142-96-1Relevant articles and documents
Acid catalysts based on Cu/Ru alumina: Conversion of butyraldehyde to dibutyl ether
Jansen, Susan,Palmieri, Michael,Gomez, Maria,Lawrence, Steve
, p. 262 - 270 (1996)
A system made by combining two nonalloying metals, ruthenium and copper, using alumina as the oxide support was studied. This bimetallic supported catalyst has been used mainly in hydrogenolysis, dehydrogenation, and oxidation reactions of hydrocarbons. The preparation of such materials has been proposed to effect the selectivity and activity of a highly active metal by inclusion of a second less active metal. The samples were characterized by electron paramagnetic resonance spectrometry (EPR), X-ray diffraction (XRD), surface area, and surface acidities. The techniques EPR and XRD are ideal for studying the electronic and structural changes of the samples at different temperatures and concentrations. The primary reaction involved in this study was the hydrogenation of an aldehyde to the corresponding alcohol. A secondary reaction occurred as well. The acid catalyzed, substitution or bimolecular dehydration of the alcohol to the dibutyl ether was observed under certain catalytic conditions. These catalysts appeared to act as acid/base. Therefore this reaction to produce the ether is of special importance. A correlation between the electronic, structural and catalytic properties has been made to understand molecular processes' role in catalytic phenomena.
Etherification of n-butanol to di-n-butyl ether over Keggin-, wells-Dawson-, and preyssler-type heteropolyacid catalysts
Kim, Jeong Kwon,Choi, Jung Ho,Park, Dong Ryul,Song, In Kyu
, p. 8121 - 8126 (2013)
Etherification of n-butanol to di-n-butyl ether was carried out over various structural classes of heteropolyacid (HPA) catalysts, including Keggin- (H3PW12O40), Wells-Dawson- (H6P2W18O62), and Preyssler-type (H14[NaP5W30O110]) HPA catalysts. Successful formation of HPA catalysts was well confirmed by FT-IR, 31P NMR, and ICP-AES analyses. Acid properties of HPA catalysts were determined by NH3-TPD (temperature-programmed desorption) measurements. Acid strength of the catalysts increased in the order of H14 [NaP5W30O110] 6P2W18O62 3PW12O40. The catalytic performance of HPA catalysts was closely related to the acid strength of the catalysts. In the etherification of n-butanol to di-n-butyl ether over various structural classes of HPA catalysts, Conversion of n-butanol and yield for di-n-butyl ether increased with increasing acid strength of HPA catalysts. Among the catalysts tested, Keggin-type (H3PW12O40) HPA catalyst with the strongest acid strength showed the best catalytic performance. Acid strength of HPAs served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-butyl ether. Copyright
Influence of butanol isomers on the reactivity of cellulose towards the synthesis of butyl levulinates catalyzed by liquid and solid acid catalysts
Démolis, Alexandre,Eternot, Marion,Essayem, Nadine,Rataboul, Franck
, p. 3747 - 3754 (2016)
Butyl esters of levulinic acid form an interesting class of bio-based compounds that can be used, for example, as fuel additives. Their preparation mainly proceeds through the esterification of levulinic acid while the few reported studies on their direct synthesis from cellulose give limited information. In the present work, we studied for the first time in detail the influence of butanol isomers on the non-catalyzed cellulose liquefaction and the acid catalyzed formation of butyl levulinates from cellulose. In the absence of catalysts there was no influence of the alcohol class on liquefaction which reached 70-85% after 2 hours at 300 °C. In the presence of catalysts, we showed that the class of the alcohol had a significant influence on the butyl levulinate yield. With primary alcohols yields of 50% were obtained in the presence of H2SO4 (200 °C, 30 min). This level of yield can be considered as very interesting for these kinds of one-pot transformations involving cellulose. With secondary alcohols, yields less than 20% were obtained while no butyl levulinate was formed with tertiary alcohols. We also report for the first time this transformation in the presence of solid acids. Insoluble Cs2HPW12O40 or sulfated zirconia catalyzed the reaction heterogeneously despite deactivation leading to limited yields of 13% (200 °C, 1 hour). We finally show that water in butanol had an ambivalent role in enhancing the cellulose reactivity but limiting the esterification step and found that 5-7 wt%/butanol of water was the optimum amount.
