- Production of liquid hydrocarbon fuels with acetoin and platform molecules derived from lignocellulose
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Acetoin, a novel C4 platform molecule derived from new ABE (acetoin-butanol-ethanol) type fermentation via metabolic engineering, was used for the first time as a bio-based building block for the production of liquid hydrocarbon fuels. A series of diesel or jet fuel range C9-C14 straight, branched, or cyclic alkanes were produced in excellent yields by means of C-C coupling followed by hydrodeoxygenation reactions. Hydroxyalkylation/alkylation of acetoin with 2-methylfuran was investigated over a series of solid acid catalysts. Among the investigated candidates, zirconia supported trifluoromethanesulfonic acid showed the highest activity and stability. In the aldol condensation step, a basic ionic liquid [H3N+-CH2-CH2-OH][CH3COO-] was identified as an efficient and recyclable catalyst for the reactions of acetoin with furan based aldehydes. The scope of the process has also been studied by reacting acetoin with other aldehydes, and it was found that abnormal condensation products were formed from the reactions of acetoin with aromatic aldehydes through an aldol condensation-pinacol rearrangement route when amorphous aluminium phosphate was used as a catalyst. And the final hydrodeoxygenation step could be achieved by using a simple and handy Pd/C + H-beta zeolite system, and no or a negligible amount of oxygenates was observed after the reaction. Excellent selectivity was also observed using the present system, and the clean formation of hydrocarbons with a narrow distribution of alkanes occurred in most cases.
- Zhu, Chenjie,Shen, Tao,Liu, Dong,Wu, Jinglan,Chen, Yong,Wang, Linfeng,Guo, Kai,Ying, Hanjie,Ouyang, Pingkai
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supporting information
p. 2165 - 2174
(2016/04/19)
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- Br?nsted Acid-Catalyzed Transfer Hydrogenation of Imines and Alkenes Using Cyclohexa-1,4-dienes as Dihydrogen Surrogates
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Cyclohexa-1,4-dienes are introduced to Br?nsted acid-catalyzed transfer hydrogenation as an alternative to the widely used Hantzsch dihydropyridines. While these hydrocarbon-based dihydrogen surrogates do offer little advantage over established protocols in imine reduction as well as reductive amination, their use enables the previously unprecedented transfer hydrogenation of structurally and electronically unbiased 1,1-di- and trisubstituted alkenes. The mild procedure requires 5.0 mol % of Tf2NH, but the less acidic sulfonic acids TfOH and TsOH work equally well.
- Chatterjee, Indranil,Oestreich, Martin
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supporting information
p. 2463 - 2466
(2016/06/09)
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- B(C6F5)3-Catalyzed Transfer of Dihydrogen from One Unsaturated Hydrocarbon to Another
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A transition-metal-free transfer hydrogenation of 1,1-disubstituted alkenes with cyclohexa-1,4-dienes as the formal source of dihydrogen is reported. The process is initiated by B(C6F5)3-mediated hydride abstraction from the dihydrogen surrogate, forming a Bronsted acidic Wheland complex and [HB(C6F5)3]-. A sequence of proton and hydride transfers onto the alkene substrate then yields the alkane. Although several carbenium ion intermediates are involved, competing reaction channels, such as dihydrogen release and cationic dimerization of reactants, are largely suppressed by the use of a cyclohexa-1,4-diene with methyl groups at the C1 and C5 as well as at the C3 position, the site of hydride abstraction. The alkene concentration is another crucial factor. The various reaction pathways were computationally analyzed, leading to a mechanistic picture that is in full agreement with the experimental observations.
