629-50-5Relevant articles and documents
CONTINUOUS PROCESS FOR THE PRODUCTION OF ALKANES
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Page/Page column 12-13, (2021/11/13)
Continuous reductive dehydroxymethylation process for the preparation of alkanes from primary aliphatic alcohols, having 3 to 25 carbon atoms, in the presence of hydrogen and a catalyst in a reactor at a pressure of ≥ 2 bar, characterized in that the dehydroxymethylation takes place in the vapor phase.
Highly stable and selective catalytic deoxygenation of renewable bio-lipids over Ni/CeO2-Al2O3 for N-alkanes
Ba, Wenxia,Cui, Huamin,Fu, Lin,Li, Yongfei,Liu, Yuejin
, (2021/07/31)
Ni-based catalysts are easy deactivated in bio-lipids deoxygenation due to metal aggregation and Ni leaching. They also suffer from the hydrocracking of C–C bonds due to strong acidity at high reaction temperature (≥ 300 ℃). Herein, a series of Ni/CeO2-Al2O3 catalysts with different Ce/Al ratio were prepared by one-pot sol-gel method. The characteristic results showed that an appropriate addition of Ce both increase the catalytic activity and stability in bio-lipids deoxygenation. The oxygen vacancies formed by Ce introduction weaken the strong interaction of Ni-Al, thus improving Ni sites dispersion. Additional, Ce-addition in NiCeAl system increases weak and medium acidity and decreases strong acidity, preventing the C–C bond cleavage of hydrocarbon. As the result, the Ni/CeAl-3.0 catalyst afforded a 97.1 % n-C17 yield at 99.9 % MO conversion under 2.5 MPa H2 at 300 ℃ for 6 h. Minor C15-16 alkanes (17 yield). After simple regeneration, n-C17 yield was recovered to 95 %. Furthermore, non-edible bio-lipids (JO and WCO) can be converted to C13-18 alkanes with 95.2 % and 93.8 % yields, respectively.
Light-Driven Enzymatic Decarboxylation of Dicarboxylic Acids
Chen, Bi-Shuang,Liu, Lan,Zeng, Yong-Yi,Zhang, Wuyuan
, p. 553 - 559 (2021/06/25)
Photodecarboxylase from Chlorella variabillis (CvFAP) is one of the three known light-activated enzymes that catalyzes the decarboxylation of fatty acids into the corresponding C1-shortened alkanes. Although the substrate scope of CvFAP has been altered by protein engineering and decoy molecules, it is still limited to mono-fatty acids. Our studies demonstrate for the first time that long chain dicarboxylic acids can be converted by CvFAP. Notably, the conversion of dicarboxylic acids to alkanes still represents a chemically very challenging reaction. Herein, the light-driven enzymatic decarboxylation of dicarboxylic acids to the corresponding (C2-shortened) alkanes using CvFAP is described. A series of dicarboxylic acids is decarboxylated into alkanes in good yields by means of this approach, even for the preparative scales. Reaction pathway studies show that mono-fatty acids are formed as the intermediate products before the final release of C2-shortened alkanes. In addition, the thermostability, storage stability, and recyclability of CvFAP for decarboxylation of dicarboxylic acids are well evaluated. These results represent an advancement over the current state-of-the-art.
An unconventional DCOx favored Co/N-C catalyst for efficient conversion of fatty acids and esters to liquid alkanes
Li, Jiang,Liu, Jiaxing,Zhang, Junjie,Wan, Tong,Huang, Lei,Wang, Xintian,Pan, Runze,An, Zhidong,Vlachos, Dionisios G.
