Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / Developments in the field of liquid detergents and cosmetics have increased the demand for surfactants, processing aids and emollients. Alcohols are often used in liquid products where they serve as solvents for the detergent ingredients, adjust the viscosity and prevent product separation. Industrial scale oxygenation of the alkane to the alcohol is often incomplete, resulting in a significant amount of residual alkane. Application of these alcohols often requires a low residual alkane content and a post-production separation process is thus required. Traditional separation methods such as distillation and crystallisation are not technically viable as crossover melting and boiling points prevent the successful implementation of such processes and it is envisaged to use supercritical extraction to separate a mixture of n-alkanes and 1- alcohols. The project scope revolves around a product stream consisting of detergent range alcohols and corresponding n-alkanes that need to be separated. To model such a system, a typical detergent range alkane – alcohol feed with an average of 13 carbon atoms was selected, although a large number of the molecules have between 12 and 14 carbon atoms each. Generally the presence of the hydroxyl group as well as an increase in the number of carbon atoms decreases the solubility in supercritical solvents [17]-[19]. The most difficult separation will therefore be that of the alcohol with the least number of carbon atoms, that is 1-dodecanol (alcohol with 12 carbon atoms, CH3-(CH2)9-CH2-OH ) and the alkane with the most number of carbon atoms, that is n-tetradecane (alkane with 14 carbon atoms, CH3-(CH2)12-CH3 ). To model the system, it is assumed that the hydrocarbon backbone is linear and the alcohol is primary. Therefore 1-dodecanol and n-tetradecane are used. If it is possible to separate 1-dodecanol and ntetradecane with the use of supercritical fluids, it should be possible to separate an industrial mixture. The deliverables of this study are: a comparison of the high pressure solubility of n-tetradecane and 1-dodecanol with a selection of possible solvents; a selection of potential solvents to be tested on a pilot plant to confirm practical separation. From the literature and measured phase equilibria, all three solvents (carbon dioxide, ethane and propane) have the ability to distinguish (based on a difference in the pressure required for solubility) between 1-dodecanol and n-tetradecane. Both carbon dioxide and ethane have favourable temperature considerations. Propane has superior solubility of n-tetradecane and 1- dodecanol. Carbon dioxide demonstrates the highest selectivity. Pilot plant experiments have shown that both carbon dioxide and ethane have the ability to separate a 50-50% (mass percentage) mixture of 1-dodecanol and n-tetradecane. Both solvents perform at their best at low temperatures. Carbon dioxide shows the best results at low temperature and conditions of reflux. The highlight of pilot plant experiments with supercritical carbon dioxide is achieving a selectivity of 16.4 with the mass percentage of n-tetradecane at 5% and 82% for the bottoms and overheads product respectively. Very good separation is achieved using supercritical ethane as solvent even without reflux. Attention is drawn to pilot plant experiments where the selectivity is as high as 82 with the mass percentage of n-tetradecane in the bottoms and overheads product at 1% and 82% respectively. It is recommended to measure ternary phase equilibria for the system n-tetradecane, 1-dodecanol and carbon dioxide/ethane to establish the interaction between n-tetradecane and 1-dodecanol. The measured binary phase equilibrium data need to be expanded to include the vapour mass fraction composition in the isothermal solubility data.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2007. / Adequate provision of oxygen to aerobic bioprocesses is essential for the optimisation of process kinetics. In bioprocesses in which the feedstock is an alkane, the supply of sufficient oxygen is of particular concern because the alkane molecular structure is deficient in oxygen. As a result, the oxygen demand has to be met solely by transfer of oxygen to the culture, necessitating a proportionately higher requirement for oxygen transfer. Maximisation of the rate of oxygen transfer is therefore of key importance in optimising the potential for alkane bioconversion, with respect to both operation and scale up. Nevertheless, the oxygen transfer rate (OTR), and its dependence on the overall volumetric mass transfer coefficient (KLa) in alkane-aqueous dispersions is not yet well understood. In view of the importance of an adequate OTR in the optimisation of alkane bioconversion, this study has focused on the identification and elucidation of the factors which underpin the behaviour of KLa in an alkane-aqueous dispersion. KLa behaviour was quantified in terms of the pressures imposed by turbulence and alkane fluid properties, through their influence on the Sauter mean diameter (D32), gas hold up, gas-liquid interface rigidity and gas-liquid interfacial area per unit volume. These properties were correlated with KLa over a wide range of agitation rates and alkane concentrations in alkane-aqueous dispersions. Experiments were conducted