- Chatterjee, Indranil,Qu, Zheng-Wang,Grimme, Stefan,Oestreich, Martin
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supporting information
p. 12158 - 12162
(2015/10/12)
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- Effects of oxidant acid treatments on carbon-templated hierarchical SAPO-11 materials: Synthesis, characterization and catalytic evaluation in n-decane hydroisomerization
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Hierarchical SAPO-11 was synthesized using a commercial Merck carbon as template. Oxidant acid treatments were performed on the carbon matrix in order to investigate its influence on the properties of SAPO-11. Structural, textural and acidic properties of the different materials were evaluated by XRD, SEM, N2 adsorption, pyridine adsorption followed by IR spectroscopy and thermal analyses. The catalytic behavior of the materials (with 0.5 wt.% Pt, introduced by mechanic mixture with Pt/Al2O3), were studied in the hydroisomerization of n-decane. The hierarchical samples showed higher yields in monobranched isomers than typical microporous SAPO-11, as a direct consequence of the modification on both porosity and acidity, the later one being the most predominant.
- Bértolo, Raquel,Silva, Jo?o M.,Ribeiro, Filipa,Maldonado-Hódar, Francisco J.,Fernandes, Auguste,Martins, Angela
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p. 230 - 237
(2014/12/10)
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- PdAu alloy nanoparticles encapsulated by PPI-g-MWCNTs as a novel catalyst for chemoselective hydrogenation of alkenes under mild conditions
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The synthesis, characterization and catalytic applications of bimetallic PdAu encapsulated on polypropylene imine grafted multi-wall carbon nanotubes hybrid materials have been reported. The results show that the catalyst induces a highly activity and chemoselective hydrogenation of less hindered alkenes to the corresponding alkanes using hydrogen gas in environmentally friendly solvents H2O/EtOH at 50 °C with high yields. The characterization of catalyst was confirmed by FT-IR, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction.
- Shaabani, Ahmad,Mahyari, Mojtaba
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p. 1277 - 1284
(2014/01/06)
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- Solvent-free synthesis of C10 and C11 branched alkanes from furfural and methyl isobutyl ketone
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Our best results jet: C10 and C11 branched alkanes, with low freezing points, are synthesized through the aldol condensation of furfural and methyl isobutyl ketone from lignocellulose, which is then followed by hydrodeoxygenation. These jet-fuel-range alkanes are obtained in high overall yields (≈90 %) under solvent-free conditions. Copyright
- Yang, Jinfan,Li, Ning,Li, Guangyi,Wang, Wentao,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
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p. 1149 - 1152
(2013/07/26)
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- High-performance ring-opening catalysts based on iridium-containing zeolite Beta in the hydroconversion of decalin
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Decalin was converted in a flow-type reactor under a hydrogen pressure of 5.2 MPa on Ir/H,A-Beta zeolite catalysts, where A stands for an alkali metal cation. In one series of catalysts, the Ir content was 3 wt.%, and the nature of A was varied from lithi
- Santi, Dominic,Holl, Tobias,Calemma, Vincenzo,Weitkamp, Jens
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- METHOD TO CONVERT FERMENTATION MIXTURE INTO FUELS
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The present disclosure provides methods to produce ketones suitable for use as fuels and lubricants by catalytic conversion of an acetone-butanol-ethanol (ABE) fermentation product mixture that can be derived from biomass.
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Page/Page column 78-79
(2013/02/27)
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- New zeolite Al-COE-4: Reaching highly shape-selective catalytic performance through interlayer expansion
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A ferrierite-type layered aluminosilicate, Al-RUB-36, was prepared for the first time and its interlayer expansion resulted in new zeolite catalysts denoted Al-COE-3 and Al-COE-4. Decane hydroconversion tests demonstrated the highly active and shape-selective nature of the new Al-COE-4 catalyst with an unprecedented isomerization yield, highlighting the potential of this material as a hydroisomerization catalyst. This is the first report on achieving shape-selectivity via interlayer expansion. The Royal Society of Chemistry 2012.
