Estudo de pirólise catalítica de biomassa em escala piloto para melhoramento da qualidade do bio-óleo

A pirólise rápida é um processo para conversão térmica de uma biomassa sólida em altos rendimentos de um produto líquido chamado de bio-óleo. Uma das alternativas para geração de um bio-óleo com menor teor de oxigênio é uso de catalisadores nos reatores de pirólise, ao invés de um inerte, num processo chamado de pirólise catalítica. O objetivo deste trabalho foi testar catalisadores comerciais, um ácido e outro básico, em uma unidade piloto de leito fluidizado circulante. O catalisador ácido utilizado foi o Ecat, proveniente de uma unidade industrial de craqueamento catalítico fluido (FCC), e como catalisador básico foi utilizado uma hidrotalcita. Os resultados foram comparados com testes utilizando um material inerte, no caso uma sílica. Uma unidade piloto de FCC do CENPES foi adaptada para realizar os testes de pirólise catalítica. Após fase de modificação e testes de condicionamento, foi comprovada a viabilidade na utilização da unidade piloto adaptada. Contudo, devido a limitações operacionais, maiores tempos de residência tiveram que ser aplicados no reator, configurando o processo como pirólise intermediária. Foram então realizados testes com os três materiais nas temperaturas de 450C e 550C. Os resultados mostraram que o aumento do tempo de residência dos vapores de pirólise teve um impacto significativo nos rendimentos dos produtos quando comparada com o perfil encontrado na literatura para pirólise rápida, pois devido ao incremento das reações secundárias, produziu maiores rendimentos de coque e água, e menores rendimentos de bio-óleo. O Ecat e a hidrotalcita se apresentaram mais efetivos em termos de desoxigenação. O primeiro apresentou maiores taxas de desoxigenação via desidratação e a hidrotalcita apresentou maior capacidade para descarboxilação. Contudo, o uso de Ecat e hidrotalcita não se mostrou adequado para uso em reatores de pirólise intermediária, pois acentuou ainda mais as reações secundárias, gerando um produto com alto teor de água e baixo teor de compostos orgânicos no bio-óleo, além de produzirem mais coque. À temperatura de 450C estes efeitos foram mais pronunciados. Em termos de caracterização química, a condição de pirólise intermediária apontou para a produção de bio-óleos com perfil fenólico, sendo a sílica o que proporcionou os melhores rendimentos, principalmente a temperatura de 550C, sendo superiores aos encontrados na literatura. Analisando as composições dos bio-óleos sob a ótica da produção de biocombustíveis, nenhum dos materiais testados apresentou rendimentos consideráveis em hidrocarbonetos. De maneira geral, a sílica foi o que proporcionou os melhores resultados em termos de rendimento e qualidade do bio-óleo. Sua menor área superficial e sua característica de inerte se mostraram mais adequados para o processo de pirólise intermediária, onde a contribuição das reações secundárias em fase gasosa é elevada em função do tempo de residência no reator

Biofiltração de compostos orgânicos voláteis e gás sulfídrico em estações de despejos industriais de processamento de hidrocarbonetos.

Neste trabalho foi estudado o tratamento simultâneo por biofiltração de emissões de compostos orgânicos voláteis, COV e gás sulfídrico, H2S, em estações de tratamento de despejos industriais, de refinaria de petróleo, ETDI. A biofiltração dos gases emanados da EDTI mostrou ser uma técnica de alta eficiência, atingindo valores de 95 a 99 % para tratamento simultâneo de COV e H2S em concentrações de 1000 e 100 ppmv, respectivamente. Foram realizados testes em 95 dias consecutivos de operação, em uma planta piloto instalada na Superintendência da Industrialização do Xisto, SIX, em São Mateus do Sul, Paraná, de março a agosto de 2006. O biofiltro foi do tipo fluxo ascendente, com 3,77 m3 de leito orgânico, composto de turfa, carvão ativado, lascas de madeira, serragem brita fina além de outros componentes menores. Foi realizada inoculação biológica com lodo filtrado de estação de tratamento de esgoto sanitário. As vazões de gás aplicadas variaram de 85 a 407 m3/h, resultando em taxas de carga de massa de 11,86 a 193,03 g de COV/h.m3 de leito e tempos de residência de 24 segundos a 6,5 minutos, com tempo ótimo de 1,6 minutos. A capacidade máxima de remoção do sistema encontrada, nas condições testadas, foi de 15 g de COV/h. m3, compatível com os valores encontrados na literatura para depuração biológica de COV na escala praticada. Também foi verificada a redução de componentes específicos de BTX, demonstrando boa degradabilidade dos compostos orgânicos. Finalmente o biofiltro demonstrou boa robustez biológica diante dos desvios operacionais intencionalmente provocados, tais como falta de umidade do leito, baixa temperatura, alta vazão, falta de carga de COV e baixo pH do leito. Depois de retomada a condição de operação estável, a biofiltração rapidamente atingiu o estado de equilíbrio, assegurando o uso eficiente e confiável da técnica no tratamento de gases de EDTI na indústria do hidrocarbonetos ou em refinarias de petróleo.

