols with acetyl, oleoyl and tigloyl groups, although the stereo- and regioisomers of 1 (1A and 1B), 2 (2A and 2B), and 3 (3A, 3B, and 3C) could not be distinguished from each other by MS alone.
Lanthanum nanocluster/ZIF-8 for boosting catalytic CO2/glycerol conversion using MgCO3as a dehydrating agent
Hu, Chechia,Chang, Chien-Wei,Yoshida, Masaaki,Wang, Ke-Hsuan
, p. 7048 - 7058 (2021/03/29)
A lanthanum-modified zeolitic imidazolate framework (La/ZIF-8) was developed to produce glycerol carbonate using CO2and glycerol as raw materials. La/ZIF-8 provides a high catalytic glycerol conversion efficiency owing to its surface-attached nanoclusters of La2O3, which can be viewed as La3+-O2?pairs that strengthen the Lewis basicity and acidity, and the large specific surface area of ZIF-8. The catalytic glycerol conversion and the yield of glycerol carbonate were 46.5% and 35.3%, respectively, using CH3CN as a dehydrating agent. With increase in the amount of CH3CN, the water molecules could react with CH3CN to reduce the selectivity. When an inorganic dehydrating agent, MgCO3, was used to physically adsorb and remove water molecules in the reaction, the selectivity of the reaction could be increased to over 95%, which is the highest ever reported. Reaction kinetics analysis also revealed that the activation energy of using MgCO3(5.4 kJ mol?1) as a dehydrating agent is lower than that using CH3CN (7.8 kJ mol?1). Moreover, the La/ZIF-8 could be recycled and reused at least three times with high catalytic performance. This study provides an effective material with dual Lewis basicity and acidity for CO2/glycerol conversion and significantly improves the catalytic performance using an inorganic dehydrating agent.
A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions
Hou, Zhaoyin,Jiang, Yuanyuan,Long, Yihua,Wang, Zhengbao,Ye, Boyong,Zhao, Huaiyuan,Zhou, Ruru
, p. 1772 - 1781 (2021/06/28)
Solid acid catalyst plays a crucial role in the petroleum refinery industry and bio-refinery technology. In this work, p-phenolsulfonic acid (PSA) was successfully grafted onto the surface of KH560-modified zirconium phosphate (K-ZrP) in a facile routine. The structure and property of this organic-inorganic combined solid acid PSA/K-ZrP-x were characterized via XRD, FTIR, 13C solid-state NMR, TG, N2 adsorption-desorption, SEM, pyridine-adsorption FTIR and XPS technologies. The characterization results showed that KH560 can bond with ZrP and promote the grafting of PSA on the surface of K-ZrP via the condensation reaction between its epoxy ring and the phenolic hydroxyl group in PSA. Consequently, PSA/K-ZrP-2 exhibited excellent performance and stability in the transesterification between glycerol and methyl acetate among the tested H3PW12O40, Amberlyst-45, HBEA, HZSM-5, ZrP, AlCl3 and FeCl3 catalysts. The calculated conversion of glycerol reached 81.3% with a 97.9% selectivity for monoacetin (MAG) and diacetin (DAG) with a 2.2% dosage of [H+] at 100 °C for 4 h. The highest specific activity of PSA/K-ZrP-2 reached 24028.2 mg-glycerol/g-cat/h in a short reaction time (at 0.17 h), and it could be recycled five times without obvious deactivation.