- Yilmaz, Bilge,Müller, Ulrich,Feyen, Mathias,Zhang, Haiyan,Xiao, Feng-Shou,De Baerdemaeker, Trees,Tijsebaert, Bart,Jacobs, Pierre,De Vos, Dirk,Zhang, Weiping,Bao, Xinhe,Imai, Hiroyuki,Tatsumi, Takashi,Gies, Hermann
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p. 11549 - 11551
(2013/01/15)
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- Al-RUB-41: A shape-selective zeolite catalyst from a layered silicate
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A new zeolite catalyst, Al-RUB-41, was synthesized for the first time. It was tested as a catalyst in methanol amination, and showed a shape-selective performance that results in a highly favorable product distribution. The shape-selective nature was also evidenced by using Pt-Al-RUB-41 as a bifunctional catalyst for decane hydroconversion. With its unique pore architecture and remarkable shape-selective character, Al-RUB-41 presents a significant commercial potential in industrial catalysis.
- Yilmaz, Bilge,Mueller, Ulrich,Tijsebaert, Bart,Vos, Dirk De,Xie, Bin,Xiao, Feng-Shou,Gies, Hermann,Zhang, Weiping,Bao, Xinhe,Imai, Hiroyuki,Tatsumi, Takashi
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supporting information; experimental part
p. 1812 - 1814
(2011/03/22)
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- Exploring the void structure and activity of RUB-39 based expanded materials using the hydroconversion of decane
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The layered silicate RUB-39 can be transformed by topotactic condensation into RUB-41 (RRO), a zeolite with 8- and 10- ring pores. If the layered RUB-39 is first silylated with dichlorodimethylsilane (DCDMS) or hexamethyldisiloxane (HMDS), an interlayer expanded structure is created after calcination. The DCDMS expanded material contains 10- and 12-ring pores instead of 8- and 10-ring pores. Detailed physicochemical characterization showed that the Al content is not significantly changed during the expansion. In the hydroconversion of decane, the expanded materials have a significantly increased activity, as demonstrated by the lower temperatures at which isomerization and cracking occur. Detailed comparison of the product selectivities obtained with RUB-41 or with its expanded analogs shows that the void structure of the expanded materials is significantly less constrained, as reflected in the distribution of methylnonane isomers, of the ethyloctane vs. methylnonane isomers, and in the ratio of monobranched vs. dibranched isomers.
- Tijsebaert, Bart,Henry, Mathieu,Gies, Hermann,Xiao, Feng-Shou,Zhang, Weiping,Bao, Xinhe,Imai, Hiroyuki,Tatsumi, Takashi,Mueller, Ulrich,Yilmaz, Bilge,Jacobs, Pierre,Vos, Dirk De
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experimental part
p. 47 - 53
(2011/10/13)
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- CATALYTIC PROCESS FOR CONVERTING RENEWABLE RESOURCES INTO PARAFFINS FOR USE AS DIESEL BLENDING STOCKS
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A process for converting renewable resources such as vegetable oil and animal fat into paraffins in a single step which comprises contacting a feed which is a renewable resources with hydrogen and a catalyst which comprises molybdenum, a non-precious metal and an oxide to produce a hydrocarbon product having a ratio of even-numbered hydrocarbons to odd-numbered hydrocarbons of at least 2:1.
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Page/Page column 7
(2009/01/24)
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- Zeolite SSZ-53: An extra-large-pore zeolite with interesting catalytic properties
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(Figure Presented) Wide pores for wide applications: The catalytic properties of SSZ-53, an extra-large-pore high-silica zeolite, were explored by using ethylbenzene disproportionation and the isomerization and hydrocracking of n-decane as test reactions. High activity together with a very open channel system render this zeolite an attractive candidate as catalyst for applications in petroleum refining.
- Tontisirin, Supak,Ernst, Stefan
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p. 7304 - 7306
(2008/09/18)
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- Transformations of Saturated Hydrocarbons at Room Temperature in the Presence of the Fullerene C60-Aluminum Bromide-Hydrochloric Acid System
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The fullerene C60-aluminum bromide-hydrochloric acid system can mediate the isomerization, alkylation, and dehydrogenation reactions of n-decane, decalin, and 1,3-dimethyladamantane at room temperature and atmospheric pressure. The saturated hydrocarbons can be arranged according to reactivity in the following series: decalin > n-decane > 1,3-dimethyladamantane.