Migratory and within-estuary behaviors of adult Summer Flounder (Paralichthys dentatus) in a lagoon system of the southern mid-Atlantic Bight

We monitored the movements of 45 adult Summer Flounder (Paralichthys dentatus) between June 2007 and July 2008 through the use of passive acoustic telemetry to elucidate migratory and within-estuary behaviors in a lagoon system of the southern mid-Atlantic Bight. Between 8 June and 10 October 2007, fish resided primarily in the deeper (>3 m) regions of the system and exhibited low levels of large-scale (100s of meters) activity. Mean residence time within this estuarine lagoon system was conservatively estimated to be 130 days (range: 18–223 days), which is 1.5 times longer than the residence time previously reported for Summer Flounder in a similar estuarine habitat ~250 km to the north. The majority of fish remained within the lagoon system until mid-October, although some fish dispersed earlier and some of them appeared to disperse temporarily (i.e., exited the system for at least 14 consecutive days before returning). Larger fish were more likely to disperse before mid-October than smaller fish and may have moved to other estuaries or the inner continental shelf. Fish that dispersed after mid-October were more likely to return to the lagoon system the following spring than were fish that dispersed before mid-October. In 2008, fish returned to the system between 7 February and 7 April. Dispersals and returns most closely followed seasonal changes in mean water temperature, but photoperiod and other factors also may have played a role in large-scale movements of Summer Flounder.

The distribution of larval fishes of the Charleston Gyre Region off the southeastern United States in winter shaped by mesoscale, cyclonic eddies

Serial, cyclonic, mesoscale eddies arise just north of the Charleston Bump, a topographical rise on the continental slope and Blake Plateau, and characterize the U.S. outer shelf and upper slope in the region of the Charleston Gyre. This region was transected during the winters of 2000, 2001, and 2002, and hydrographic data and larval fishes were collected. The hydrodynamics of the cyclonic eddies of the Charleston Gyre shape the distribution of larval fishes by mixing larvae from the outer continental shelf and the Gulf Stream and entraining them into the eddy circulation at the peripheral margins, the wrap-around filaments. Over all years and transects (those that intercepted eddies and those that did not), chlorophyll a concentrations, zooplankton displacement volumes, and larval fish concentrations were positively correlated. Chlorophyll a concentrations were highest in filaments that wrapped around eddies, and zooplankton displacement volumes were highest in the continental shelf–Gulf Stream–frontal mix. Overall, the concentration of all larval fishes declined from inshore to offshore with highest concentrations occurring over the outer shelf. Collections produced larvae from 91 fish families representing continental shelf and oceanic species. The larvae of shelf-spawned fishes—Atlantic Menhaden Brevoortia tyrannus, Round Herring Etrumeus teres, Spot Leiostomus xanthurus, and Atlantic Croaker Micropogonias undulatus—were most concentrated over the outer shelf and in the continental shelf–Gulf Stream–frontal mix. The larvae of ocean-spawned fishes—lanternfishes, bristlemouths, and lightfishes—were more evenly dispersed in low concentrations across the outer shelf and upper slope, the highest typically in the Gulf Stream and Sargasso Sea, except for lightfishes that were highest in the continental shelf–Gulf Stream–frontal mix. Detrended correspondence analysis rendered groups of larval fishes that corresponded with a gradient between the continental shelf and Gulf Stream and Sargasso Sea. Eddies propagate northeastward with a residence time on the outer shelf and upper slope of ∼1 month, the same duration as the larval period of most fishes. The pelagic habitat afforded by eddies and fronts of the Charleston Gyre region can be exploited as nursery areas for feeding and growth of larval fishes within the southeastern Atlantic continental shelf ecosystem of the U.S. Eddies, and the nursery habitat they provide, translocate larvae northeastward.

