Coupling Fatty Acids by Ketonic Decarboxylation Using Solid Catalysts for the Direct Production of Diesel, Lubricants, and Chemicals

Corma, Avelino; Renz, Michael; Schaverien, Colin J.

doi:10.1002/cssc.200800103

Cited by 69 publications

(78 citation statements)

References 12 publications

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“…Then, in order to obtain liquid hydrocarbon fuels, a bifunctional catalytic system bearing a hydrogenating function (Pt, Pd, Ru) and basic sites was designed in order to perform a cascade process involving a condensationhydrogenation-dehydration-hydrogenation sequence (Scheme 39). 237 In order to decrease the reductive decarboxylation of the fatty acid on the metal sites, the process was performed in a two-bed reactor containing in the first catalytic bed MgO and the second bed either a metal/MgO or a metal/Al 2 O 3 catalyst. Among the different catalytic systems tested, the best results were obtained with the MgO + Pt/MgO system, achieving up to 70 % selectivity to n-alkanes at 98.8 % conversion.…”

Section: Fatty Acids As Platform For Liquid Hydrocarbon Fuelsmentioning

confidence: 99%

Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

2014

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In this work some relevant processes for the preparation of liquid hydrocarbon fuels and fuel additives from cellulose, hemicellulose and triglycerides derived platform molecules are discussed. Thus, it is shown that a series of platform molecules such as levulinic acid, furans, fatty acids and polyols can be converted into a variety of fuel additives through catalytic transformations that include reduction, esterification, etherification, and acetalization reactions. Moreover, we will show that liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenolysis, hydrogenation, decarbonylation/descarboxylation etc.) with the adjustment of the molecular weight via C-C coupling reactions (e.g. aldol condensation, hydroxyalkylation, oligomerization, ketonization) of the reactive platform molecules.

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Section: Fatty Acids As Platform For Liquid Hydrocarbon Fuelsmentioning

confidence: 99%

Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

2014

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“…While it is challenging to completely separate roles of two acids in their decarboxylative ketonic condensation, any shift toward acid's specialization increases the cross-selectivity. This criterion is formulated by equations (18) and (19) as described by the theoretical analysis below.…”

Section: Factors Controlling the Cross-selectivitymentioning

confidence: 99%

“…The interest to ketonization has been recently revived in connection with the bio-oil upgrading [17]. One possibility is to condense acetic acid with bio-derived fatty acids into methyl ketones [6,18]. In this process it is necessary to minimize consumption of acetic acid into the symmetrical ketone, acetone, which is an undesired by-product.…”

Section: Introductionmentioning

confidence: 99%

Cross-selectivity in the catalytic ketonization of carboxylic acids

Ignatchenko

DeRaddo

Marino

et al. 2015

Applied Catalysis A: General

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a b s t r a c tA mixture of acetic and 2-methylpropanoic (isobutyric) acids representing non-branched and branched acids, respectively, was catalytically converted to a mixture of ketones in a set of statistically designed experiments (DOE). The selectivity toward the cross-ketonization product was analyzed depending on (a) temperature within 300-450 • C range, (b) molar fraction of each acid in the mixture, from 10% to 90%, and (c) liquid hourly space velocity (LHSV) within 2-12 h −1 , and compared against the selectivity toward two symmetrical ketones. Six metal oxide catalysts were tested and ranked on their ability to yield the cross-product as opposed to the self-condensation product. The catalysts were based on either the anatase form of titania or monoclinic form of zirconia and treated with either KOH or K 2 HPO 4 . The titania catalyst treated by KOH outperformed all other catalysts by providing the cross-selectivity above the statistically expected binomial distribution. The criterion for having a high cross-selectivity in the decarboxylative ketonization is formulated mathematically as the separation of roles of two acids, one being a more active enolic component, and the other being the preferred carbonyl component. According to the suggested criterion, the less branched acetic acid reacts as both the preferred carbonyl and enolic component with untreated catalysts. Therefore, untreated catalysts promote selective formation of the symmetrical ketone, acetone, thereby decreasing the selectivity to the cross-ketone. After alkaline treatment, both the anatase form of titania and monoclinic form of zirconia increase the isobutyric acid participation as the carbonyl component. Acetic acid remains as the preferred enolic component with all treated catalysts, thus increasing the selectivity toward the cross-product in the ketonization of a mixture of carboxylic acids. The condition for achieving a high cross-selectivity by polarizing roles of the two reactants can be extended to other types of cross-condensations.

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“…[1,2] When regarding the concept of Green Chemistry,t he reaction can be considered as environmentally benign becauseahigh percentage of the substrate atoms are recovered in the product and, apart from the carboxylic acid,n of urther reagents are required. [9][10][11][12] An additional desired characteristic in biomass transformations is the formationo fac arbon-carbon bond, joining small molecules into molecules with more advantageous properties for fuels and chemicals. [3][4][5][6][7][8] The last oxygen atom in the ketone can be removed by hydrodeoxygenation via alcohol and olefin to producel inear alkanes, which can serve as fuels or lubricants.…”

Section: Introductionmentioning

confidence: 99%

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Oliver-Tomas

Renz

Corma

2017

Chemistry A European J

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For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a β-keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the α-position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing α-proton atoms. Hence, the latter are suitable to react through the β-keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2 % yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the β-keto acid intermediate.

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Coupling Fatty Acids by Ketonic Decarboxylation Using Solid Catalysts for the Direct Production of Diesel, Lubricants, and Chemicals

Cited by 69 publications

References 12 publications

Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

Cross-selectivity in the catalytic ketonization of carboxylic acids

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

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