- Nekhaev,Bagrii
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p. 383 - 386
(2007/10/03)
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- Scope and utility of a new soluble copper catalyst [CuBr-LiSPh-LiBr-THF]: A comparison with other copper catalysts in their ability to couple one equivalent of a Grignard reagent with an alkyl sulfonate
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A mixture of equal amounts of CuBr-SMe2, LiBr, and LiSPh in THF at 0°C furnished a new soluble copper catalyst that was highly efficient at coupling primary, secondary, tertiary, aryl, vinyl, and allylic Grignard reagents to primary tosylates and primary Grignard reagents to secondary tosylates and mesylates, all with the use of only 1 equiv of Grignard reagent. The new catalyst was shown to be much more reactive than copper catalysts CuBr and Li2CuCl4 and more efficient in the transference of secondary and tertiary alkyl groups than lower order cuprates (Gilman reagents) and demonstrated more reactivity than the lower order cuprates with its ability to couple primary Grignard reagents to secondary sulfonates. The Grignard reagent/catalyst system was compatible with an ester functionalized tosylate, thus proving to be more chemoselective than a Grignard reagent without the catalyst. The catalyst exhibited good reactivity below room temperature, and with the addition of 6% v/v of HMPA to the catalyst solution, excellent yields of coupled product were obtained within a 25-67°C temperature range. 1H NMR demonstrated that the catalyst solution consisted of several species that most likely were composed of copper ligated with thiophenol, THF, and LiBr in aggregated forms.
- Burns, Dennis H.,Miller, Jeffrey D.,Chan, Ho-Kit,Delaney, Michael O.
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p. 2125 - 2133
(2007/10/03)
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- Geminal dialkylation, alkylative reduction and olefination of aliphatic aldehydes. Reaction of gem-bistriflates with higher order dialkylcyanocuprates
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gem-Dialkylation or alkylative reduction of α-unbranched aliphatic aldehydes 1 is advantageously achieved by reaction of the corresponding gem-bistriflates 2 with di-n-alkylcyanocuprates or di-sec- and di-tert-alkylcyanocuprates respectively. The reaction of α-branched gem-bistriflates 2 with dialkylcyanocuprates in the presence of boron trifluoride affords the olefins 6 in good yield.
- Garcia Martinez,Osio Barcina,Ruiz Diez,Subramanian
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p. 13231 - 13238
(2007/10/02)
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- Geminal Dialkylation and Alkylative Reduction of Alyphatic Aldehydes.
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gem-Dialkylation or alkylative reduction of α-unbranched aliphatic aldehydes is easily carried out by replacing the carbonyl oxygen with the gem-dihalide functionality followed by substitution of each halogen (bromine or iodine) by two n-alkyl groups or one sec- or tert-alkyl group and one hydrogen atom using higher-order dialkyl-lithium cyanocuprates.
- Martinez, A. Garcia,Fernandez, A. Herrera,Alvarez, R. Martinez,Barcina, J. Osio,Gomez, C. Garcia,Subramanian, L. R.
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p. 1063 - 1064
(2007/10/02)
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- HYDROISOMERIZATION AND HYDROCRACKING OF METHYLNONANES OVER Pt/HZSM-5
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The hydrocracking and hydroisomerization of n-decane and the methylnonanes over Pt/HZSM-5 are investigated.Detailed product distributions are reported at low and high conversions.The differences in the products obtained from the different tested alkanes are discussed in terms of the classical bifunctional mechanism.
- Martens, Johan A.,Tielen, Mia,Jacobs, Peter A.
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p. 203 - 212
(2007/10/02)
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