Individual growth rates and movement of juvenile white shrimp (Litopenaeus setiferus) in a tidal marsh nursery

We measured growth and movements of individually marked free-ranging juvenile white shrimp (Litopenaeus setiferus) in tidal creek subsystems of the Duplin River, Sapelo Island, Georgia. Over a period of two years, 15,974 juvenile shrimp (40−80 mm TL) were marked internally with uniquely coded microwire tags and released in the shallow upper reaches of four salt marsh tidal creeks. Subsequent samples were taken every 3−6 days from channel segments arranged at 200-m intervals along transects extending from the upper to lower reach of each tidal creek. These collections included 201,384 juvenile shrimp, of which 184 were marked recaptures. Recaptured shrimp were at large an average of 3−4 weeks (range: 2−99 days) and were recovered a mean distance of <0.4 km from where they were initially marked. Mean residence times in the creek subsystems ranged from 15.2 to 25.5 days and were estimated from exponential decay functions describing the proportions of marked individuals recaptured with increasing days at large. Residence time was not significantly correlated with creek length (Pearson=−0.316, P=0.684 ), but there was suggestive evidence of positive associations with either intertidal (Pearson r=0.867, P=0.133) or subtidal (Pearson r=0.946, P=0.054) drainage area. Daily mean specific growth rates averaged 0.009 to 0.013 among creeks; mean absolute growth rates ranged from 0.56−0.84 mm/d, and were lower than those previously reported for juvenile penaeids in estuaries of the southeastern United States. Mean individual growth rates were not significantly different between years (t-test, P>0.30) but varied significantly during the season, tending to be greater in July than November. Growth rates were size-dependent, and temporal changes in size distributions rather than temporal variation in physical environmental factors may have accounted for seasonal differences in growth. Growth rates differed between creeks in 1999 (t-test, P<0.015), but not in 1998 (t-test, P>0.5). We suggest that spatial variation in landscape structure associated with access to intertidal resources may have accounted for this apparent interannual difference in growth response.

Movements, behavior, and habitat selection of bigeye tuna (Thunnus obesus) in the eastern equatorial Pacific, ascertained through archival tags

Ninety-six bigeye tuna (88– 134 cm fork length) were caught and released with implanted archival (electronic data storage) tags near fish-aggregating devices (FADs) in the equatorial eastern Pacific Ocean (EPO) during April 2000. Twenty-nine fish were recaptured, and the data from twenty-seven tags were successfully downloaded and processed. Time at liberty ranged from 8 to 446 days, and data for 23 fish at liberty for 30 days or more are presented. The accuracy in geolocation estimates, derived from the light level data, is about 2 degrees in latitude and 0.5 degrees in longitude in this region. The movement paths derived from the filtered geolocation estimates indicated that none of the fish traveled west of 110°W during the period between release and recapture. The null hypothesis that the movement path is random was rejected in 17 of the 22 statistical tests of the observed movement paths. The estimated mean velocity was 117 km/d. The fish exhibited occasional deep-diving behavior, and some dives exceeded 1000 m where temperatures were less than 3°C. Evaluations of timed depth records, resulted in the discrimination of three distinct behaviors: 54.3% of all days were classified as unassociated (with a floating object) type-1 behavior, 27.7% as unassociated type-2 behavior, and 18.7% as behavior associated with a floating object. The mean residence time at floating objects was 3.1 d. Data sets separated into day and night were used to evaluate diel differences in behavior and habitat selection. When the fish were exhibiting unassociated type-1 behavior (diel vertical migrations), they were mostly at depths of less than 50 m (within the mixed layer) throughout the night, and during the day between 200 and 300 m and 13° and 14°C. They shifted their average depths in conjunction with dawn and dusk events, presumably tracking the deep-scattering layer as a foraging strategy. There were also observed changes in the average nighttime depth distributions of the fish in relation to moon phase.

