- Preparation and catalytic performance of NiO-MnO2/Nb2O5-TiO2 for one-step synthesis of 2-ethylhexanol from n-butyraldehyde
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One-pot synthesis of 2-ethylhexanol(2EHO) from n-butyraldehyde is of commercialimportance. The promotion of 2EHO selectivity requires suppressing direct hydrogenation of n-butyraldehyde. In this work, a series of NiO-MOx/Nb2O5-TiO2 catalysts were prepared and utilized by means of reduction-in-reaction technique, aiming at delaying the formation of metal sites and suppressing the direct hydrogenation. NiO-MnO2/Nb2O5-TiO2 with a Ni/Mn mass ratio of 10 and NiO-MnO2 loading of 14.3 wt% shows the best catalytic performance; 2-EHO selectivity could reach 90.0% at a complete conversion of n-butyraldehyde. Furthermore the catalyst could be used for four times without a substantial change in its catalytic performance.
- An, Hualiang,Li, Sibo,Wang, Yanji,Zhang, Jiaxun,Zhao, Xinqiang
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- Non-Oxidative Dehydrogenation Pathways for the Conversion of C2-C4 Alcohols to Carbonyl Compounds
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Gold nanoparticles (NPs) supported on hydrotalcite (Au/HT) are highly active and selective catalysts for the continuous, gas-phase, non-oxidative dehydrogenation of bioderived C2-C4 alcohols. A sharp increase in turn over frequency (TOF) is noted when the size of Au NPs is less than 5 'nm relating to the strong synergy between metallic Au NPs and the acid-base groups on the support surface. It is shown that catalytic activity depends critically on Au NP size, support composition, and support pretreatments. A reaction pathway elucidated from kinetic isotope effects suggests that the abstraction of β-H by Au NPs (C-H activation) is the rate-determining step in the dehydrogenation of bioderived C2-C4 alcohols. All that′s good is gold: Gold nanoparticles supported on calcined hydrotalcite (Au/HT) are highly active and very selective catalysts for the continuous, gas-phase, non-oxidative dehydrogenation of bioderived C2-C4 alcohols.
- Shylesh, Sankaranarayanapillai,Kim, Daeyoup,Ho, Christopher R.,Johnson, Gregory R.,Wu, Jason,Bell, Alexis T.
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- Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst
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The mineral hydroxyapatite [HAP; Ca10(PO4)6(OH)2] is the chief component of animal bones and teeth. It also is known to function as a catalyst with both acid and base sites, depending on the manner in which it is synthesized. We closely studied the reaction of ethanol over HAP using catalysts of different Ca/P molar ratios. These were prepared by controlling the pH of the solution during precipitation synthesis. We found that the distribution of acid sites and basic sites on the catalyst surface varied with the Ca/P ratio of HAP. The yields of ethylene, 1-butanol, and 1,3-butadiene were correlated with the ratio of acid sites and basic sites. We further found that yields of higher alcohols, such as 1-butanol, that are known as Guerbet alcohols and are characteristic products of ethanol over HAP, are functions of the probability of ethanol activation (α) on the catalyst surface.
- Tsuchida, Takashi,Kubo, Jun,Yoshioka, Tetsuya,Sakuma, Shuji,Takeguchi, Tatsuya,Ueda, Wataru
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- Catalytic Upgrading of Ethanol to n-Butanol via Manganese-Mediated Guerbet Reaction
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Replacement of precious metal catalysts in the Guerbet upgrade of ethanol to n-butanol with first-row metal complex catalysts is highly appreciated due to their economic and environmental friendliness. The manganese pincer complexes of the type [(RPNP)MnBr(CO)2] (R = iPr, Cy, tBu, Ph or Ad) are found to be excellent catalysts for upgrading ethanol to n-butanol. Under suitable reaction conditions and with an appropriate base, about 34% yield of n-butanol can be obtained in high selectivity. A detailed account on the effect of the temperature, solvent, nature, and proportion of base used and the stereoelectronic effects of the ligand substituents on the catalytic activity of the catalysts as well as the plausible deactivation pathways is presented.
- Kulkarni, Naveen V.,Brennessel, William W.,Jones, William D.
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- Transformations of butyraldehyde in the presence of catalysts based on large-pore molecular sieves VPI-5 and AlPO4-8
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It was found that zeolite-like ctystalline aluminophosphates VPI-5, Si-VPI-5, and Mn-VPI-5 as well as those derived from them, AlPO4-8, SAPO4-8, and MnAPO4-8, are capable of catalyzing aldol condensation and crotonization of butyraldehyde (BA).Pd/AlPO4-8 is catalytically active in hydrocondensation of BA with H2 at atmospheric pressure.The activities in BA conversion to 2-ethylhexane-3-ol-1-al increase in following order: Mn-VPI-5 +NaX (CsNaX), but they are much more stable.Pd/AlPO4-8 catalyzes BA conversion to 2-ethylhexanal even in the absence of H2 feed to the reaction zone.The influence of catalyst pretreatments and experimental conditions on the catalyst structures and catalytic activities is discussed. - Key words: butyraldehyde; condendation; crystalline aluminophosphates; molecular sieves; VPI-5; AlPO4-8; catalysis.
- Isakov, Ya. I.,Minachev, Kh. M.,Tome, R.,Tissler, A.,Oehlmann, G.,et al.
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- SODIUM SULFIDE AS A SELECTIVE REDUCING REAGENT FOR ALDEHYDES TO ALCOHOLS. USE OF ALUMINA AS AN EFFECTIVE CATALYST
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Intrinsic reactivity of sodium sulfide is well controlled by impregnating it on alumina, so that aldehydes can be readily reduced to the corresponding alcohols, while ketones, esters and even nitro compounds are all inert toward this reagent.
- Kamitori, Yasuhiro,Hojo, Masaru,Masuda, Ryoichi,Yamamoto, Masaki
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- Direct self-condensation of bio-alcohols in the aqueous phase
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Bio-alcohols (e.g. ethanol, butanol) are primarily obtained as diluted aqueous solutions from biomass fermentation, and thus the subsequent isolation is a very costly process. So the direct transformation of bio-alcohols in water will have great advantages. This study describes the development of catalysts used for the self-condensation of bio-alcohols in water (that mimic the primary fermentation solutions). Efficient iridium catalysts have been developed rationally from homogeneous to heterogeneous, and the immobilized catalysts could be reused without any loss of activity, which is very important for the development of practical processes. The expected self-condensation could be realized with 80-90% selectivity in water and air. Such a protocol might be used for producing butanol from ethanol solution directly, which is an improved higher-alcohol biofuel. Other useful chemicals, such as 2-ethylhexanol, could also be obtained from renewable resources through this condensation reaction. This journal is the Partner Organisations 2014.
