- Production of liquid hydrocarbon fuels with 3-pentanone and platform molecules derived from lignocellulose
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Diesel or jet fuel range C10-C17 branched and cyclic alkanes were produced by reaction of 3-pentanone derived from lactic acid with bio-based aldehydes through aldol condensation followed by hydrodeoxygenation. DBU (1,8-diazabicycloundec-7-ene) was identified as an efficient catalyst for the aldol reaction of 3-pentanone with furan based aldehydes, and the selectivity of single or double aldol condensation product could be easily controlled by adjusting the reaction temperature. For the reaction with aromatic aldehydes, aluminium phosphate demonstrated a higher catalytic activity than DBU and mechanisms were proposed for the difference in the catalytic activity. The final hydrodeoxygenation step could be achieved by using a simple Pd/C + H-beta zeolite system, excellent selectivity was observed under the present system, the clean formation of hydrocarbons with a narrow distribution of alkanes occurred in most cases.
- Shen, Tao,Zhu, Chenjie,Tang, Chenglun,Cao, Zhi,Wang, Linfeng,Guo, Kai,Ying, Hanjie
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p. 62974 - 62980
(2016/07/13)
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- Solvent-free synthesis of C9 and C10 branched alkanes with furfural and 3-pentanone from lignocellulose
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Jet fuel range branched alkanes were first synthesized under solvent-free conditions by the aldol condensation of furfural and 3-pentanone from lignocellulose followed by the one-step hydrodeoxygenation (HDO). Among the investigated solid base catalysts,
- Chen, Fang,Li, Ning,Li, Shanshan,Yang, Jinfan,Liu, Fei,Wang, Wentao,Wang, Aiqin,Cong, Yu,Wang, Xiaodong,Zhang, Tao
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p. 229 - 232
(2015/01/09)
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- Conversion of levulinic acid derived valeric acid into a liquid transportation fuel of the kerosene type
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In the transformation of lignocellulosic biomass into fuels and chemicals carboncarbon bond formations and rising hydrophobicity are highly desired. The ketonic decarboxylation fits these requirements perfectly as it converts carboxylic acids into ketones forming one carboncarbon bond and eliminates three oxygen atoms as carbon dioxide and water. This reaction is used, in a cascade process, together with a hydrogenation and dehydration catalyst to obtain hydrocarbons in the kerosene range from hexose-derived valeric acid. It is shown that zirconium oxide is a very selective and stable catalyst for this process and when combined with platinum supported on alumina, the oxygen content was reduced to almost zero. Furthermore, it is demonstrated that alumina is superior to active carbon, silica, or zirconium oxide as support for the hydrogenation/dehydration/hydrogenation sequence and a palladium-based catalyst deactivated more rapidly than the platinum catalyst. Hence, under optimized reaction conditions valeric acid is converted into n-nonane with 80% selectivity (together with a 10% of C10-C15 hydrocarbons) in the organic liquid phase upto a 100:1 feed to catalyst ratio [w/w]. The oxygen free hydrocarbon product mixture (85% yield) meets well with the boiling point range of kerosene as evidenced by a simulated distillation. In the gas phase, butane was detected together with mainly carbon dioxide.
- Corma, Avelino,Oliver-Tomas, Borja,Renz, Michael,Simakova, Irina L.
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p. 116 - 122
(2014/06/09)
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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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- 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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- Selective dimerisation of α-olefins using tungsten-based initiators
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The selective dimerisation of the α-olefins 1-pentene through to 1-nonene is reported using an in situ-generated catalyst derived from tungsten hexachloride, aniline, triethylamine and alkylaluminium halide. The influence of reagent identity and reaction stoichiometry, along with activator, solvent and α-olefin substrate choice are probed. The catalyst is found to be highly selective towards dimerisation, minimising the formation of undesired heavier oligomers. Notably, the selectivity within the dimer fraction is found to favour the formation of products with methyl branches. The selectivity towards individual olefin isomers has been determined and the system is found to also produce trace levels of dienes and alkanes. A kinetic study of the system reveals a second order dependence on substrate. Comparison of the products observed, with those expected for metallacyclic and Cossee-type mechanisms, suggests that the latter is in operation, something confirmed by the results of a C2H4/C2D4 co-dimerisation experiment which showed full isotopic scrambling in the products. Thus a mechanistic proposal is made to account for the observed behaviour of the system, including the diene and alkane formation. The Royal Society of Chemistry 2010.