in a 5 litre aerated and agitated bioreactor at agitation rates of 600, 800, 1000 and 1200 rpm and alkane (n-C10-C13 cut) concentrations of 0, 2.5, 5, 10, and 20% (v/v). KLa determination was executed using both the gassing out and pressure step methods. The accuracy and reliability of these methods were compared under the full range of agitation rates and alkane concentrations. The pressure step method was conclusively shown to be superior provided that probe response was taken into account, and was therefore used in the correlations. The interfacial areas corresponding to the KLa values were calculated from the combined effects of D32 and gas hold up. D32 was determined from the measurement of the dispersed air bubble diameters by means of a photographic technique and image analysis. Image analysis was performed by a program that was developed in Matlab® using image acquisition and image processing techniques. This program used these techniques to extract information of the gas bubbles in the image. The gas hold up was determined using the dispersion height technique. The behaviour of KLa was shown to be dependent on both agitation and alkane concentration. Increasing agitation from 600 to 1200 rpm increased KLa for each of the alkane concentrations. The influence of agitation on the interfacial area was evaluated over the same range of agitation rates and the relationship between the corresponding KLa values and interfacial areas assessed. Increasing agitation rate similarly enhanced the interfacial area available for transfer for each of the alkane concentrations, resulting in the concomitant increase in KLa. This increase in interfacial area was related directly to a shear-induced decease in D32 and indirectly to an increased gas holdup as a result of the lower rise velocity of the smaller bubbles. In addition to the agitation, the presence of alkane markedly influenced KLa behaviour, but in different ways, depending on the alkane concentration. Alkane concentration between 2.5 and 5% (v/v) reduced D32 at constant agitation of 800, 1000 and 1200 rpm, a likely consequence of decreased surface tension and retarded coalescence conferred by the alkane. The smaller D32 and the consequential enhanced gas hold up served to amplify KLa through increased interfacial area. However, as alkane concentration was increased above 5% (v/v), the gas hold up decreased despite a continued decrease in D32, resulting in a corresponding decrease in both the interfacial area and KLa. This suggests that at the higher alkane concentrations, the influence of viscosity predominated, exerting multiple negative influences on the interfacial area and oxygen transfer coefficient. The trends were however, not observed at the low agitation of 600 rpm, where turbulence was significantly reduced and KLa was repressed for all alkane concentrations. The pressures imposed by turbulence and alkane properties on the interfacial area defined locales of KLa behaviour and three distinct KLa behavioural trends were identified, depending on the agitation rate and alkane concentration. Regime 1 was constrained between 2.5 and 5% (v/v) for agitation rates of 800 rpm and above. Here KLa enhancement was directly associated with increased interfacial area which was the major factor defining KLa in this regime. Regime 2 was constrained by alkane concentrations higher than 5% (v/v) for agitation rates of 800 rpm and above. In this regime, the KLa depression was observed with increasing alkane concentration suggesting a predominant influence of viscosity which would be likely to exert multiple negative influences on KLa, through both the interfacial area and KL. The interfacial area in this regime decreased mainly due to the negative effect of viscosity on gas holdup. Regime 3, characterised by a decline in KLa irrespective of the alkane concentration, occurred at agitation rates smaller than 800 rpm. It is likely that at low agitation rates, the contribution of turbulence was insufficient to exert a positive influence on the interfacial area In this regime, the interfacial decreased through the combined negative effect of increased D32 and decreased gas holdup. The resultant variation in OTR depended directly on the relative magnitudes of the KLa and oxygen solubility and indirectly on the process conditions which defined these magnitudes. Under conditions of enhanced KLa, OTR benefited from the combined increases in KLa and oxygen solubility. However, under conditions of KLa depression, the elevated oxygen solubility did not invariably outweigh the influence of KLa depression on OTR. Consequently, despite the considerably increased solubility of oxygen in alkane-based bioprocesses a potential decrease in OTR through depressed KLa underlines the critical importance of the quantification of this parameter in alkane-aqueous dispersions and the necessity for a definition of the locales of optimal KLa. Through the identification of the parameters which underpin the behaviour of KLa in alkane-aqueous dispersions and the quantification of the effect of process conditions on these parameters, a fundamental understanding of the KLa and OTR in alkane-aqueous dispersions has been developed. This provides a knowledge base for the prediction of optimal KLa in these systems and has wide application across all alkane-based bioprocesses.