- Xu, Guoqiang,Lammens, Tijs,Liu, Qiang,Wang, Xicheng,Dong, Linlin,Caiazzo, Aldo,Ashraf, Nadim,Guan, Jing,Mu, Xindong
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- Conversion of ethanol into linear primary alcohols on gold, nickel, and gold–nickel catalysts
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The direct conversion of ethanol into the linear primary alcohols CnH2n+1OH (n = 4, 6, and 8) in the presence of the original mono- and bimetallic catalysts Au/Al2O3, Ni/Al2O3, and Au–Ni/Al2O3 was studied. It was established that the rate and selectivity of the reaction performed under the conditions of a supercritical state of ethanol sharply increased in the presence of Au–Ni/Al2O3. The yield of target products on the bimetallic catalyst was higher by a factor of 2–3 than that reached on the monometallic analogs. Differences in the catalytic behaviors of the Au, Ni, and Au–Ni systems were discussed with consideration for their structure peculiarities and reaction mechanisms.
- Chistyakov,Zharova,Tsodikov,Nikolaev,Krotova,Ezzhelenko
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- Antimicrobial and Antioxidant Potential of Berberisinol, a New Flavone from Berberis baluchistanica
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A new flavone, berberisinol (1), has been isolated from the EtOAc fraction of the MeOH extract of Berberis baluchistanica, along with known compounds, palmatine (2), berberine (3), 8-oxoberberine (4), β-sitosterol (5), oleanolic acid (6), and gallic acid (7), isolated for the first time from this species. Spectroscopic techniques including two-dimensional NMR were used for structural elucidation. Berberisinol (1) showed significant antibacterial and antioxidant potential.
- Pervez, Samreen,Saeed, Muhammad,Ali, Muhammad Shaiq,Fatima, Itrat,Khan, Haroon,Ullah, Irfan
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- Cascade engineered synthesis of 2-ethyl-1-hexanol from n-butanal and 2-methyl-1-pentanol from n-propanal using combustion synthesized Cu/Mg/Al mixed metal oxide trifunctional catalyst
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2-Ethyl-1-hexanol (2-EH) is a commercially important chemical that requires cost effective catalytic processes for synthesis. The cascade engineered synthesis of 2-EH was done in a single pot from n-butanal using solventless conditions with trifunctional mixed metal oxide containing 5% Cu and Mg/Al ratio of 3. This trifunctional catalyst was made by combustion synthesis technique which resulted in a porous network with narrow pore size distribution. The catalyst was characterized before and after reuse by FTIR, XRD, SEM, TEM, CO2-TPD, NH3-TPD, TPR, TGA and nitrogen BET analysis. The kinetics of reaction and selectivity profile of 2-EH are reported. The work was extended to one pot cascade engineered synthesis of 2-methyl-1-pentanol (2-MP) from n-propanal using the same catalyst. There was a significant effect of molecular size on rate of reaction and selectivity of the product. This is the first ever report on the one pot synthesis of 2-MP from n-propanal.
- Patankar, Saurabh C.,Yadav, Ganapati D.
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- Decomposition of trichlorobenzene with different radicals generated by alternating current electrolysis in aqueous solution
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Trichlorobenzenes can be easily decomposed by alternating current electrolysis in aqueous solution. The mechanism of the decomposition was found to be based on selective redox reactions with different radicals - hydrogen atoms and hydroxyl radicals - generated by water electrolysis. Copyright
- Nakamura, Akinobu,Hirano, Keiji,Iji, Masatoshi
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- Hydrogenation of 2-Ethylhexenal Using Supported-Metal Catalysts for Production of 2-Ethylhexanol
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Abstract: The catalytic hydrogenation of 2-ethylhexenal was investigated over Pd supported on ZrO2, CeO2, Al2O3, MCM-41, MAS-7 and SBA-15. The activities and the selectivities of the catalysts were strongly affected by the nature of the support. Pd/ZrO2 had an excellent catalytic performance for the hydrogenation. The superior dispersion of Pd on the support ZrO2, and the stable structure of active components on ZrO2 as well as the synergistic effect of the bifunctional metal-support interaction enhanced the catalytic performance of Pd/ZrO2. The conversion of 2-ethylhexenal and the selectivity for 2-ethylhexanol were 100 and 99.1% respectively when the reaction was carried out at 240 °C for 7?h. The product was easily separated from the catalyst and the catalyst was of good reusability when it was repeated six times. In addition, the aggregation of Pd nanoparticles and the coking of ZrO2 the catalysts were the main cause for the catalyst deactivation. Graphical Abstract: [Figure not available: see fulltext.]
- Liu, Guoxiu,Liu, Shiwei,Liu, Siyuan,Yu, Shitao,Li, Lu,Liu, Fusheng,Xie, Congxia,Song, Xiuyan
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- Base catalyzed hydrolysis of aerosol OT in aqueous and aquo-dioxane media
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The OH- ion catalyzed hydrolysis of AOT and sodium mono-methyl succinate m aqueous and aquo-dioxane media has been studied. The second-order rate constant for the former has been found to be nearly ten times slower than that of the latter. At AOT concentrations above CMC, the rate constants become insensitive to the concentration in the studied range of temperature, 25 °C-40 °C. The activation parameters for the kinetic process have been found to be reasonable, negative entropy of activation has supported a stable transition state complex. A good enthalpy-entropy compensation of the kinetic process has been found both for AOT and sodium monomethyl succinate in aqueous and aquo-dioxane media supporting similar nature of the transition state complexes in the hydrolytic reactions. The enthalpies of hydrolysis of AOT and the half ester of succinic acid in aqueous and aquo-dioxane media have been also reported.
- Mukherjee,Moulik,Mukherjee
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- Successive vapour phase Guerbet condensation of ethanol and 1-butanol over Mg-Al oxide catalysts in a flow reactor
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The successive vapour phase condensation of ethanol and 1-butanol (via Guerbet reaction) in a flow reactor under atmospheric pressure was studied over catalytic Mg-Al oxide compositions. Wherein the vapour phase condensation of 1-butanol to 2-ethyl-1-hexanol in flow has been investigated for the first time. The acid/base capacity ratio, which is determined by the Mg/Al ratio, is an important characteristic for the activity and selectivity of Mg-Al oxide catalysts in the abovementioned processes. The carbon chain length of the reacting alcohols, an arrangement of surface active sites and other steric factors also have an impact on Guerbet condensation in the vapour phase. High productivity of Mg-Al oxide system to the Guerbet alcohols: 1-butanol – 25 g/(Lcat·h), 2-ethyl-1-hexanol – 19 g/(Lcat·h), has been achieved. The results have shown a prospect of successive conversion realization: 1) ethanol → 1-butanol; 2) 1-butanol → 2-ethyl-1-hexanol for the production of 2-ethyl-1-hexanol from ethanol.
