- Ruthenium-catalysed hydroxycarbonylation of olefins
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State-of-the-art catalyst systems for hydroxy- and alkoxycarbonylations of olefins make use of palladium complexes. In this work, we report a complementary ruthenium-catalysed hydroxycarbonylation of olefins applying an inexpensive Ru-precursor (Ru3(CO)12) and PCy3as a ligand. Crucial for the success of this transformation is the use of hexafluoroisopropanol (HFIP) as the solvent in the presence of an acid co-catalyst (PTSA). Overall, moderate to good yields are obtained using aliphatic olefins including the industrially relevant substrate di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various carboxylic acids from unfunctionalized olefins.
- Dühren, Ricarda,Kucmierczyk, Peter,Jackstell, Ralf,Franke, Robert,Beller, Matthias
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p. 2026 - 2030
(2021/04/09)
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- An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins
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A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh1/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CH3I led to high activity and superb stability.
- Yuan, Qiao,Song, Xiangen,Feng, Siquan,Jiang, Miao,Yan, Li,Li, Jingwei,Ding, Yunjie
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supporting information
p. 472 - 475
(2021/01/25)
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- Mild C-H functionalization of alkanes catalyzed by bioinspired copper(ii) cores
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Three new copper(ii) coordination compounds formulated as [Cu(H1.5bdea)2](hba)·2H2O (1), [Cu2(μ-Hbdea)2(aca)2]·4H2O (2), and [Cu2(μ-Hbdea)2(μ-bdca)]n (3) were generated by aqueous medium self-assembly synthesis from Cu(NO3)2, N-butyldiethanolamine (H2bdea) as a main N,O-chelating building block and different carboxylic acids [4-hydroxybenzoic (Hhba), 9-anthracenecarboxylic (Haca), or 4,4′-biphenyldicarboxylic (H2bdca) acid] as supporting carboxylate ligands. The structures of products range from discrete mono- (1) or dicopper(ii) (2) cores to a 1D coordination polymer (3), and widen a family of copper(ii) coordination compounds derived from H2bdea. The obtained compounds were applied as bioinspired homogeneous catalysts for the mild C-H functionalization of saturated hydrocarbons (cyclic and linear C5-C8 alkanes). Two model catalytic reactions were explored, namely the oxidation of hydrocarbons with H2O2 to a mixture of alcohols and ketones, and the carboxylation of alkanes with CO/S2O82- to carboxylic acids. Both processes proceed under mild conditions with a high efficiency and the effects of different parameters (e.g., reaction time and presence of acid promoter, amount of catalyst and solvent composition, substrate scope and selectivity features) were studied and discussed in detail. In particular, an interesting promoting effect of water was unveiled in the oxidation of cyclohexane that is especially remarkable in the reaction catalyzed by 3, thus allowing a potential use of diluted, in situ generated solutions of hydrogen peroxide. Moreover, the obtained values of product yields (up to 41% based on alkane substrate) are very high when dealing with the C-H functionalization of saturated hydrocarbons and the mild conditions of these catalytic reactions (50-60 °C, H2O/CH3CN medium). This study thus contributes to an important field of alkane functionalization and provides a notable example of new Cu-based catalytic systems that can be easily generated by self-assembly from simple and low-cost chemicals.
- Kirillova, Marina V.,Fernandes, Tiago A.,André, Vania,Kirillov, Alexander M.
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supporting information
p. 7706 - 7714
(2019/08/30)
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- PROCESS FOR THE DIRECT CONVERSION OF ALKENES TO CARBOXYLIC ACIDS
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Process for the direct conversion of alkenes to carboxylic acids.
- -
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Paragraph 0029-0032
(2019/07/10)
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- Carbonylative Transformation of Allylarenes with CO Surrogates: Tunable Synthesis of 4-Arylbutanoic Acids, 2-Arylbutanoic Acids, and 4-Arylbutanals
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In this Communication, procedures for the selective synthesis of 4-arylbutanoic acids, 2-arylbutanoic acids, and 4-arylbutanals from the same allylbenzenes have been developed. With formic acid or TFBen as the CO surrogate, reactions proceed selectively and effectively under carbon monoxide gas-free conditions.