Palladium-catalyzed reactions for carbon-carbon bond formation have had a significant impact on the field of organic chemistry in recent decades. Illustrative is the 2010 Nobel Prize, awarded for “palladium-catalyzed cross couplings in organic synthesis”, and the numerous applications of these transformations in industrial settings. This thesis describes recent developments in C(sp2)-C(sp3) bond formation, focusing on alkane arylation reactions and arylative dearomatization transformations. In the first part, our contributions to the development of intramolecular C(sp3)-H arylation reactions from aryl chlorides are described (Chapter 2). The use of catalytic quantities of pivalic acid was found to be crucial to observe the desired reactivity. The reactions are highly chemoselective for arylation at primary aliphatic C-H bonds. Theoretical calculations revealed that C-H bond cleavage is facilitated by the formation of an agostic interaction between the palladium centre and a geminal C-H bond. In the following section, the development of an alkane arylation reaction adjacent to amides and sulfonamides is presented (Chapter 3). The mechanism of C(sp3)-H bond cleavage in alkane arylation reactions is also addressed through an in-depth experimental and theoretical mechanistic study. The isolation and characterization of an intermediate in the catalytic cycle, the evaluation of the roles of both carbonate and pivalate bases in reaction mechanism as well as kinetic studies are reported. Our serendipitous discovery of an arylation reaction at cyclopropane methylene C-H bonds is discussed in Chapter 4. Reaction conditions for the conversion of cyclopropylanilines to quinolines/tetrahydroquinolines via one-pot palladium(0)-catalyzed C(sp3)-H arylation with subsequent oxidation/reduction are described. Initial studies are also presented, which suggest that this transformation is mechanistically unique from other Pd catalyzed cyclopropane ring-opening reactions. Preliminary investigations towards the development of an asymmetric alkane arylation reaction are highlighted in Chapter 5. Both chiral carboxylic acid additives and phosphine ligands have been examined in this context. While high yields and enantiomeric excesses were never observed, encouraging results have been obtained and are supported by recent reports from other research groups. Finally, in part two, the use of Pd(0)-catalysis for the intramolecular arylative dearomatization of phenols is presented (Chapter 7). These reactions generate spirocyclohexadienones bearing all-carbon quaternary centres in good to excellent yields. The nature of the base, although not well understood, appears to be crucial for this transformation. Preliminary results in the development of an enantioselective variant of this transformation demonstrate the influence of catalyst activation on levels of enantiomeric excess.