农牧交错区主要植物的氮素利用效率

Berendse&Aerts (1987)认为氮素利用效率(nitrogen use efficiency，NUE)可以分为两部分的乘积，即：①氮素生产力(nitrogen productivity，NP)，②氮素的平均滞留时间(mean residencetime，MRT)。本文利用这一概念对处于我国北方农牧交错带的内蒙古自治区多伦县典型植物的氮素利用策略进行了研究。研究假设：植物在贫瘠生境上所采取的氮素适应策略主要是提高对所吸收氮素的保持能力(较长的MRT)，而不是提高NUE。 在不同土壤生境上，属于不同生活型的不同物种其NP和MRT之间存在负相关关系。在不同生境、生活型和物种之间，作为NP与MRT乘积的NUE比NP、MRT的变化相对要小，结果表明植物主要通过延长MRT来适应氮素贫瘠的生境。因为NP与MRT相反的方向变化，二者不能同时增加或减少，所以NP与MRT之间存在相互协调(trade-off)的关系。 在群落和生态系统水平上，NP与MRT之间也存在相互协调关系，不同水平上的NUE之间也存在一定的联系。除了在种间存在这种关系外，通过对多伦县和十三里滩两种针茅（大针茅、克氏针茅）的氮素利用特征的研究，发现在种内，NP与MRT之间也存在这种相互协调关系。NUE与土壤供氮能力有关，随着土壤供氮能力的下降，NUE呈上升趋势。植物的NUE不仅与土壤的供氮能力有关，其它因素如土壤水分供应状况也会对植物的NUE产生影响，例如，与生长在河岸上的植物相比，生长在河滩湿地上的植物具有较高的NP，但MRT却较低。在群落中，不同植物个体的NUE及其组成参数NP和MRT也存在较大的差异，较大的植株具有较高的NP和MRT，因而NUE也高于个体较小的植株。本文研究结果表明，植物的NUE与氮素回收转移特性密切相关，植物提高氮素回收效率(nitrogen resorption efficiency，NRE)可以延长MRT，从而提高NUE。

Salt and water balance in the Mundel Lake: a strongly choked coastal lagoon

The Mundel Lake is an extremely shallow lagoon on the west coast of Sri Lanka. It is connected to the Puttalam Lagoon through 15 km long Dutch Canal. Salinity measurements and daily sea level data were obtained fortnightly from January 1993 to March 1994 and they were used to quantify the salt and water budget along with precipitation, evaporation and freshwater runoff. Extreme fluctuations of salinity and sea level are striking features of the system. Salinity of the Mundel Lake and Dutch Canal varied from 5-46.5 and 6 61 ppt respectively while the sea level ranged from -0.25 to +1.2 m. Tidal variations were not seen in the lagoon due to its long narrow canal system. Salt budget showed that the deposition of salt on the lagoon bottom during periods of decreasing water level. During increasing water level, salt is dissolved again. Flow of water through the Dutch Canal between the Puttalam Lagoon and Mundel Lake is driven by the changes in sea level. These changes are mainly due to seasonal changes of net freshwater supply and, to a lesser degree, to seasonal changes in sea surface height. As the flow rates are small due to the long and narrow canal, the residence time ranges between two months and several months in the Mundel Lake, except during season of high freshwater supply. As the water exchange is weak, the Mundel Lake becomes hyper saline with strong fluctuations in salinity. This implies a stress to all lagoon dwelling aquatic organisms and also to aquaculture practices in the area.

PCB desorption kinetics under realistic shear and turbulence [progress report]

We hypothesize that the impact of PCB desorption from resuspended sediments depends upon the intensity of the resuspension (which scales to bottom stress in the absence of organisms), the rate at which each congener desorbs (which depends on the size and hydrophobicity of the chemical, the relative amount of 'labile' and 'resistant' forms, and the size distribution of the suspended particles), and the residence time of the particles in the water column (which depends on the time-variable water column turbulence regime and the particle settling velocities). In order to accurately quantify the impact of PCB desorption from Hudson River sediments, we are conducting experiments that realistically mimic bottom shear stress and water column turbulence and rapidly measure PCB congener release. The objectives of this study are to measure the kinetics of PCB congener desorption from Hudson River sediments under realistic bottom shear and water column turbulence conditions and to quantify the impact of shear stress and contaminant aging on PCB desorption kinetics.

Frictional flow of damp granular material in a conical centrifuge

An analysis is given of velocity and pressure-dependent sliding flow of a thin layer of damp granular material in a spinning cone. Integral momentum equations for steady state, axisymmetric flow are derived using a boundary layer approximation. These reduce to two coupled first-order differential equations for the radial and circumferential sliding velocities. The influence of viscosity and friction coefficients and inlet boundary conditions is explored by presentation of a range of numerical results. In the absence of any interfacial shear traction the flow would, with increasing radial and circumferential slip, follow a trajectory from inlet according to conservation of angular momentum and kinetic energy. Increasing viscosity or friction reduces circumferential slip and, in general, increases the residence time of a particle in the cone. The residence time is practically insensitive to the inlet velocity. However, if the cone angle is very close to the friction angle then the residence time is extremely sensitive to the relative magnitude of these angles. © 2011 Authors.