- Wu, Fu-Peng,Li, Da,Peng, Jin-Bao,Wu, Xiao-Feng
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supporting information
p. 5699 - 5703
(2019/08/01)
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- Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
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Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
- Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
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supporting information
p. 3967 - 3970
(2018/04/23)
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- Three-component 1D and 2D metal phosphonates: structural variability, topological analysis and catalytic hydrocarboxylation of alkanes
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Herein, we report the use of diphosphonate building blocks and chelating auxiliary N,N-ligands to generate novel polymeric architectures. Specifically, we report new 1D and 2D coordination polymers incorporating three components: transition metal ions (Co2+, Cu2+, Mn2+ or Zn2+), diphosphonate ligands (methane-diphosphonate, MDPA, or 1,2-ethanediphosphonate, EDPA) and N,N-heterocyclic chelators (1,10-phenanthroline, phen, or 2,2′-bipyridine, bpy). Six compounds were isolated under mild synthesis (ambient temperature) conditions: [Cu2(phen)2(EDPA)2(H2O)4]∞ (1), [Co(phen)(EDPA)(H2O)2]∞ (1a), {[Cu(phen)(MDPA)]·H2O]}∞ (2), [Mn(bpy)(EDPA)(H2O)2]∞ (3), [Zn(bpy)(EDPA)]∞ (4), and, lastly, a discrete Ni2+ molecular derivative [Ni(phen)(H2O)4](EDPA) (5). Synthetic details, crystal structures, and intermolecular interactions (π-π stacking and hydrogen bonding) in 1-5 are discussed. Topological analyses and classification of the underlying metal-organic networks in 1-4 were performed, revealing the uninodal 1D chains with the 2C1 topology in 1-3 and the binodal 2D layers with the 3,4L13 topology in 4. In 1-3 and 5, multiple hydrogen bonds lead to the extension of the structures to give 3D H-bonded nets with the seh-4,6-C2/c topology in 1 and 3, 2D H-bonded layers with the 3,5L52 topology in 2, and a 3D H-bonded net with the 6,6T1 topology in 5. The catalytic activity of compounds 1 and 1a was evaluated in a single-step hydrocarboxylation of cyclic and linear C5-C8 alkanes to furnish the carboxylic acids with one more carbon atom. These reactions proceed in the presence of CO, K2S2O8, and H2O at 60 °C in MeCN/H2O medium. Compound 1 showed higher activity than 1a and was studied in detail. Substrate scope was investigated, revealing that cyclohexane and n-pentane are the most reactive among the cyclic and linear C5-C8 alkanes, and resulting in the total yields of carboxylic acids (based on substrate) of up to 43 and 36%, respectively. In the case of cycloalkane substrates, only one cycloalkanecarboxylic acid is produced, whereas a series of isomeric monocarboxylic acids is generated when using linear alkanes; an increased regioselectivity at the C(2) position of the hydrocarbon chain was also observed.
- Demadis, Konstantinos D.,Anagnostou, Zafeiria,Panera, Aggeliki,Mezei, Gellert,Kirillova, Marina V.,Kirillov, Alexander M.
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p. 17788 - 17799
(2017/03/30)
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- Method for Producing Isononanoic Acid Esters, Starting from 2-Ethyl Hexanol
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A Process for preparing carboxylic esters of a mixture of structurally branched C9 monocarboxylic acids proceeding from 2-ethylhexanol is characterized in that (a) 2-ethylhexanol is dehydrated to an octene mixture in the presence of a catalyst; (b) the octene mixture obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give a mixture of isomeric isononanals; (c) the mixture of isomeric isononanals obtained in step b) is oxidized to a mixture of structurally branched C9 monocarboxylic acids; and (d) the mixture of structurally branched C9 monocarboxylic acids obtained in step c) is reacted with alcohols to give carboxylic esters.
- -
-
Paragraph 0081-0087
(2015/06/17)
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- Method for Producing Isononanoic Acids from 2-Ethyl Hexanol
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Process for preparing isononanoic acid proceeding from 2-ethylhexanol, characterized in that (a) 2-ethylhexanol is dehydrated to octene in the presence of a catalyst; (b) the octene obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give isononanal; and (c) the isononanal obtained in step b) is oxidized to isononanoic acid.
- -
-
Paragraph 0062-0071
(2015/07/15)
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- How to force a classical chelating ligand to a metal non-chelating bridge: The observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n
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The novel chain coordination polymer {[Cu2(Piv) 4(H3tBuDea)](Piv)}n (1) has been prepared through the self-assembly reaction of copper(ii) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H2tBuDea) in acetonitrile solution. Crystallographic analysis revealed the extremely rare non-chelating bridging coordination mode of diethanolamine ligand in 1, observed for the first time in transition metal complexes, as well as in complexes of diethanolamine having a non-coordinating aliphatic group at the N atom. Possible reasons for such a coordination and analysis of the main coordination modes of diethanolamine-based ligands are discussed. Variableerature (1.8-300 K) magnetic susceptibility measurements showed that 1 represents a rare example of dicopper(ii) tetracarboxylate that is a diamagnetic solid at room temperature. This behaviour is compared with literature examples and discussed on the basis of DFT calculations. Furthermore, 1 acts as an efficient catalyst for the mild hydrocarboxylation of linear and cyclic C5-C8 alkanes into the corresponding carboxylic acids.
- Nesterova, Oksana V.,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Boca, Roman,Pombeiro, Armando J. L.