The most efficient homogeneous catalysts for hydroxylation of light alkanes utilize transition metals in superacid solvent and operate by tandem electrophilic C-H activation/metal-alkyl (M-R) functionalization. An emerging alternative strategy to transition metals is the use of high-oxidation state main-group metals (e.g. TlIII, PbIV, IIII) that hydroxylate light alkanes. This dissertation reports density-functional theory calculations that reveal the mechanisms, reactivity, and selectivity of TlIII promoted alkane C-H functionalization in trifluoroacetic acid and TlIII-dialkyl functionalization in water. Calculations reveal that TlIII oxidizes alkanes via a closed-shell C-H activation and M-R functionalization mechanism that is similar to transition-metal C-H functionalization mechanisms. Comparison of TlIII to similar transition metals reveals that while TlIII and transition metals can have similar activation barriers for C-H activation, TlIII M-R functionalization is significantly faster due to a highly polar Tl-C bond and large TlIII/TlI reduction potential. The combination of a moderate C-H activation barrier combined with a low M-R functionalization barrier is critical to the success for TlIII promoted alkane C-H oxidation. The proposed TlIII C-H activation/M-R functionalization mechanism also provides an explanation for ethane conversion to a mixture of ethyl trifluoroacetate and ethane-1,2-diyl bis(2,2,2-trifluoroacetate). The reactivity of TlIII contrasts the lack of alkane oxidation by HgII. The C-H activation transition state and frontier-orbital interactions provide a straightforward explanation for the higher reactivity of TlIII versus HgII. This frontier-orbital model also provides a rationale for why the electron-withdrawing group in EtTFA provides "protection" against overoxidation. Calculations also reveal that TlIII-dialkyl functionalization by inorganic TlIII in water occurs by alkyl group transfer to form a TlIII-monoalkyl complex that is rapidly functionalized.

Palladium-catalyzed reactions for carbon-carbon bond formation have had a significant impact on the field of organic chemistry in recent decades. Illustrative is the 2010 Nobel Prize, awarded for “palladium-catalyzed cross couplings in organic synthesis”, and the numerous applications of these transformations in industrial settings. This thesis describes recent developments in C(sp2)-C(sp3) bond formation, focusing on alkane arylation reactions and arylative dearomatization transformations. In the first part, our contributions to the development of intramolecular C(sp3)-H arylation reactions from aryl chlorides are described (Chapter 2). The use of catalytic quantities of pivalic acid was found to be crucial to observe the desired reactivity. The reactions are highly chemoselective for arylation at primary aliphatic C-H bonds. Theoretical calculations revealed that C-H bond cleavage is facilitated by the formation of an agostic interaction between the palladium centre and a geminal C-H bond. In the following section, the development of an alkane arylation reaction adjacent to amides and sulfonamides is presented (Chapter 3). The mechanism of C(sp3)-H bond cleavage in alkane arylation reactions is also addressed through an in-depth experimental and theoretical mechanistic study. The isolation and characterization of an intermediate in the catalytic cycle, the evaluation of the roles of both carbonate and pivalate bases in reaction mechanism as well as kinetic studies are reported. Our serendipitous discovery of an arylation reaction at cyclopropane methylene C-H bonds is discussed in Chapter 4. Reaction conditions for the conversion of cyclopropylanilines to quinolines/tetrahydroquinolines via one-pot palladium(0)-catalyzed C(sp3)-H arylation with subsequent oxidation/reduction are described. Initial studies are also presented, which suggest that this transformation is mechanistically unique from other Pd catalyzed cyclopropane ring-opening reactions. Preliminary investigations towards the development of an asymmetric alkane arylation reaction are highlighted in Chapter 5. Both chiral carboxylic acid additives and phosphine ligands have been examined in this context. While high yields and enantiomeric excesses were never observed, encouraging results have been obtained and are supported by recent reports from other research groups. Finally, in part two, the use of Pd(0)-catalysis for the intramolecular arylative dearomatization of phenols is presented (Chapter 7). These reactions generate spirocyclohexadienones bearing all-carbon quaternary centres in good to excellent yields. The nature of the base, although not well understood, appears to be crucial for this transformation. Preliminary results in the development of an enantioselective variant of this transformation demonstrate the influence of catalyst activation on levels of enantiomeric excess.