- Larina, Olga V.,Valihura, Karina V.,Kyriienko, Pavlo I.,Vlasenko, Nina V.,Balakin, Dmytro Yu.,Khalakhan, Ivan,?endak, Toma?,Soloviev, Sergiy O.,Orlyk, Svitlana M.
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- Electronic and steric factors for enhanced selective synthesis of 2-ethyl-1-hexanol in the Ir-complex-catalyzed Guerbet reaction of 1-butanol
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1-Butanol is a potential bio-based fermentation product obtained from cellulosic biomass. As a value-added chemical, 2-ethyl-1-hexanol (2-EH) can be produced by Guerbet conversion from 1-butanol. This work reports the enhanced catalytic Guerbet reaction of 1-butanol to 2-EH by a series of Cp*Ir complexes (Cp*: 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) coordinated to bipyridine-type ligands bearing an ortho-hydroxypyridine group with an electron-donating group and a Cl? anion. The catalytic activity of the Cp*Ir complex increased by increasing the electron density of the bipyridine ligand when functionalized with the para-NMe2 and ortho-hydroxypyridine groups. A record turnover number of 14047 was attained. A mechanistic study indicated that the steric effect of the ethyl group on the α-C of 2-ethylhexanal (2-EHA) and the conjugation effect of C=C–C=O in 2-ethylhex-2-enal (2-EEA) benefits the high selectivity of 2-EH from 1-butanol by inhibiting the cross-aldol reaction of 2-EHA and 2-EEA with butyraldehyde. Nuclear magnetic resonance study revealed the formation of a carbonyl group in the bipyridine-type ligand via the reaction of the Cp*Ir complex with KOH.
- Xu, Zhanwei,Yan, Peifang,Liang, Changhui,Jia, Songyan,Liu, Xiumei,Zhang, Z. Conrad
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- THE RUTHENIUM COMPLEX-CATALYZED REDUCTION OF KETONES BY FORMIC ACID
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An equimolar mixture of a ketone and formic acid was heated without solvent at 125 degC for 3 h in the presence of catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II) to give the corresponding secondary alcohols in excellent yields.
- Watanabe, Yoshihisha,Ota, Tetsuo,Tsuji, Yasushi
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- Hollow Ni-Co-B amorphous alloy nanospheres: Facile fabrication via vesicle-assisted chemical reduction and their enhanced catalytic performances
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In this paper, we develop a simple vesicle-assisted chemical reduction approach for synthesizing hollow Ni-Co-B nanospheres. With various characterization techniques, the resulting Ni-Co-B nanospheres are identified as amorphous alloys with a hollow chamber. Coexistence of NiII and CoII species plays a significant role in fabricating hollow nanospheric structures, because only solid nanoparticles can be obtained in the presence of a mono-metallic precursor. During liquid-phase hydrogenation of 2-ethyl-2-hexenaldehyde, hollow Ni-Co-B catalyst displays significant bi-site catalysis from bimetals and delivers much greater activity as well as better selectivity than associated with the dense Ni-Co-B catalyst. Additionally, this catalyst is also easily handled in liquid-phase reactions due to its lower density and magnetic property. The material design concept presented in this work opens a new avenue for the development of hollow non-noble metallic nanospheres and will draw more attention in the foreseeable future.
- Wei,Zhao,Peng,Zhang,Bian,Li,Li
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- Guerbet Reaction over Strontium-Substituted Hydroxyapatite Catalysts Prepared at Various (Ca+Sr)/P Ratios
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The Guerbet reaction of ethanol to heavier products was performed over a series of extensively characterized Sr-substituted hydroxyapatites (HAPs) with different (Ca+Sr)/P ratios, and thus different structural, textural, and acid–base properties. The acid–base properties were correlated with the reactivity of the solids and an optimal ratio between the amount of acid and basic sites was determined (ca. 4), whereas the ethanol conversion was mainly depending on the specific surface area of the solids. The stoichiometric 100 mol % Sr-substituted sample (SrAp-100) was especially efficient in higher alcohols production, which can be illustrated by a total alcohol selectivity (76.4 %) higher than that of all the other solids at a 13 % ethanol isoconversion.
- Silvester, Lishil,Lamonier, Jean-Fran?ois,Lamonier, Carole,Capron, Micka?l,Vannier, Rose-No?lle,Mamede, Anne-Sophie,Dumeignil, Franck
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- Direct synthesis of 2-ethylhexanol via n-butanal aldol condensation-hydrogenation reaction integration over a Ni/Ce-Al2O3 bifunctional catalyst
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Direct synthesis of 2-ethylhexanol from n-butanal via the reaction integration of n-butanal self-condensation with 2-ethyl-2-hexenal hydrogenation is of crucial interest for industrial production of 2-ethylhexanol. Furthermore, as an important and versatile chemical, n-butanol can be produced simultaneously by reaction integration. In the present work, several bifunctional catalysts based on γ-Al2O3 were prepared by the impregnation method and were characterized by means of H2-TPR, XRD, TEM and H2-TPD, and their catalytic performance for direct synthesis of 2-ethylhexanol from n-butanal was investigated. The results showed that Co/Al2O3 had a low activity for hydrogenation and Cu/Al2O3 had a high selectivity for the hydrogenation of the C=O group while a Ru/Al2O3 catalyst only favored the hydrogenation of n-butanal to n-butanol. Among them, the Ni/Al2O3 catalyst showed the best catalytic performance and the yield of 2-ethylhexanol was the highest (49.4%). Ce-modified Ni/Al2O3 enhanced the competitiveness of aldol condensation versus hydrogenation of n-butanal and improved the selectivity of 2-ethylhexanol; the yield of 2-ethylhexanol rose to 57.8%. Then the influence of preparation conditions on the catalytic performance of Ni/Ce-Al2O3 was investigated and the suitable preparation conditions were obtained as follows: Ni loading = 10%, calcined at 550 °C for 5 h, and reduced at 570 °C for 4 h. The effect of reaction conditions on the integration reaction catalyzed by Ni/Ce-Al2O3 was investigated and the suitable reaction conditions were obtained as follows: weight percentage of Ni/Ce-Al2O3 = 15%, reaction temperature = 170 °C, reaction pressure = 4.0 MPa and reaction time = 8 h. Under the above reaction conditions, the yield of 2-ethylhexanol attained 66.9% and that of n-butanol was 18.9%. In addition, the components existing in the integration reaction system were identified by GC-MS analysis, and the main by-products were n-butyl butyrate, 2-ethylhexyl butyrate, n-butyric acid, etc. Based on the analysis of the reaction system, a reaction network for the direct synthesis of 2-ethylhexanol from n-butanal was proposed. Finally, an evaluation of the reusability of Ni/Ce-Al2O3 showed that the recovered Ni/Ce-Al2O3 catalyst lost its catalytic activity for the hydrogenation of the C=O group. The main reason for deactivation was that Ni species were covered by the flaky boehmite γ-AlO(OH) formed from the hydration of γ-Al2O3 in the reaction process.