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p. 775 - 783
(2014/01/17)
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- PROCESS FOR PRODUCING 2-ETHYLHEPTANOIC ACID
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Process for producing 2-ethylheptanoic acid.
- -
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Page/Page column 0052
(2014/07/22)
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- Carbon dioxide as a C1 building block for the formation of carboxylic acids by formal catalytic hydrocarboxylation
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A happy marriage of two processes: An effective catalytic system was identified for the direct synthesis of carboxylic acids from non-activated olefins or alcohols, CO2, and H2. Detailed analysis together with labeling studies indicated that the overall hydrocarboxylation of simple olefins results from a combination of the reverse water-gas shift (rWGS) reaction and a hydroxycarbonylation step, each promoted by a rhodium catalyst (see scheme). Copyright
- Ostapowicz, Thomas G.,Schmitz, Marc,Krystof, Monika,Klankermayer, Juergen,Leitner, Walter
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p. 12119 - 12123
(2013/12/04)
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- Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(ii) complexes: Magnetism and catalytic activity towards mild hydrocarboxylation of alkanes
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Three new tetranuclear copper(ii) complexes [Cu(HL1)] 4·4EtOH (1·4EtOH), [Cu(HL2)]4 (2) and [Cu(H2L3)]4(NO3) 4·2H2O (3·2H2O) have been synthesized using three different hydrazone Schiff base ligands derived from the condensation of the aromatic acid hydrazides 2-hydroxybenzo-, 2-aminobenzo- or benzo-hydrazide, with 2,3-dihydroxybenzaldehyde. Complexes 1 and 3 have been characterized by single crystal X-ray diffraction analysis. The coordinating behaviour of the ligand depends on the nature of the ortho substituent present in the hydrazide moiety. The ligands bearing a strong electron donating group (by resonance) in the ortho position undergo complexation via enolization and deprotonation, whereas the absence of such an effect leads to complexation via the keto form, and two different types of tetranuclear Cu(ii) clusters, viz. open-cubane and cubane, are obtained. Variable temperature magnetic susceptibility measurements of complexes 1 and 3 have been carried out to examine the nature of magnetic interaction between the Cu(ii) centres. All the three complexes (1-3) act as good catalyst precursors towards mild hydrocarboxylation of linear and cyclic alkanes into carboxylic acids in water-acetonitrile medium.
- Sutradhar, Manas,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Liu, Cai-Ming,Pombeiro, Armando J. L.
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p. 16578 - 16587
(2013/12/04)
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- Topologically unique 2D heterometallic CuII/Mg coordination polymer: Synthesis, structural features, and catalytic use in alkane hydrocarboxylation
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The new two-dimensional (2D) heterometallic CuII/Mg coordination polymer [Cu2Mg2(μ-Htea)2(μ6- pma)(H2O)6]n?6nH2O (1) with an unprecedented [Cu2Mg(μ-O)2(μ-COO)2] - core has been easily generated by aqueous medium self-assembly from copper(II) nitrate, triethanolamine (H3tea), magnesium hydroxide, and pyromellitic acid (H4pma). The crystal structure of 1 is composed of infinite interdigitated 2D metal-organic layers that extend via H-bonds into an intricate 3D supramolecular framework. The topological analysis of 1 discloses a binodal 2,4-connected underlying 2D net with the unique topology described by the point symbol of (64?8?10)(6), further simplification of which leads to an uninodal 4-connected net with the sql topology. Apart from representing a very rare example of the heterometallic Cu/Mg coordination network, compound 1 also acts as an efficient catalyst precursor for the mild single-pot hydrocarboxylation of linear and cyclic C n (n = 5-9) alkanes into the corresponding Cn+1 carboxylic acids.
- Kirillov, Alexander M.,Karabach, Yauhen Y.,Kirillova, Marina V.,Haukka, Matti,Pombeiro, Armando J. L.
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scheme or table
p. 1069 - 1074
(2012/06/18)
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- Mild oxidative functionalization of alkanes and alcohols catalyzed by new mono- and dicopper(II) aminopolyalcoholates
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The new mono- and dicopper(II) complexes [Cu(H3L 1)(NCS)] (1) and [Cu2(μ-HL2) 2(NCS)2] (2) were easily self-assembled from Cu(CH 3COO)2·H2O, NaNCS, NaOH and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H 4L1) or N-ethyldiethanolamine (H2L 2), respectively. They were fully characterized by IR spectroscopy, ESI-MS(±), elemental and single-crystal X-ray diffraction analyses, and applied as homogeneous catalysts for (i) the oxidation of alkanes by t-BuOOH in air to alkyl peroxides, alcohols and ketones, and in turn the oxidation of alcohols to ketones, and (ii) the single-pot aqueous medium hydrocarboxylation, by CO, H2O and K2S2O8, of various linear and cyclic Cn (n = 5-8) alkanes into the corresponding C n+1 carboxylic acids. Compound 1 was significantly more active in the oxygenation of alkanes and oxidation of alcohols, allowing to achieve 18% yield (TON = 800) of oxygenates in the oxidation of cyclohexane, and 78% yield (TON = 780) of cyclohexanone in the oxidation of cyclohexanol. In alkane hydrocarboxylations, 1 and 2 exhibited comparable activities with the total yields (based on alkane) of carboxylic acids attaining 39%. The selectivity parameters for oxidative transformations were measured and discussed, supporting free-radical mechanisms.