Unspecific peroxygenase (EC 1.11.2.1) represents a group of secreted hemethiolate proteins that are capable of catalyzing the selective mono-oxygenation of diverse organic compounds using only H2O2 as a cosubstrate. In this study, the peroxygenase from Agrocybe aegerita (AaeUPO) was found to catalyze the hydroxylation of various linear (e.g n-hexane), branched (e.g. 2,3-dimethylbutane) and cyclic alkanes (e.g. cyclohexane). The size of n-alkane substrates converted by AaeUPO ranged from gaseous propane (C3) to n-hexadecane (C16). They were mono-hydroxylated mainly at the C2 and C3 position, rather than at the terminal carbon, and the corresponding ketones were formed as a result of overoxidation. In addition, a number of alkenes were epoxidized by AaeUPO, including linear terminal (e.g. 1-heptene), branched (2-methyl-2-butene) and cyclic alkenes (e.g. cyclopentene), as well as linear and cyclic dienes (buta-1,3-diene, cyclohexa-1,4-diene). Furthermore, the conversion of terminal alkynes (e.g. 1- octyne) gave the corresponding 1-alkyn-3-ol in low yield. Some of the reactions proceeded with complete regioselectivity and - in the case of linear alkanes, terminal linear alkenes and alkynes - with moderate to high stereoselectivity. The conversion of n-octane gave (R)-3-octanol with 99% enantiomeric excess (ee) and the preponderance of the (S)-enantiomer reached up to 72% ee of the epoxide product for the conversion of 1-heptene. Catalytic efficiencies (kcat/ Km) determined for the hydroxylation and respectively epoxidation of the model compounds cyclohexane and 2-methyl-2-butene were 2.0 × 103 M-1 s-1 and 2.5 × 105 M−1 s−1. The results obtained in the deuterium isotope effect experiment with semideuterated n-hexane and the radical clock experiment with norcarane clearly demonstrated that the hydroxylation of alkanes proceeds via hydrogen abstraction, the formation of a substrate radical and a subsequent oxygen rebound mechanism. Moreover, stopped-flow experiments and substrate kinetics proved the involvement of a porphyrin radical cation species (compound I; AaeUPO-I) as reactive intermediate in the catalytic cycle of AaeUPO, similar to other hemethiolate enzymes (e.g. cytochrome P450 monooxygenases, P450s). / Die Gruppe der Unspezifischen Peroxygenasen (EC 1.11.2.1) umfasst extrazelluläre Häm-Thiolat-Enzyme, die mittels H2O2 als Cosubstrat die selektive Monooxygenierung unterschiedlicher organischer Verbindungen katalysieren. In der vorliegenden Arbeit konnte gezeigt werden, dass die von Agrocybe aegerita sekretierte Peroxygenase (AaeUPO) verschiedene lineare (z. B. n-Hexan), verzweigte (z. B. 2,3-Dimethylbutan) und zyklische Alkane (z. B. Cyclohexan) hydroxyliert. Die Größe der von der AaeUPO umgesetzten Substrate reichte vom gasförmigen Propan (C3) bis hin zu n-Hexadekan (C16). Die Alkane wurden bevorzugt am zweiten und dritten Kohlenstoffatom (C2 und C3) hydroxyliert; eine Hydroxylierung am terminalen Kohlenstoff konnte nur