, (2019/12/26)
Cobalt (Co) catalysis has recently attracted significant attention in the field of biomass conversion. However, the fabrication of highly dispersive Co nanoparticles at high metal loading with selective facet exposure to achieve specific selectivity is still questionable. In this work, a nitrogen-doped carbon-supported Co catalyst is fabricated for efficient conversion of fatty acids and esters to liquid alkanes. Nitrogen-doping facilitates a highly uniform dispersion of Co nanoparticles even at a high Co loading of 10 wt% and after recycling for 5 runs. The Co/N-C catalyst affords an unconventional decarbonylation/decarboxylation (DCOx) dominant selectivity probably due to partial reduction of cobalt oxides to α-Co0 with only exposure of the (111) facet. Co-existence of Co and N-C leads to strong Lewis acidity and basicity, facilitating the interaction between catalyst and –COOH group, and some important acid-catalyzed step-reactions. The versatility of the Co/N-C catalyst is demonstrated through conversion of various fatty acids and esters.
Production of Bio Hydrofined Diesel, Jet Fuel, and Carbon Monoxide from Fatty Acids Using a Silicon Nanowire Array-Supported Rhodium Nanoparticle Catalyst under Microwave Conditions
Baek, Heeyoel,Fujii, Takashi,Fujikawa, Shigenori,Kashimura, Keiichiro,Sato, Takuma,Tsubaki, Shuntaro,Uozumi, Yasuhiro,Wada, Yuji,Yamada, Yoichi M. A.
, p. 2148 - 2156 (2020/02/11)
Biodiesel was efficiently produced from biomass fatty acids using renewable gas H2 and a reusable heterogeneous catalyst under low-energy-consumption microwave conditions. As the decarboxylation of fatty acids to alkanes is an important transformation in the production of bio hydrofined diesel (BHD) and jet fuel, we herein report the development of a highly active and reusable Rh nanoparticle catalyst supported by a silicon nanowire array (SiNA-Rh) and its application in the decarboxylation of fatty acids to alkanes under mild conditions. More specifically, SiNA-Rh (500 mol ppm) selectively promoted the hydrogenative decarboxylation reaction at 200 °C under microwave irradiation (～40 W) in a H2 atmosphere (10 bar) to afford the corresponding alkanes in high yields selectively. The only coproduct observed was carbon monoxide, an important and essential staple for the chemical industry. Importantly, carbon dioxide formation was not observed. Moreover, the aldehydes were efficiently converted to alkanes by SiNA-Rh, and this catalyst was reused 20 times without any loss in catalytic activity. Finally, to investigate the effects of microwave irradiation on the enhancement of this chemical transformation based on the Si nanorod structures present in the SiNA-Rh catalyst, the effect of the microwave electric field and magnetic field in the microwave to the reaction was experimentally investigated, and the spatial distribution of the electric field intensity around the surface of the Si nanostructure was simulated using the finite element method.
Photocatalytic degradation of benzothiophene by a novel photocatalyst, removal of decomposition fragments by MCM-41 sorbent
Hosseini, Asma,Faghihian, Hossein
, p. 2383 - 2401 (2019/01/29)
In this study, a catalyst was synthesized by introduction of ZnO onto the surface of FSM-16 catalyst support (ZnO/FSM-16). Impregnation of catalyst support by ZnO proceeded through reacting of FSM-16 nanoparticles with Zn(CH3COO)2 solution followed by calcination of the product. The synthesized photocatalyst was then identified by different methods, and the optical property of the photocatalyst was studied by the DRS method. The results showed that after deposition of photocatalyst on FSM-16 support, the photocatalyst band gap was shifted to the visible region. The photoluminescence studies revealed lower recombination of electron–holes of the photocatalyst after immobilization on FSM-16. The influence of different variables on the photocatalytic performance of the samples was studied. Under optimized conditions, the high degradation efficiency of 97% was obtained by ZnO/FSM-16. The compounds produced from degradation of benzothiophene were recognized by the GC–MS method, and the products containing sulfur were properly adsorbed by MCM-41 sorbent. The photocatalyst showed high regeneration capability, and its activity was mostly preserved after six regeneration cycles.