Ordered mesoporous zirconium silicates as a catalyst for biofuel precursors synthesis
Bu, Quan,Cai, Jin,Mao, Hanping,Vasudevan, Srinivasan Vinju
, (2021/11/16)
Zirconium incorporated three-dimensional ordered mesoporous silica (FDU-5) catalysts with different Si/Zr (100, 50 and 25) ratios were synthesized using an Evaporation Induced Self Assembly (EISA) method to maximize the incorporation of zirconium sites in the silica framework. The physicochemical properties of the synthesized materials were characterized by several techniques such as XRD, N2 sorption, diffuse reflectance UV–Vis, TEM, ammonia TPD, ICP-OES and pyridine adsorbed FT-IR. The catalytic activity was evaluated in acid-catalyzed esterification of glycerol with acetic acid. The effects of different reaction parameters were studied to optimize the maximum yields, such as reaction temperature, catalyst loading, acid/alcohol molar ratio, and reaction time. Esterification of glycerol with levulinic acid and levulinic acid with ethanol was also performed to synthesize fuel precursors. Reaction results showed that the prepared Zr-FDU-5(25) material was a very high catalytic activity, which depended mostly on the zirconium species' availability on the surfaces and framework. This zirconium containing FDU-5 material was very active in the esterification reaction and selective product formation at certain reaction conditions. The selected catalyst was recycled five times without significant loss in its activity.
Biodiesel Glycerin Valorization into Oxygenated Fuel Additives
Catarino, Mónica,Gomes Fonseca, Frederico,Gomes, Jo?o,Soares Dias, Ana Paula
, (2021/05/26)
Current industrial methods of biodiesel production lead to an excess of crude glycerin which requires costly purification before commercialization. Production of oxygenated fuel additives is a potential route for glycerin valorization. Glycerin acetylation was carried out over heterogeneous acid catalysts (15%, glycerol weight basis) using glacial acetic acid (molar ratio = 9). The catalysts, containing different amounts of phosphate species (P/Si from 10 to 20 atomic ratio), were prepared by wet impregnation of commercial silica with aqueous solutions of diammonium phosphate and ortho-phosphoric acid. X-ray diffraction patterns of calcined solids presented amorphous patterns like raw silica. The prepared catalysts presented, at 120?°C, glycerol conversion higher than 89.5% after 1?h of reaction, been diacetin the major product, with triacetin selectivities lower than 26.1%. Diacetin selectivity was found to be almost invariant with catalyst acidity thus underlining the relevance of catalyst porosity due to the large acetins molecules sizes. The slow rate of triacetin diffusion in narrow pores of catalyst might be responsible for the relatively low yield obtained. Surface phosphate species showed a slow rate of leaching in the reaction medium showing high catalyst stability. Graphical Abstract: [Figure not available: see fulltext.]
A transesterification-acetalization catalytic tandem process for the functionalization of glycerol: The pivotal role of isopropenyl acetate
Calmanti, Roberto,Perosa, Alvise,Rigo, Davide,Selva, Maurizio
, p. 5487 - 5496 (2020/09/23)
At 30 °C, in the presence of Amberlyst-15 as a catalyst, a tandem sequence was implemented by which a pool of innocuous reactants (isopropenyl acetate, acetic acid and acetone) allowed upgrading of glycerol through selective acetylation and acetalization processes. The study provided evidence for the occurrence of multiple concomitant reactions. Isopropenyl acetate acted as a transesterification agent to provide glyceryl esters, and it was concurrently subjected to an acidolysis reaction promoted by AcOH. Both these transformations co-generated acetone which converted glycerol into the corresponding acetals, while acidolysis sourced also acetic anhydride that acted as an acetylation reactant. However, tuning of conditions, mostly by changing the reactant molar ratio and optimizing the reaction time, was successful to steer the set of all reactions towards the synthesis of either a 1?:?1 mixture of acetal acetates (97% of which was solketal acetate) and triacetin, or acetal acetates in up to 91% yield, at complete conversion of glycerol. To the best of our knowledge, a one-pot protocol with such a degree of control on the functionalization of glycerol via transesterification and acetalization reactions has not been previously reported. The procedure was also easily reproduced on a gram scale, thereby proving its efficiency for preparative purposes. Finally, the design of experiments with isotopically labelled reagents, particularly d4-acetic acid and d6-acetone, helped to estimate the contribution of different reaction partners (iPAc/AcOH/acetone) to the formation of final products. This journal is