vereinzelt und in geringem Umfang beobachtet werden. Die Überoxidationen der primär gebildeten, sekundären Alkohole führte außerdem zur Entstehung der entsprechenden Ketonderivate. Darüber hinaus wurde eine Vielzahl linearer terminaler (z. B. 1-Hepten), verzweigter (z. B. 2-Methyl-2-Buten) und zyklischer Alkene (z. B. Cyclopenten) sowie linearer und zyklischer Diene (1,3-Butadien, 1,4-Cyclohexadien) durch die AaeUPO epoxidiert. Die Umsetzung terminaler Alkine (z. B. 1-Octin) führte zur Entstehung der jeweiligen 1-Alkin-3-ole. Manche dieser Reaktionen verliefen ausgeprägt regioselektiv und, im Falle der linearen Alkane sowie der linearen terminalen Alkene und Alkine, mit mittlerer bis hoher Stereoselektivität. So ergab beispielsweise die Umsetzung von n-Octan einen Enantiomerenüberschuss größer 99% für (R)-3-Octanol; die Epoxidierung von 1-Hepten lieferte einen Enatiomeerenüberschuss (ee) von bis zu 72% für das (S)-Enantiomer. Die katalytischen Effizienzen, die für die Hydroxylierung bzw. Epoxidierung der Modellverbindungen Cyclohexan und 2-Methyl-2-Buten ermittelt wurden, betragen 2.0 × 103 M-1 s-1 und 2.5 × 105 M−1 s−1. Der ausgeprägte Deuterium-Isotopen-Effekt, der im Zuge der Umsetzung von semideuteriertem n-Hexan beobachtet wurde sowie die Ergebnisse des Radical-Clock-Experiments mit Norcarane als Substrat bestätigten, dass die Hydroxylierung von Alkanen über Wasserstoffabstraktion, die Bildung eines Substratradikals und anschließende direkte Sauerstoffrückbindung verläuft. Die Stopped-Flow-Experimente belegen zudem das Auftreten eines Porphyrin-Kationradikal-Intermediates (Compound I; AaeUPO-I) im katalytischen Zyklus der AaeUPO (vergleichbar mit dem reaktiven Intermediat der P450-Monooxygenasen).

Diese Arbeit charakterisiert die Solvatation des organischen Farbstoffes Coumarin 153 in Gemischen aus jeweils einem Alkan und einem Alkohol. Dabei werden Methoden der statischen und zeitaufgeloesten optischen Spektroskopie sowie klassische molekulardynamische Simulationen fuer die Untersuchungen angewendet. Die experimentellen Ergebnisse zeigen, dass der Farbstoff im Gemisch selektiv durch den Alkohol solvatisiert ist. Die Staerke dieser Solvatation ist für den elektronischen Grund- und Anregungszustand des Farbstoffes unterschiedlich. Aus diesem Grund wird die Solvatationsdynamik in Alkohol/Alkan Gemischen durch einen Translationsdiffusionsprozess bestimmt. Die molekulardynamischen Simulationen veranschaulichen die selektive Solvatation des Coumarin 153 in einem Methanol/Hexan Gemisch. Die Solvathuelle enhaelt im Anregungszustand des Farbstoffes bis zu dreimal mehr Molekuele als im Grundzustand. Im Unterschied zur Solvatation in reinem Methanol spielen spezifische Bindungen wie Wasserstoffbrueckenbindungen in einem Methanol/Hexan Gemisch eine wesentliche Rolle.

Chemnitz, Techn. Univ., Diss., 1998. / Teilw. u.d.T.: Solvatation eines Coumarinfarbstoffes in Gemischen aus Alkanen und Alkanolen.

Essen, Universiẗat, Diss., 2004--Duisburg.