Etherification of n-butanol to di-n-butyl ether over HnXW 12O40 (XCo2+, B3+, Si4+, and P5+) Keggin heteropolyacid catalysts
Kim, Jeong Kwon,Choi, Jung Ho,Song, Ji Hwan,Yi, Jongheop,Song, In Kyu
, p. 5 - 8 (2012)
Etherification of n-butanol to di-n-butyl ether was carried out over heteroatom-substituted HnXW12O40 (XCo 2+, B3+, Si4+, and P5+) Keggin heteropolyacid (HPA) catalysts. Acid properties of HPA catalysts were determined by NH3-TPD measurements. Acid strength of HnXW 12O40 Keggin HPA catalysts increased in the order of H6CoW12O40 5BW 12O40 4SiW12O40 3PW12O40. Yield for di-n-butyl ether increased with increasing acid strength of the catalysts. Acid strength of HPAs served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-butyl ether.
AQUIVION perfluorosulfonic acid resin for butyl levulinate production from furfuryl alcohol
Bernal, Hilda Gómez,Oldani, Claudio,Funaioli, Tiziana,Raspolli Galletti, Anna Maria
, p. 14694 - 14700 (2019)
This study reports the sustainable production of butyl levulinate (BL) from furfuryl alcohol (FA), a highly abundant biomass derived platform obtained from C5 sugars in hemicellulose. FA upgrading is performed adopting a robust and easily recyclable commercial perfluorosulfonic acid resin, Aquivion P87S, used as cylinder shaped pellets. This approach avoids the use of corrosive and harmful mineral acids allowing a simple separation of the catalyst from the reaction mixture, reducing the cost of equipment materials and disposal or neutralization issues, also resulting in reduced solvent dehydration. Moreover, FA alcoholysis to BL involves butanol as a sustainable reaction medium, also readily obtained from biomass. The catalyst remains stable up to 6 recycles. Furthermore, the absence of heavy by-products and the stability of the catalyst allowed us to perform successive additions of the substrate to the reaction medium to increase the BL concentrations up to 0.66 M (13 wt%).
Ion exchange resins as catalysts for the liquid-phase dehydration of 1-butanol to di-n-butyl ether
Pérez,Bringué,Iborra,Tejero,Cunill
, p. 38 - 48 (2014)
This work reports the production of di-n-butyl ether (DNBE) by means of 1-butanol dehydration in the liquid phase on acidic ion-exchange resins. Dehydration experiments were performed at 150 °C and 40 bar on 13 styrene-codivinylbenzene ion exchangers of different morphology. By comparing 1-butanol conversions to DNBE and initial reaction rates it is concluded that oversulfonated resins are the most active catalysts for 1-butanol dehydration reaction whereas gel-type resins that swell significantly in the reaction medium as well as the macroreticular thermostable resin Amberlyst 70 are the most selective to DNBE. The highest DNBE yield was achieved on Amberlyst 36. The influence of typical 1-butanol impurities on the dehydration reaction were also investigated showing that the presence of 2-methyl-1-propanol (isobutanol) enhances the formation of branched ethers such as 1-(1-methylpropoxy) butane and 1-(2-methylpropoxy) butane, whereas the presence of ethanol and acetone yields ethyl butyl ether and, to a much lesser extent, diethyl ether.