- Liang, Ning,Zhang, Xiaolong,An, Hualiang,Zhao, Xinqiang,Wang, Yanji
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- Efficient conversion of ethanol to 1-butanol and C5-C9 alcohols over calcium carbide
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Production of 1-butanol or alcohols with 4-9 carbon atoms (C4-C9 alcohols) from widely available bio-ethanol has attracted much interest in recent years in academia and industry of renewable chemicals and liquid fuels. This work discloses for the first time that calcium carbide (CaC2) has a superior catalytic activity in condensation of ethanol to C4-C9 alcohols at 275-300 °C. The 1-butanol yield reached up to 24.5% with ethanol conversion of 62.4% at the optimized conditions. The by-products are mainly alcohols with 5-9 carbons besides 2-butanol, and the total yield of all the alcohols reached up to 56.3%. The reaction route was investigated through controlled experiments and quantitative analysis of the products. Results indicated that two reaction routes, aldol-condensation and self-condensation, took place simultaneously. The aldol-condensation route involves coupling of ethanol with acetaldehyde (formed from ethanol dehydrogenation) to form 2-butenol, which is subsequently hydrogenated to 1-butanol. The alkynyl moiety in CaC2 plays an important role in the catalytic pathways of both routes and affords the good activity of CaC2. CaC2 is converted to acetylene [C2H2] and calcium hydroxide [Ca(OH)2] simultaneously by the H2O that was generated from the condensation of alcohols.
- Wang, Dong,Liu, Zhenyu,Liu, Qingya
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- Metal-Organic Framework-Derived Guerbet Catalyst Effectively Differentiates between Ethanol and Butanol
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RuNi nanoparticles supported on a metal-organic framework (RuNi?MOF) and formed in situ from a ruthenium complex enclosed inside a nickel-based MOF act as a highly active catalyst for the Guerbet reaction of ethanol to 1-butanol, providing turnover numbers up to 725 000 Ru-1. Negligible activity of the RuNi?MOF ethanol upgrading catalyst system toward chemically similar 1-butanol makes it possible to synthesize the competent Guerbet substrate 1-butanol with >99% selectivity.
- Neumann, Constanze N.,Rozeveld, Steven J.,Yu, Mingzhe,Rieth, Adam J.,Dincǎ, Mircea
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- Highly Efficient Process for Production of Biofuel from Ethanol Catalyzed by Ruthenium Pincer Complexes
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A highly efficient ruthenium pincer-catalyzed Guerbet-type process for the production of biofuel from ethanol has been developed. It produces the highest conversion of ethanol (73.4%, 0.02 mol% catalyst) for a Guerbet-type reaction, including significant amounts of C4 (35.8% yield), C6 (28.2% yield), and C8 (9.4% yield) alcohols. Catalyst loadings as low as 0.001 mol% can be used, leading to a record turnover number of 18 ?209. Mechanistic studies reveal the likely active ruthenium species and the main deactivation process.
- Xie, Yinjun,Ben-David, Yehoshoa,Shimon, Linda J. W.,Milstein, David
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- Catalytic performance of Ni/Γ-Al2O3 for hydrogenation of 2-ethyl-2-hexenal
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The effect of reaction conditions on the catalytic performance of Ni/γ-Al2O3 was investigated and the result showed that Ni/γ-Al2O3 showed excellent catalytic activity. However, the catalytic performance of the recovered Ni/γ-Al2O3 catalyst declined dramatically. The fresh and the recovered catalysts were comparatively analyzed by means of XRD, XPS and FT-IR techniques. The result demonstrated that the main reason for the activity decline of the recovered Ni/γ-Al2O3 catalyst is that the surface Ni has been reoxidized to NiO. After calcination and reduction, the recovered Ni/γ-Al2O3 catalyst could be reused four times without a significant decrease in its catalytic performance.
- Zhao, Lili,Wang, Yi,An, Hualiang,Zhao, Xinqiang,Wang, Yanji
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- Thermally induced structural transformations of linear coordination polymers based on aluminum tris(diorganophosphates)
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The thermal transitions of inorganic-organic hybrid polymers composed of linear aluminum tris(diorganophosphate) chains with a general formula of catena-Al[O2P(OR)2]3 (where R = C1-C8 alkyl group or phenyl moiety) have been studied by means of DSC, powder XRD, TGA and TG-QMS, as well as optical spectroscopy. DSC and XRD reveal that most of them undergo reversible structural transformations in the solid state between ?100 and 200 °C caused by the changes in conformation of their organic substituents; however, a translational displacement of the rigid polymeric chains occurs only in the case of the derivative bearing long 2-ethylhexyl groups, which becomes liquid at about 140 °C. The thermal decomposition of the studied polymers begins between 200 and 265 °C depending on the type of organic substituent R decorating their aluminophospate core. TGA combined with mass spectrometry of the evolved gaseous products shows that the pyrolytic decomposition of Al[O2P(OR)2]3 proceeds either through β-elimination of olefin (for compounds with C2-C8 aliphatic ligands), or a homolytic cleavage of the P-OR bond (for methyl and phenyl derivatives); both processes are accompanied by condensation of the newly formed POH groups and liberation of water. Powder XRD, FTIR and SEM analyses of the solid residues indicate that thermolysis of Al[O2P(OR)2]3 accompanied by olefin elimination leads to the formation of condensed aluminum phosphates, mainly aluminum cyclohexaphosphate, exhibiting porous morphology. On the other hand, thermal degradation of methyl or phenyl derivatives results in amorphous aluminophosphate residues, and the latter contains conducting carbonaceous phases.
- D?bowski, Maciej,?okaj, Krzysztof,Ostrowski, Andrzej,Zachara, Janusz,Wiecińska, Paulina,Falkowski, Pawe?,Krztoń-Maziopa, Anna,Florjańczyk, Zbigniew
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- Ir(NHC)-Catalyzed Synthesis of β-Alkylated Alcohols via Borrowing Hydrogen Strategy: Influence of Bimetallic Structure
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Multi N-heterocyclic carbene(NHC)-modified iridium catalysts were employed in the β-alkylation of alcohols; dimerization of primary alcohols (Guerbet reaction), cross-coupling of secondary and primary alcohols, and intramolecular cyclization of alcohols. Mechanistic studies of Guerbet reaction, including kinetic experiments, mass analysis, and density functional theory (DFT) calculation, were employed to explain the fast reaction promoted by bimetallic catalysts, and the dramatic reactivity increase of monometallic catalysts at the late stage of the reaction. (Figure presented.).