O trabalho foi conduzido na EEA-UFRGS, em Eldorado do Sul/RS, entre dez/2011 e nov/2013 com o objetivo de estudar o efeito da estrutura do pasto no consumo de matéria seca e na emissão de metano e relacionar essa emissão com o desempenho animal em pastagem nativa submetida a níveis de oferta diária de forragem de 4, 8, 8.12, 12 e 16 kg de MS/100 kg de PV, ou %PV. Esses tratamentos foram distribuídos num delineamento experimental de blocos com duas repetições. Em pastoreio contínuo foram utilizadas novilhas mestiças com 24 meses de idade e 223 ± 24 kg em 2012 e 12 meses e 274 ± 17 kg em 2013 quando da entrada dos animais no protocolo experimental. As variáveis para descrever a estrutura do pasto foram: massa de forragem, taxa de acúmulo de forragem, altura do pasto e frequência de touceiras. Na avaliação de consumo de matéria seca utilizou-se a técnica dos n-alcanos a partir da teoria do duplo n-alcano. As emissões de metano foram estimadas pela técnica do marcador hexafluoreto de enxofre. Foi utilizado o delineamento experimental de blocos com duas repetições. As ofertas 4 e 8% emitiram menores quantidades de CH4/animal que as ofertas de forragem 16, 12 e 8.12% do PV. Os modelos estudados demonstraram que a variabilidade das emissões é explicada, em maior proporção, pelo conjunto de estrutura do pasto (R2=0.53), e que a relação entre emissão de CH4 e consumo de matéria seca foi altamente significativa (P<0.001), porém o consumo explicou a variância dos dados em proporção limitada (R2= 0.20). Anualmente a emissão de CH4 foi determinada por mudanças no consumo e na estrutura do pasto, principalmente, na taxa de acúmulo de forragem. Com baixa taxa de acúmulo, principalmente no inverno, há maior gasto de energia para realização da metanogênese. A relação observada entre a quantidade de CH4 emitido por kg de MS consumida em função do consumo diário de MS apresentou comportamento inversamente proporcional. O aumento da OF até níveis moderados de intensidade de pastejo proporcionam maiores GPV e maiores emissões de CH4 por animal que oferta de forragem baixa. Porém as ofertas de forragens alta e moderadas (16,12 e 8.12 ) emitiram menor quantidade de metano por área e por kg de peso vivo produzido. Portanto a busca por estruturas de pasto ideal através de manejos com intensidades de pastejo moderadas aliada a altas taxas de acúmulo do pasto, formam ambientes de pastejos na qual os bovinos mitigam metano por kg de MS consumida, por ha e por kg de PV produzido. / The study was conducted at the EEA-UFRGS, in Eldorado do Sul/ RS, from Dec/2011 to Nov/2013 in order to study the effect of the structure and dry matter intake in methane emissions and relate that to animal performance in native grassland. The treatments consisted of the following forage allowance levels: 4, 8, 8:12, 12 and16 kg DM / 100 kg live weight (LW), or % LW. The animal testers were crossbred heifers with 24 months of age and 223 ± 24 kg in 2012 and 12 months and 274 ± 17 kg in 2013 when the entry of animals in the experimental protocol. The variables to describe the pasture structure were: herbage mass, herbage accumulation rate, pasture height and frequency of tussocks. For the dry matter intake evaluation, it was used the technique of nalkanes technique based on the double alkane teory. Methane emissions were measured by the sulfur hexafluoride tracer technique. The experimental design was a randomized block design with two replications (paddocks) was used. The 4 and 8% LW herbage allowance treatments emited less CH4/animal than 16, 12 and 12.8% LW. The models showed that the variability of the emission is explained in a greater proportion, the set of pasture structure (R2 = 0,53), and that the relationship between emission of methane emission and dry matter intake was highly significant (P <0.001). On the other hand, consumption explained a smaller amount of the data variance (R2 = 0.20). Annuall methane emission was determined by changes in herbage consumption and sward structure, mainly herbage accumulation rate. With low herbage accumulation rate, especially in winter, there was a greater, waste of energy for methanogenesis. There was an inverse relationship between the amount of methane emitted per kg dry matter intake as a function of daily dry matter consumption. Increasing herbage allowance to moderate grazing intensity levels resulted in a greater LW gain and also higher CH4 emission per animal. However, high to moderate herbage allowance tratments (16, 12 and 8-12) emited less methane per area and per kg of LW produced. Managing native grasslands under moderate levels of herbage allowance can creat canopy strutures that favor both consumption and herbage accumulation rate, and also mitigate beff cattle methane emissions per kg of DM, per area and per kg LW produced.