Tandem Isomerization-Decarboxylation for Converting Alkenoic Fatty Acids into Alkenes

Murray, Rex E.; Walter, Erin L.; Doll, Kenneth M.

doi:10.1021/cs501019t

Cited by 44 publications

(38 citation statements)

References 36 publications

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“…[12][13][14][15][16][17][18][19] Am ajor drawback of this approach is that besides the expected product, ac oproduct is formed in a1 :1 ratio. [34][35][36][37][38][39] The Pd-catalyzedd ecarbonylative dehydration of fatty acids was performed using al ow loading of Pd catalyst stabilized by the Xantphos ligands and proceededu nder solvent-free conditions. [20][21][22][23][24][25] Although thesec oproducts are interesting bi-or trifunctional molecules with potentially valuable applications,t he overall yield of a-olefins is low,f or example, only 43 %w /w of glycerolt rioleate is converted into the desired high-value LAO.…”

Section: Introductionmentioning

confidence: 99%

“…[31][32][33] Better results were obtained using homogeneous catalysts. [34][35][36][37][38][39] The Pd-catalyzedd ecarbonylative dehydration of fatty acids was performed using al ow loading of Pd catalyst stabilized by the Xantphos ligands and proceededu nder solvent-free conditions. [40,41] Ir and Fe catalysts were also effective to decarbonylate saturated fatty acids.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Decarbonylation of Biosourced Substrates

et al. 2015

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Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5 h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Decarbonylation of Biosourced Substrates

et al. 2015

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“…Catalytic pyrolysis at mild temperature is a promising way to save energy input, and the key is to develop an effective catalyst. Triruthenium dodecacarbonyl (TD) is an environmental‐friendly catalyst, owing to its acid‐free, non‐corrosive and non‐toxic characteristics,, and it was found that TD is active in the catalytic decarboxylation of long‐chain fatty acid from plant oil ,. In this work, TD was applied for the catalytic depolymerization of PHB, with the aim to obtain propylene at relatively mild temperature (240 °C).…”

Section: Figurementioning

confidence: 99%

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

et al. 2019

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Poly(3-hydroxybutyrate) (PHB), a renewable feedstock from microorganisms, was a good resource for propylene production by a simple one-pot reaction. The reaction was catalyzed by triruthenium dodecacarbonyl (TD) at relatively mild temperature (240°C), and the yield and selectivity of propylene reached 22.9 wt% and 46.8%, respectively. A small part of hydrocarbon oils reached 9 wt% was also obtained, which contained 79.1 wt% of carbon and 12.3 wt% of hydrogen, with a theoretical high heating value of 41.2 MJ/kg. Poly(3-hydroxybutyrate) (PHB) [(C 4 H 6 O 2 ) n ], a material accumulated in a variety of microorganisms, is one kind of renewable aliphatic biomass. [1,2] PHB has been regarded as a potential material for the production of valuable compounds, e. g., crotonic acid (CA) and propylene, due to its special structural property and renewability. [3,4] Propylene, the second most important starting product in petrochemical industry, has been widely used for production of valuable chemicals, including polypropylene, propylene oxide, acrylonitrile, etc. [5][6][7] Recently, propylene from biomass has attained much more attention for the production of gasoline through oligomerization of olefins. [8,9] The conventional pathways of PHB conversion usually require high temperature (see Figure 1). The direct production of propylene from PHB by a conventional non-catalytic pyrolysis is not advocated, due to a low yield even at high temperature (> 300°C, Figure 1-1). [10][11][12] Propylene with a yield of 23.4 wt% can be also obtained from PHB through hydrothermal reforming. However, the temperature of the hydrothermal reforming was still high (370°C, Figure 1-2), [13] and heating the huge reaction solvent water to high temperature also increased the energy input. Catalytic pyrolysis at mild temperature is a promising way to save energy input, and the key is to develop an effective catalyst. Triruthenium dodecacarbonyl (TD) is an environmental-friendly catalyst, owing to its acid-free, non-corrosive and non-toxic characteristics, [14,15] and it was found that TD is active in the catalytic decarboxylation of long-chain fatty acid from plant oil. [16,17] In this work, TD was applied for the catalytic depolymerization of PHB, with the aim to obtain propylene at relatively mild temperature (240°C).Since no former information was reported on what is the lowest temperature or temperature range that the TD can catalytically depolymerize PHB, comprehensive thermal analysis (TG, DTG and DSC) of PHB, TD, and PHB-TD mixture were conducted (see Figure 2). Both the TG and DTG curves showed that the decomposition of TD begins at about 245°C, and therefore the highest catalytic pyrolysis temperature should be less than 245°C. PHB is a polyester with high crystallinity, which melted at around 180°C, according to the endothermic peak by the DSC curve at Figure 2B. This means that the reaction was changed from solid-solid contacting reaction to liquidphase involved reaction (solid-liquid or homogeneous phase) when the temperature was above 18...

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“…LAOs may be obtained from fatty acids using homogenous- [12][13][14][15][16][17], heterogeneous- [18], and bio-catalysts [19][20][21]. The highest activities and selectivities have so far been obtained with homogenous catalysts [2,14,22].…”

Section: Introductionmentioning

confidence: 99%

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

et al. 2017

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Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh 3) 2 Rh(CO)Cl. This complex largely draws its stability from the strength of the Rh(I)-CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III). However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction.

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Tandem Isomerization-Decarboxylation for Converting Alkenoic Fatty Acids into Alkenes

Cited by 44 publications

References 36 publications

Catalytic Decarbonylation of Biosourced Substrates

Catalytic Decarbonylation of Biosourced Substrates

One‐Pot Catalytic Conversion of Poly(3‐hydroxybutyrate) to Propylene at 240 °C

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

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