Chemoselective Hydrodeoxygenation of Carboxylic Acids to Hydrocarbons over Nitrogen-Doped Carbon-Alumina Hybrid Supported Iron Catalysts
Li, Jiang,Zhang, Junjie,Wang, Shuai,Xu, Guangyue,Wang, Hao,Vlachos, Dionisios G.
, p. 1564 - 1577 (2019/02/03)
The establishment of catalyst systems for the chemoselective hydrodeoxygenation (HDO) of carboxylic acids to hydrocarbons, such as the HDO of long-chain fatty acids to alkanes, is important for biomass to biofuel conversion. As the most abundant and probably the cheapest transition metal on the earth, iron is a promising non-noble-metal alternative to precious metals for large-scale conversion of biomass. However, it usually suffers from unsatisfactory activity. In this work, a nitrogen-doped carbon-alumina hybrid supported iron (Fe-N-C@Al2O3) catalyst is established for chemoselective HDO of carboxylic acids to hydrocarbons. By using stearic acid HDO as the model reaction, n-octadecane and n-heptadecane are produced with yields of 91.9% and 6.0%, respectively. Triglycerides can also be converted into liquid alkanes with a total molar yield of >92%. In addition, the iron catalyst can chemoselectively catalyze the HDO of the carboxylic acid group in the presence of other functional groups such as an aromatic ring. This chemoselectivity has rarely been seen before because the aromatic ring is usually more easily hydrogenated in comparison to HDO of the carboxylic acid group. The characterization results showed that both the formation of a nitrogen-doped carbon-alumina hybrid and the iron loading are important for the Lewis basicity of these catalysts, in order to adsorb the acid substrates. The addition of melamine as the nitrogen precursor during pyrolysis eliminates undesired reactions between the iron precursor and alumina support to form an inactive hercynite phase, leading to the formation of an Fe3C active phase for the hydrogenation of -COOH to -CH2OH and the hybrid of N-C and alumina for the HDO of -CH2OH to -CH3.
Iron-catalysed allylation-hydrogenation sequences as masked alkyl-alkyl cross-couplings
Bernauer, Josef,Wu, Guojiao,Von Wangelin, Axel
, p. 31217 - 31223 (2019/10/19)
An iron-catalysed allylation of organomagnesium reagents (alkyl, aryl) with simple allyl acetates proceeds under mild conditions (Fe(OAc)2 or Fe(acac)2, Et2O, r.t.) to furnish various alkene and styrene derivatives. Mechanistic studies indicate the operation of a homotopic catalyst. The sequential combination of such iron-catalysed allylation with an iron-catalysed hydrogenation results in overall C(sp3)-C(sp3)-bond formation that constitutes an attractive alternative to challenging direct cross-coupling protocols with alkyl halides.
Cross-coupling reaction of alkyl halides with alkyl grignard reagents catalyzed by cp-iron complexes in the presence of 1,3-butadiene
Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
supporting information, p. 763 - 766 (2018/05/29)
Iron-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents by the combined use of cyclopentadienyl ligand and 1,3-butadiene additive is described. The reaction smoothly proceeds at room temperature using unactivated alkyl bromides and fluorides via non-radical mechanism, which is in sharp contrast with hitherto known Fe-catalyzed cross-coupling reactions of alkyl halides.
Light-Driven Enzymatic Decarboxylation of Fatty Acids
Huijbers, Mieke M. E.,Zhang, Wuyuan,Tonin, Fabio,Hollmann, Frank
supporting information, p. 13648 - 13651 (2018/09/21)
The photoenzymatic decarboxylation of fatty acids to alkanes is proposed as an alternative approach for the synthesis of biodiesel. By using a recently discovered photodecarboxylase from Chlorella variabilis NC64A (CvFAP) we demonstrate the irreversible preparation of alkanes from fatty acids and triglycerides. Several fatty acids and their triglycerides are converted by CvFAP in near-quantitative yield and exclusive selectivity upon illumination with blue light. Very promising turnover numbers of up to 8000 were achieved in this proof-of-concept study.