Polymer-supported catalysts for clean preparation of n-butanol
Jiang, Haibin,Lu, Shuliang,Zhang, Xiaohong,Peng, Hui,Dai, Wei,Qiao, Jinliang
, p. 2499 - 2503 (2014)
A new type of RANEY metal catalyst supported by polymer was developed for the clean preparation of n-butanol. Unlike traditional supported catalysts, the newly developed alkalescent polyamide 6 (PA6) supported RANEY nickel catalyst provided a 100.0% conversion of n-butyraldehyde without producing any detectable n-butyl ether, the main byproduct in industry. The significantly enhanced catalyst selectivity of the polymer-supported RANEY metal catalyst was attributed to the elimination of the acid-catalyzed side reaction associated with RANEY metals and traditional catalyst supports, such as Al2O3 and SiO2. By eliminating acid-catalyzed side reactions, therefore, green chemistry could be achieved through reducing resources and energy consumption in chemical reactions. Furthermore, the preparation and recycling of the polymer-supported catalysts are also much more eco-friendly than for traditional Al2O3-/SiO 2-supported catalysts. The methodology developed in this study to use alkalescent polymers as the catalyst support could be applied to the whole catalyst family, including a series of important RANEY metal catalysts (e.g., RANEY nickel, RANEY cobalt, RANEY copper) used routinely in the chemical industry.
A catalytic symmetrical etherification
Bagnell, Laurence,Cablewski, Teresa,Strauss, Christopher R.
, p. 283 - 284 (1999)
A novel, catalytic, thermal etherification produces minimal waste and can be carried out under almost neutral conditions.
The Guanidine-Promoted Direct Synthesis of Open-Chained Carbonates
Shang, Yuhan,Zheng, Mai,Zhang, Haibo,Zhou, Xiaohai
, p. 933 - 938 (2019)
In order to reduce CO2 accumulation in the atmosphere, chemical fixation methodologies were developed and proved to be promising. In general, CO2 was turned into cyclic carbonates by cycloaddition with epoxides. However, the cyclic carbonates need to be converted into open-chained carbonates by transesterification for industrial usage, which results in wasted energy and materials. Herein, we report a process catalyzed by tetramethylguanidine (TMG) to afford linear carbonates directly. This process is greener and shows potential for industrial applications.
Reactions of Ionized Dibutyl Ether
Bowen, Richard D.,Suh, Dennis,Terlouw, Johan K.
, p. 791 - 805 (1994)
The reactions of ionized di-n-butyl ether are reported and compared with those of ionized n-butyl sec-butyl and di-sec-butyl ether.The main fragmentation of metastable (CH3CH2CH2CH2)O+. is C2H5. loss (ca. 85percent), but minor amounts (2-4percent of CH3., C4H7., C4H9., C4H10 and C4H10O are also eliminated.In contrast, C2H5. elimination is of much lower abundance (20 and 4percent, respectively) from metastable CH3CH2CH2CH2OCH(CH3)CH2CH3+. and 2O+., which expel mainly C2H6 and CH3. (35percent-55percent).Studies on collisional activation spectra of the C6H13O+ oxonium ions reveal that C2H5. loss from (CH3CH2CH2CH2)2O+. gives the same product, (CH3CH2CH2CH2+O=CHCH3) as that formed by direct cleavage of CH3CH2CH2CH2OCH(CH3)CH2CH3+..Elimination of C2H5. from (CH3CH2CH2CH2O+. is interpreted by means of a mechanism in which a 1,4-H shift to the oxygen atom initiates a unidirectional skeletal rearrangement to CH3CH2CH2CH2OCH(CH3)CH2CH3+., which than undergoes cleavage to CH3CH2CH2CH2+O=CHCH3 and C2H5..Further support for this mechanism is obtained from considering the collisional activation and neutralization-reionization mass spectra of the (C4H9)2O+. species and the behaviour of the labelled analogues of the (CH3CH2CH2CH2)2O+..The rate of ethyl radical loss is suppressed relative to those of alternative dissociations by deuteriation at the γ-position of either or both butyl substituents.Moreover, C2H5. loss via skeletal rearrangement and fragmentation of the unlabelled butyl group in CH3CH2CH2CH2OCH2CH2CD2CH3+. occurs approximately five times more rapidly than C2H4D. expulsion via isomerization and fission of the labelled butyl substituent.These findings indicate that the initial 1,4-hydrogen shift is influenced by a significant isotope effect, as would be expected if this step is rate limiting in ethyl radical loss.