- Hanton, Martin J.,Daubney, Louisa,Lebl, Tomas,Polas, Stacey,Smith, David M.,Willemse, Alex
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p. 7025 - 7037
(2010/09/17)
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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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- Selective ring opening of naphthenic molecules
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Ring opening as practiced in hydrocracking of naphthenic molecules results from multiple cleavages of both endo- and exocyclic C-C bonds. Selective ring opening requires that only one endocyclic C-C bond per naphthene ring be severed, preserving thereby reactant molecular weight. The products of selective ring opening are alkanes and alkylnaphthenes. Over hydrocracking catalysts the yield of alkanes with the same number of carbon atoms as the reactant naphthenes is unacceptably low as a result of extensive dealkylation of alkylnaphthenes and secondary cracking of alkanes. Alkylcyclopentanes, in contrast, selectively ring open by hydrogenolysis over a number of noble metal catalysts. Under similar reaction conditions the selective ring-opening rates of alkylcyclohexanes are, however, one to two orders slower than those of alkylcyclopentanes. Addition of a ring-contraction acidity function converts alkylcyclohexanes into more easily ring-opened alkylcyclopentanes, greatly facilitating selective ring opening. Selective ring-opening rates and selectivities are optimum when ring isomerization occurs by a nonbranching ring contraction. Branching ring contraction, creating increased numbers of ring substituents, is detrimental to both ring-opening rates and selectivities. When an effective acidity function is coupled with a high-activity hydrogenolysis metal, such as iridium, the resulting bifunctional catalyst system greatly outperforms conventional hydrocracking catalysts for the selective conversion of naphthenes to alkanes.
- McVicker,Daage,Touvelle,Hudson,Klein,Baird Jr.,Cook,Chen,Hantzer,Vaughan,Ellis,Feeley
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p. 137 - 148
(2007/10/03)
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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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- Anodic Oxidation of Organoboranes
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Organoboranes are converted into more easily oxidizable borates by reaction with nucleophiles and the alkyl groups are dimerized by anodic oxidation.The oxidation potentials (Ep) of the borates depend strongly on the nature of the complexing nucleophile, for instance Ep = +0.37 V (vs.SCE) with OH- or +1.65 V with tetrahydrofuran.The dimer yields are optimized with trioctylborane (5) by variation of the electrode material and the elctrolyte.At the platinum anode in sodium hydroxide-methanol/tetrahydrofuran yields of 80percent are obtained for acyclic alkyl groups, and lo wer ones for cycloalkyl groups.They exceed those obtained by the Kolbe electrolysis or the oxidation with neutral hydrogen peroxide and they are comparable to those of the AgNO3 oxidation. - The selective preparation of unsymmetrical products from borates with different alkyl groups is not possible, the dimerization proceeds likely via free radicals that couple statistically.Good yields of unsymmetrical coupling products are achieved, when one olefin is used in excess.With choro-, ethoxy-, acetoxy-, and aryl-substituted alkyl groups the dimers are obtained in 21 - 66percent yield, with bromide the yield are lower and with nitriles the dimerization fails.
- Schlegel, Guenter,Schaefer, Hans J.
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p. 1400 - 1423
(2007/10/02)
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- FORMATION OF SULFUR COMPOUNDS IN THE HYDRODENITROGENATION OF PIPERIDINE, PYRIDINE, 1-PENTYLAMINE AND 1-PENT-4-ENYLAMINE ON A NICKEL-TUNGSTEN CATALYST IN THE PRESENCE OF HYDROGEN SULFIDE
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Hydrogenations of piperidine, pyridine, 1-pentylamine, and 1-pent-4-enylamine were carried out in an autoclave at 300 deg C on a sulfidized nickel-tungsten catalyst using either pure hydrogen or a mixture of hydrogen with hydrogen sulfide.Hydrogen sulfide was found to raise the degree of conversion of the starting substances and accelerate the hydrodenitrogenation by formation of sulfur compounds; 1-pentanethiol, di(1-pentyl)sulfide, 2-methylthiacyclopentane, thiacyclohexane and other sulfur compounds were detected in the reaction mixtures in the presence of hydrogensulfide.A reaction pathway is suggested of the hydrodenitrogenation of piperidine in the presence of hydrogen sulfide, accounting for the favourable effect of the latter on the hydrodenitrogenation of nitrogen compounds.
- Cerny, Mirko
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p. 928 - 935
(2007/10/02)
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