- Sung, Kihyuk,Lee, Mi-hyun,Cheong, Yeon-Joo,Kim, Yu Kwon,Yu, Sungju,Jang, Hye-Young
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supporting information
p. 3090 - 3097
(2021/05/10)
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- Covalent Adaptable Networks Using β-Amino Esters as Thermally Reversible Building Blocks
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In this study, β-amino esters, prepared by the aza-Michael addition of an amine to an acrylate moiety, are investigated as building blocks for the formation of dynamic covalent networks. While such amino esters are usually considered as thermally nondynamic adducts, the kinetic model studies presented here show that dynamic covalent exchange occurs via both dynamic aza-Michael reaction and catalyst-free transesterification. This knowledge is transferred to create β-amino ester-based covalent adaptable networks (CANs) with coexisting dissociative and associative covalent dynamic exchange reactions. The ease, robustness, and versatility of this chemistry are demonstrated by using a variety of readily available multifunctional acrylates and amines. The presented CANs are reprocessed via either a dynamic aza-Michael reaction or a catalyst-free transesterification in the presence of hydroxyl moieties. This results in reprocessable, densely cross-linked materials with a glass transition temperature (Tg) ranging from -60 to 90 °C. Moreover, even for the low Tg materials, a high creep resistance was demonstrated at elevated temperatures up to 80 °C. When additional β-hydroxyl group-containing building blocks are applied during the network design, an enhanced neighboring group participation effect allows reprocessing of materials up to 10 times at 150 °C within 30 min while maintaining their material properties.
- Du Prez, Filip E.,Guerre, Marc,Taplan, Christian
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supporting information
p. 9140 - 9150
(2021/07/01)
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- READILY BIODEGRADABLE ALKOXYLATE MIXTURES
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A mixture of octanols, nonanols and decanols is useful for the preparation of alkoxylates, which alkoxylates may be used as surfactants, which surfactants have surprisingly good biodegradability.
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Paragraph 0040-0043
(2021/05/14)
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- Hydrogen borrowing catalysis using 1° and 2° alcohols: Investigation and scope leading to α and β branched products
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The alkylation of a variety of ketones using 1° or 2° alcohols under hydrogen borrowing catalysis is described. Initial research focused on the α-alkylation of cyclopropyl ketones with higher 1° alcohols (i.e. larger than MeOH), leading to the formation of α-branched products. Our search for additional substrates with which to explore this chemistry led us to discover that di-ortho-substituted aryl ketones were also privileged scaffolds, with Ph? (C6Me5) ketones being the optimal choice. Further investigations revealed that this motif was crucial for alkylation with 2° alcohols forming β-branched products, which also provided an opportunity to study diastereoselective and intramolecular hydrogen borrowing processes.
- Frost, James R.,Cheong, Choon Boon,Akhtar, Wasim M.,Caputo, Dimitri F.J.,Christensen, Kirsten E.,Stevenson, Neil G.,Donohoe, Timothy J.
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supporting information
(2021/04/07)
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- Room temperature depolymerization of lignin using a protic and metal based ionic liquid system: an efficient method of catalytic conversion and value addition
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Lignin is one of the most abundant biopolymer which can be utilized to synthesize various chemicalsviaits depolymerization. However, depolymerization of lignin generally occurs under very harsh conditions. Herein, we report the efficient depolymerization of ligninviadissolution in a mixed ionic liquid system: ethyl ammonium nitrate (EAN) + prolinium tetrachloromanganate(ii) [Pro]2[MnCl4] at 35 °C and under atmospheric pressure conditions. The high dissolution of lignin in ethyl ammonium nitrate provided a large number of H-bonding sites leading to the cracking of lignin and subsequent oxidative conversion by [Pro]2[MnCl4]viathe formation of metal-oxo bonding between Mn and lignin molecules. The extracted yield of vanillin was found to be 18-20% on lignin weight basisviaGC-MS analysis. The depolymerization of lignin was confirmed by SEM, FT-IR and PXRD analysis. Since lignin contains UV-absorbing functional groups, the regenerated biomass after the recovery of the depolymerized products was further utilized to synthesize a UV-shielding material. The constructed films from such a material exhibited a high SPF value of 22 and were found to be very effective by limiting the UV degradation of rhodamine B thus making the lignin valorization process economically viable and environmentally sustainable.
- Mehta, Mohit J.,Kulshrestha, Akshay,Sharma, Shweta,Kumar, Arvind
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p. 1240 - 1247
(2021/02/26)
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- Improving the Catalytic Stability of Ni/TiO2 for Ethanol Guerbet Condensation: Influence of Second Metal Component
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Abstract: Ethanol Guerbet condensation (EGC) is a green process for preparing n-butanol and the development of highly effective solid catalysts is still the bottleneck of this reaction. In this work, a series of multifunctional catalysts Ni–X/TiO2 (X = Ru, Pt, Ir, Au, Cu, Mn, Co, Fe) were prepared by a co-impregnation method in order to improve the catalytic performance, especially the stability. It was found that the addition of the second metal component changed the acidity and alkalinity of Ni/TiO2 catalyst. What is more, acid site number affected ethanol conversion while alkali site number affected n-butanol selectivity. Among the Ni–X/TiO2 catalysts, Ni–Cu/TiO2 showed the best catalytic performance. The effects of preparation conditions on the catalytic performance of Ni–Cu/TiO2 were investigated and the results showed that the suitable preparation conditions were as follows: a Ni/Cu mass ratio of 59 : 1, a Ni–Cu loading of 12.5 wt %, a calcination temperature of 450°C, a calcination time of 2 h, a reduction temperature of 400°C, and a reduction time of 4?h. At a 10 wt % of catalyst loading, a reaction temperature of 210°C and a reaction time of 10 h, the ethanol conversion and the selectivity of n-butanol were 47.9 and 44.4%, respectively. Moreover, the stability of Ni–Cu/TiO2 catalyst was greatly improved due to the interaction between Ni and Cu as compared with the Ni/TiO2 catalyst: the catalytic activity of Ni–Cu/TiO2 did not decline significantly for reuse in three cycles.