- Kirillov, Alexander M.,Kirillova, Marina V.,Shul'Pina, Lidia S.,Figiel, Pawe? J.,Gruenwald, Katrin R.,Guedes Da Silva, M. Fátima C.,Haukka, Matti,Pombeiro, Armando J.L.,Shul'Pin, Georgiy B.
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experimental part
p. 26 - 34
(2012/01/14)
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- Mild, single-pot hydrocarboxylation of linear C5-C9 alkanes into branched monocarboxylic C6-C10 acids in copper-catalyzed aqueous systems
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A single-pot method has been developed for the hydrocarboxylation of the liquid C5-C9 alkanes (n-pentane, n-hexane, n-heptane, n-octane, n-nonane and 3-methylhexane) into the branched monocarboxylic C 6-C10 acids bearing one more carbon atom. This method is characterized by a direct, selective and low-temperature (60 °C) hydrocarboxylation reaction of the alkane with carbon monoxide, water (which acts as a reagent besides being a solvent component) and potassium peroxodisulfate, in H2O/MeCN medium. The hydrocarboxylations are markedly enhanced in the presence of a tetracopper(II) triethanolaminate complex as a homogeneous catalyst precursor. Total yields (based on alkane) of carboxylic acids up to 46% (with 97-99% overall selectivity) have been achieved, which are remarkable in the field of alkane functionalization under mild conditions, especially for a C-C bond formation reaction in aqueous acid-solvent-free medium. The regio- and bond selectivity parameters have been determined and a free radical mechanism has been proposed.
- Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J.L.
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experimental part
p. 106 - 113
(2012/04/04)
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- Highly efficient oxidation of alcohols to carbonyl compounds in the presence of molecular oxygen using a novel heterogeneous ruthenium catalyst
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A ruthenium cation combined with microcrystals of cobalt hydroxide and cerium oxide acted as a highly efficient heterogeneous catalyst for the oxidation of various types of alcohols to carbonyl compounds under atmospheric pressure of molecular oxygen at 60°C. Especially, primary aliphatic alcohols could be oxidized to afford the carboxylic acids in high yields.
- Ji, Hongbing,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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p. 7179 - 7183
(2007/10/03)
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- New version of the TEMPO-based catalytic system for the oxidation of alcohols to aldehydes
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A new chemoselective catalytic system for the title oxidation was developed using methyltrioxorhenium (3 mol%), KBr (10 mol%) and TEMPO (3 mol%) as co-catalysts and Oxone as a terminal oxidant.
- Kowalczyk,Skarzewski
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p. 1413 - 1417
(2007/10/03)
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- Bimetallic-Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols
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The homogeneously catalyzed reduction of carboxylic acids with hydrogen was studied. Bimetallic catalysts consisting of a group 8 or 9 late transition-metal and a second group 6 or 7 transition-metal carbonyl showed a synergistic effect allowing the conversion in good yields under moderate conditions. Besides the effect of different catalyst precursors, the influence of temperature, hydrogen pressure, and catalyst concentration was investigated. An equimolar mixture of [Rh(acac)(CO)2] and [Mo(CO)6] showed the highest activity and was therefore applied to the reduction of lactones to diols. The reduction potential of the catalyst was found to be dependent on the ring size of the lactone used. Five-membered ring lactones were hardly converted to diols whereas six- and seven- membered ring lactones reacted easily.
- Behr, Arno,Brehme, Volker A.
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p. 525 - 532
(2007/10/03)
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- Evolution of products in the combustion of scrap tires in a horizontal, laboratory scale reactor
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A horizontal laboratory reactor was used to study the evolution of byproducts from the combustion of scrap tires at five nominal temperatures (ranging from 650 to 1050 °C) and different oxygen:sample ratios A model was used to calculate the bulk air ratio (λ), and the oxygen consumption was discussed considering this ratio λ. More than 100 volatile and semivolatile compounds were identified and quantified by gas chromatography mass spectrometry, plotting their yields vs the bulk air ratio and temperature. Five different behaviors considering the bulk air ratio and the temperature were identified.
- Fullana,Font,Conesa,Blasco
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p. 2092 - 2099
(2007/10/03)
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