- An, Hualiang,Han, Xiaoxu,Li, Shuaiqi,Wang, Yanji,Zhao, Xinqiang
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p. 632 - 640
(2021/09/28)
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- SATURATED HOMOETHER MANUFACTURING METHOD FROM UNSATURATED CARBONYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for manufacturing saturated homoether from an unsaturated carboxyl compound at good efficiency. SOLUTION: There is provided a manufacturing method of saturated homoether using an unsaturated carboxyl compound and hydrogen as raw materials, and a catalyst in which a metal is carried on an acidic catalyst carrier. The metal of the catalyst is for example palladium, and the carrier of the catalyst is alumina, silica, silica-alumina, or the like. The unsaturated carbonyl compound as the raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal, and manufactured saturated homoether is dibuthylether, bis(2-ethylhexyl)ether, bis(2-ethylbuty)ether, dihexylether, or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
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Paragraph 0043-0044
(2020/05/14)
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- HIGHLY EFFICIENT METHOD FOR PRODUCING SATURATED HOMOETHER FROM UNSATURATED CARBONYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing a saturated homoether from an unsaturated carbonyl compound. SOLUTION: The method for producing an unsaturated homoether uses an unsaturated carbonyl compound and hydrogen as a raw material, uses a catalyst comprising a metal supported on an acidic catalyst carrier and performs at least once a pressure reduction operation so that a differential pressure from a reaction pressure is 0.01 MPa or more. In the method, the metal of the catalyst is, for example, palladium and the carrier of the catalyst is alumina, silica, silica-alumina or the like. The unsaturated carbonyl compound serving as a raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal or the like and the produced saturated homoether is dibutyl ether, bis(2-ethylhexyl)ether, bis(2-ethylbutyl)ether, dihexyl ether or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0041; 0048
(2020/07/16)
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- Iron-catalyzed selective production of methyl esters from aldehydes
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A process for making methyl esters in high yields is provided. The process comprises contacting aliphatic or aromatic aldehydes and methanol with an iron catalyst, to catalyze the dehydrogenative coupling between aliphatic or aromatic aldehydes and methanol. The reaction is highly selective (99.9%) toward the formation of methyl esters over homoesters and alcohols and operates at temperatures of less than 100° C. for 2-8 hours.
- -
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Page/Page column 2-3
(2020/04/01)
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- Process for the production of esters
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A process for making methyl esters in high yields. The process comprises contacting aliphatic or aromatic aldehydes and methanol with a homogeneous dimeric ruthenium catalyst, to catalyze the dehydrogenative coupling between aliphatic or aromatic aldehydes and methanol. The reaction is highly selective (99.9%) toward the formation of methyl esters over homoesters and alcohols and operates at temperatures of less than 100° C. for 2-8 hours.
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Page/Page column 2; 3
(2020/03/18)
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- Iridium Complex-Catalyzed C2-Extension of Primary Alcohols with Ethanol via a Hydrogen Autotransfer Reaction
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The development of a C2-extension of primary alcohols with ethanol as the C2 source and catalysis by [Cp*IrCl2]2 (where Cp? = pentamethylcyclopentadiene) is described. This new extension system was used for a range of benzylic alcohol substrates and for aliphatic alcohols with ethanol as an alkyl reagent to generate the corresponding C2-extended linear alcohols. Mechanistic studies of the reaction by means of intermediates and deuterium labeling experiments suggest the reaction is based on hydrogen autotransfer.
- Kobayashi, Masaki,Itoh, Satoshi,Yoshimura, Keisuke,Tsukamoto, Yuya,Obora, Yasushi
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p. 11952 - 11958
(2020/10/23)
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- ESTER SYNTHESIS USING HETEROGENEOUS AU/TIO2 CATALYST
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A process for direct esterification of an alkyl aldehyde with an alkyl alcohol to produce an alkyl ester is disclosed. The process comprises reacting an alkyl aldehyde with an alkyl alcohol in the presence of an Au/TiOa catalyst, a base and an enal or oxygen to form an ester and an aldehyde. The process avoids liberation of water and avoids the step of oxidation of the alkyl aldehyde to an alkyl acid.
- -
-
Paragraph 0034; 0035
(2020/06/05)
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- Highly selective tetrahydropyranylation/dehydropyranylation of alcohols and phenols using porous phenolsulfonic acid-formaldehyde resin catalyst under solvent-free condition
-
An efficient protocol for solvent-free chemoselective tetrahydropyranylation/depyranylation of alcohols and phenols is reported herein using mesoporous Phenolsulfonic Acid Formaldehyde Resins as a heterogeneous acid catalyst. The catalyst successfully performed chemoselective protection and deprotection reactions of a wide range of substrates ranging from primary to secondary and tertiary alcohols and also phenols. The reactions were carried out at ambient temperature under solvent-free condition (SolFC) which resulted in high yields within a very short time. FT-IR, TEM, SEM, EDS and TG-DSC analysis techniques were employed to characterize the synthesized polymeric catalyst. The chemoselective nature of our method was confirmed using 13C DEPT-135 NMR studies. The polymer catalyst was found to be recoverable even after 10th catalytic cycle without much depreciation in its activity. The heterogeneity of the catalyst was verified by hot filtration method. Good yield, energy and cost- effective method, solvent-free protocol, mild reaction conditions, no inert atmosphere, metal-free heterogeneous polymer catalyst and excellent recoverability of the catalyst are notable milestones of the reported protocol.
- Rajkumari, Kalyani,Laskar, Ikbal Bahar,Kumari, Anupama,Kalita, Bandita,Rokhum, Lalthazuala
-
-
- Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification
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Synthesis of distillate-range fuels from biomass-derived alcohols has recently received considerable attention due to projected increases in the demands of these fuels and the extensive commercialization of alcohol production. Here we present a two-stage process by which an alcohol such as ethanol or 1-butanol can be converted with high yields into distillate-range ethers and olefins by combining Guerbet coupling and intermolecular dehydration. The ethers can be used as cetane-improvers in diesel fuel, while the olefins can be hydrogenated and blended with gasoline or oligomerized and hydrogenated to jet-range paraffins. The first stage was executed using calcium hydroxyapatite to produce higher linear and branched alcohols at above 80% selectivity at up to 40% conversion with high stability for over 400 h time-on-stream operation. Increasing conversion decreases selectivity, producing predominantly mono-ene and diene byproducts. Etherification was performed using the acidic resin Amberlyst 70 at around 65% conversion. Linear alcohols were converted at above 90% selectivity while branched alcohols were far more selective to olefins (65-75%). Etherification occurs via two mechanisms: a direct mechanism involving the reaction of two alcohols and an indirect mechanism between an alcohol and equilibrated pool of olefins. Cross-etherification was observed between linear and branched alcohols, improving the selectivity to ethers in conversion of the latter. A mixture of C4+ alcohols produced from ethanol condensation at 40% conversion was effectively utilized in etherification at selectivities comparable to the model mixtures. An overall process is presented for the conversion of ethanol to diesel-range ethers and olefins with yields of approximately 80%.
- Eagan, Nathaniel M.,Moore, Benjamin M.,McCelland, Daniel J.,Wittrig, Ashley M.,Canales, Emmanuel,Lanci, Michael P.,Huber, George W.
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p. 3300 - 3318
(2019/06/24)
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- IMPROVED PROCESS FOR THE TRANSFORMATION OF PRIMARY ALIPHATIC ALCOHOLS INTO HIGHER ALIPHATIC ALCOHOLS
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A process for obtaining higher aliphatic alcohols starting from aliphatic primary alcohols by condensation reactions is disclosed. Specifically, the process comprises a step in which an aliphatic primary alcohol is contacted in a homogeneous phase with a catalyst mixture comprising a transition metal, a base and an additive; specifically, this additive can be selected from the classes of compounds of the isoquinolines N-oxide, quinolines N-oxide, pyridines N-oxide, benzoquinones, naphthoquinones, or TEMPO. In particular, the process can be carried out by contacting said aliphatic primary alcohol with a catalyst of a recycled transition metal, with a freshly added base and with a recycled additive of the aforementioned type.
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Page/Page column 18; 19
(2019/10/30)
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- METHODS AND COMPOSITIONS FOR THE CATALYTIC UPGRADING OF ALCOHOLS
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Compositions and methods of use related to metal organic frameworks (MOFs) and/or nanoparticles are generally described. In some embodiments, methods and compositions for the catalytic upgrading of alcohols using MOFs and/or nanoparticles associated with MOFs are generally described. In some embodiments, a catalytic MOF composition is provided, wherein the MOF composition comprises a MOF compound and a plurality of metal catalytic compounds. In some embodiments, an alcohol may be exposed to the MOF composition and/or a plurality of nanoparticles associated with the MOF composition such that the alcohol is converted to a higher order alcohol. Advantageously, in some embodiments, the alcohol conversion occurs at a relatively high turnover frequency and/or with a relatively high selectivity as compared to traditional methods for converting alcohols.
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-
Paragraph 0184; 0188; 0189
(2019/12/02)
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- Diastereoselective synthesis of functionally substituted alkene dimers and oligomers, catalysed by chiral zirconocenes
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The research addresses the reaction of terminal alkenes and propene with AlR3 (R = Me, Et) in the presence of chiral Zr complexes, rac-[Y(η5-C9H10)2]ZrCl2 (Y = C2H4, SiMe2) or (NMI)2ZrCl2 (NMI- η5–neomenthylindenyl), and methylaluminoxane. The effect of reaction conditions, catalyst and trialkylalane structure on the substrate conversion and the reaction chemo- and stereoselectivity has been studied. The reaction predominantly goes via the stage of alkene methyl(ethyl)zirconation with subsequent introduction of substrate molecules into the Zr-C bond. As a result, a diastereoselective one-pot method for the synthesis of functionally substituted linear terminal alkene dimers and propene oligomers was developed.
- Kovyazin, Pavel V.,Abdullin, Il'giz N.,Parfenova, Lyudmila V.
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p. 144 - 152
(2018/11/21)
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- BRANCHED TRIALKYLAMINE PRECURSORS, INTERMEDIATES, PRODUCTS MADE THEREFROM AND PROCESSES OF MANUFACTURE
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The invention provides branched hydrophobes for the production of surfactants with improved properties over linear hydrophobes. The invention also provides branched C10-12 enals and aldehydes that are oxidized to branched fatty acids or hydrogenated to branched fatty alcohols and further derivatized to surfactants, through ethoxylation or esterification and other or subsequent reactions. The invention further provides surfactants made from the branched trialkylamine intermediates, including amphoteric, cationic and nonionic surfactants.
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Paragraph 0367
(2019/07/29)
-
- Transfer-hydrogenation process
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A transfer-hydrogenation process for preparing a carbonyl compound and an alcohol compound comprises the steps of (a) contacting a first carbonyl compound with a first alcohol compound in the presence of a transfer-hydrogenation catalyst in a first reaction zone at conditions effective to form a second carbonyl compound from the first alcohol compound and a second alcohol compound from the first carbonyl compound, and (b) removing the second carbonyl compound from the first reaction zone during step (a). The first carbonyl compound is a saturated aldehyde or ketone, or an α,β-unsaturated aldehyde or ketone. The first alcohol compound is a primary or secondary alcohol. The second alcohol compound is α,β-saturated. The transfer-hydrogenation catalyst includes a Group 8 to 11 metal. This process is useful for preparing and higher value alcohols, such as butanol or 2-ethylhexanol, from the corresponding carbonyl compounds by engaging lower alcohol (C2-C4) feedstocks instead of hydrogen (H2).
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Page/Page column 19; 20; 22-25
(2018/06/19)
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- PROCESS FOR THE PRODUCTION OF 2-ALKYLALKANOL
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A process for the production of 2-alkylalkanol from an aldehyde is disclosed. The process comprises the steps of: feeding aldehyde to a reactor (42) operated under condensation and dehydration conditions such that reaction occurs and an unsaturated aldehyde is produced; recovering a stream from the reactor (42) comprising the unsaturated aldehyde and feeding said stream to a first hydrogenation reactor (45) operated under conditions such that at least some of the unsaturated aldehyde is converted to 2-alkylalkanol; recovering the stream from the first hydrogenation reactor (45) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal and heavies; passing the stream recovered from the first hydrogenation reactor (45) to a first distillation zone (48) where at least some of the heavies are separated from the stream; recovering a stream from the first distillation zone (48) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal, said stream having a reduced heavies content when compared to the stream fed to the first distillation zone (48), and feeding said stream to a second hydrogenation reactor (51) operated under conditions such that at least one of the unreacted acrolein, alkylalkenol and alkylalkanal are converted to 2-alkylalkanol; and recovering a stream from the second hydrogenation reactor (51) comprising an increased 2-alkylalkanol content compared to the stream fed to the second hydrogenation reactor (51).
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Page/Page column 10; 11
(2018/04/27)
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- Acetaldehyde as an ethanol derived bio-building block: An alternative to Guerbet chemistry
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In this work, we describe a highly selective poly-aldol condensation of acetaldehyde, which can readily be obtained via dehydrogenation of ethanol. The process operates under mild temperatures (100°C or less) using commercially available catalysts and exhibits excellent total carbon yield of C4+ products with good selectivity for C6 products. The products derived from the reactions described herein are shown to be candidate drop-in fuel replacements for compression ignition engines and precursors to valuable chemicals.
- Moore, Cameron M.,Staples, Orion,Jenkins, Rhodri W.,Brooks, Ty J.,Semelsberger, Troy A.,Sutton, Andrew D.
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supporting information
p. 169 - 174
(2017/01/24)
-
- SINGLE-STEP CONVERSION OF N-BUTYRALDEHYDE TO 2-ETHYLHEXANAL
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Disclosed is a method of making and using a titania supported palladium catalyst for the single step synthesis of 2-ethylhexanal from a feed of n-butyraldehyde. This titania supported palladium catalyst demonstrates high n-butyraldehyde conversion but also produces 2-ethylhexanal in an appreciable yield with maintained activity between runs. This method provides a single step synthesis of 2-ethylhexanal from n-butyraldehyde with a catalyst that can be regenerated that provides cleaner downstream separations relative to the traditional caustic route.
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Paragraph 00130; 00133
(2017/08/21)
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- Liquid hydrogenation apparatus of liquid aldehydes and method for preparing liquid alcohols using the apparatus
-
The present invention relates to an aldehyde hydrogenating device and a hydrogenating method using the same. According to the present invention, even when liquid aldehyde which is a raw ingredient is not gasified, productivity and aldehyde conversion rates are excellent. Production costs are remarkably reduced, and reactor heating and large capacity compressor usage can be avoided, so that energy consumption is reduced.
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Paragraph 0044 - 0051
(2016/10/07)
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- Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid
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The present application relates to a method and an apparatus for preparing alkanol, the method and apparatus according to the present application improving the preparation process to be more economical and stable, and allowing the mass production of alkanol.
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Paragraph 0068; 0069
(2016/10/31)
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- METHOD OF PREPARING ALKANOL (AS AMENDED)
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Provided are a method of preparing an alkanol and a device for preparing the same. According to the method and device, economic feasibility and stability of a preparation process may be enhanced, and mass production of an alkanol may be performed.
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Paragraph 0047
(2016/08/17)
-
- Reactivity of ethanol over hydroxyapatite-based Ca-enriched catalysts with various carbonate contents
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The Guerbet reaction of ethanol to produce heavier products was performed over a series of extensively characterized carbonate-containing hydroxyapatites (HAPs) with different Ca/P ratios and thus different densities, strengths and natures of acid and bas
- Silvester, Lishil,Lamonier, Jean-Fran?ois,Faye, Jérémy,Capron, Micka?l,Vannier, Rose-No?lle,Lamonier, Carole,Dubois, Jean-Luc,Couturier, Jean-Luc,Calais, Christophe,Dumeignil, Franck
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p. 2994 - 3006
(2015/05/13)
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- APPARATUS AND METHOD FOR PREPARING ALCOHOL FROM OLEFIN
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Disclosed are an apparatus and method for preparing alcohol from olefin. A reactor for hydroformylating olefin comprises a loop reactor for reducing high-boiling point components, a post-treatment device for separating aldehyde comprises a catalyst/aldehyde separator and a divided wall column (DWC) for removing remaining high-boiling point components, and a post-treatment device for separating alcohol comprises a divided wall column (DWC) for removing remaining high-boiling point components. The apparatus and method for preparing alcohol reduce production of high-boiling point components in the preparation of alcohols and efficiently remove remaining high-boiling point components, thus obtaining alcohol containing no high-boiling point components.
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Paragraph 0096-0098
(2014/11/13)
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- PROMOTED RUTHENIUM CATALYST FOR THE IMPROVED HYDROGENATION OF CARBOXYLIC ACIDS TO THE CORRESPONDING ALCOHOLS
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The invention relates to ruthenium-rhenium-tin and ruthenium-rhenium catalysts effective for the reduction of carboxylic acids to the corresponding alcohols and processes for the reduction of carboxylic acids to the corresponding alcohols using the ruthenium-rhenium-tin and ruthenium-rhenium catalysts.
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Paragraph 0089
(2014/05/08)
-
- Pd-catalyzed reduction of aldehydes to alcohols using formic acid as the hydrogen donor
-
Facile and selective reduction of aromatic aldehydes as well as aliphatic aldehydes to alcohols was achieved using formic acid as the hydrogen donor in the presence of a catalytic amount of Pd(OAc)2 and Cy3P. It was found that both hydrogen atoms in the formic acid molecule can serve as the hydride source. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Wang, Anwei,Yang, Zhiyong,Liu, Jidan,Gui, Qingwen,Chen, Xiang,Tan, Ze,Shi, Ji-Cheng
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supporting information
p. 280 - 288
(2013/12/04)
-
- Production of Higher Alcohols
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A reactive distillation method comprises introducing a feed stream to a reactive distillation column, contacting the feed stream with one or more catalysts in the reactive distillation column during a distillation, and removing one or more higher alcohols during the distillation from the reactive distillation column as a bottoms stream. The feed stream comprises one or more alpha hydrogen alcohols, and the feed stream reacts in the presence of the one or more catalysts to produce a reaction product comprising the one or more higher alcohols.
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Paragraph 0198-0200
(2014/09/03)
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- Highly dispersed Pd on Co-B amorphous alloy: Facile synthesis via galvanic replacement reaction and synergetic effect between Pd and Co
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In this paper, uniform Co-B amorphous alloy nanospheres with an average particle size of 50 nm were synthesized by chemical reduction of cobalt ion with borohydride in aqueous solution containing Bu4PBr and KCl. Then, Pd was introduced into this system by galvanic replacement reaction (GRR) between Co and Na2PdCl4. Pd/Co-B catalysts with different Pd content could be obtained via adjusting the amount of Na2PdCl 4 in reaction mixture. The crystal structure, morphology, and surface electronic state of as-prepared catalysts were characterized by XRD, TEM, XPS, and H2-TPD. During the liquid-phase hydrogenation of 2-ethyl-2-hexenaldehyde, the as-prepared Pd/Co-B catalysts exhibited extremely active and more selectivity to 2-ethyl-1-hexanol than the monometallic Pd and Co-B amorphous alloy, showing potential application in industry. The enhanced performances could be attributed to the highly dispersed Pd on the surface of Co-B prepared by GRR and the synergetic effect between Pd and Co.
- Li, Hui,Ma, Jinqiang,Xu, Liang,Xu, Lei,Wang, Hao,Xu, Sen,Li, Hexing,Xie, Songhai
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p. 985 - 992
(2013/07/25)
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- Asymmetric alkene cycloalumination by AlEt3, catalyzed with neomenthylindenyl zirconium η5-complexes
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The paper is devoted to a study of the reaction of terminal alkene cycloalumination by AlEt3 catalyzed with neomenthylindenyl zirconium complexes (p-S)(p-S)-bis[η5-[1-[(1S,2S,5R)-2-isopropyl-5- methylcycloh-exyl]indenyl]]zirconium dichloride (1) or (p-S)-(η5- cyclopentadienyl)[η5-[1-[(1S,2S,5R)-2-isopropyl-5- methylcyclohexyl]indenyl]]zirconium dichloride (2). It was shown that alkene and catalyst structures, as well as solvent, affect the overall yield and enantiomeric excess of the reaction product - 3-alkylsubstituted aluminacyclopentanes. The reaction of terminal alkenes with AlEt3, catalyzed by complex 1, in hydrocarbon solvents gives predominantly S-enantiomers of cyclic organoaluminum compounds with enantiomeric excess up to 37%. Complex 2 shows smaller stereoinduction effect and provides R-enantiomers of aluminacyclopentanes with 6-26%ee. The effectiveness of selenium-containing derivatizing reagent (R)-2-phenylselenopropanoic acid for the enantiomeric excess estimation in β-alkyl-1,4-butanediols obtained from cyclic organoaluminum compounds was shown.
- Parfenova, Lyudmila V.,Kovyazin, Pavel V.,Tyumkina, Tatyana V.,Berestova, Tatyana V.,Khalilov, Leonard M.,Dzhemilev, Usein M.
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-