Relating monolithic and granular leaching from contaminated soil treated with different cementitious binders.

This work employed a clayey, silty, sandy gravel contaminated with a mixture of metals (Cd, Cu, Pb, Ni and Zn) and diesel. The contaminated soil was treated with 5 and 10% dosages of different cementitious binders. The binders include Portland cement, cement-fly ash, cement-slag and lime-slag mixtures. Monolithic leaching from the treated soils was evaluated over a 64-day period alongside granular leachability of 49- and 84-day old samples. Surface wash-off was the predominant leaching mechanism for monolithic samples. In this condition, with data from different binders and curing ages combined, granular leachability as a function of monolithic leaching generally followed degrees 4 and 6 polynomial functions. The only exception was for Cu, which followed the multistage dose-response model. The relationship between both leaching tests varied with the type of metal, curing age/residence time of monolithic samples in the leachant, and binder formulation. The results provide useful design information on the relationship between leachability of metals from monolithic forms of S/S treated soils and the ultimate leachability in the eventual breakdown of the stabilized/solidified soil.

Growth kinetics and uniform scaling-up of graphene synthesis

Chemical vapor deposition on copper is the most widely used method to synthesize graphene at large scale. However, the clear understanding of the fundamental mechanisms that govern this synthesis is lacking. Using a vertical-flow, cold-wall reactor with short gas residence time we observe the early growths to study the kinetics of chemical vapor deposition of graphene on copper foils and demonstrate uniform synthesis at wafer scale. Our results indicate that the growth is limited by the catalytic dissociative dehydrogenation on the surface and copper sublimation hinders the graphene growth. We report an activation energy of 3.1 eV for ethylene-based graphene synthesis. © The Electrochemical Society.

MgO expansive cement and concrete in China: Past, present and future

Uniquely, China employs MgO already contained in cement clinker or as an expansive additive to compensate for the thermal shrinkage of mass concrete, particularly dam concrete, with almost 40 years' experience in both research activities and industrial applications. Compensating shrinkage with expansion produced by MgO has been proved to effectively prevent thermal cracking of mass concrete, and reduce the cost of temperature control measures and speed up the construction process. Moreover, the expansion properties of MgO could be designed flexibly, through adjusting its microstructure by changing the calcination conditions (calcining temperature and residence time). The collective knowledge and experience of MgO expansive cement and concrete is worthy of sharing with relevant engineers and researchers globally but dissemination has been hindered as most of the relevant literature is published in Chinese. This paper reviews the history, state-of-the-art progress and future research needs in the field of MgO expansive cement and concrete. © 2013 Elsevier Ltd.

Budgets and dynamics of nitrogen and phosphorus in a shallow, hypereutrophic lake in China

Budgets and dynamics of nitrogen and phosphorus in Lake Donghu were investigated from Oct. 1997 to Sept. 1999. The water residence time was estimated to be 89 days in 1997-1998 and 124 days in 1998-1999. The total external loadings were 53 g N m(-2) yr(-1) and 3.2 g P m(-2) yr(-1) in 1997-1998, and 42 g N m(-2) yr(-1) and 3.1 g P m(-2) yr(-1) in 1998-1999. On average, about 80% of nitrogen and phosphorus input was from sewage outlets, while the rest was from land runoff and precipitation. Ammonium ion was the most abundant form of inorganic nitrogen in the sewage. The nutrient output was mainly through water outflow and fish catch. The percentages of nutrients in fish were estimated to be 7.8%-11.2% for nitrogen and 47.6%- 49.6% for phosphorus. Lake Donghu has a very high nutrient retention (63% for nitrogen and 79% for phosphorus) mainly due to its closure and long water residence time. Sedimentation is an important nutrient retention mechanism in this lake. Using mass balance method, we estimated that denitrification of Lake Donghu involves about 50% of the retained nitrogen. Lake Donghu is rich in inorganic nitrogen and phosphorus and showed great seasonal variation.

Development of a self-thermal insulation miniature combustor

A novel miniature cylindrical combustor, whose chamber wall is made of porous material, has been designed and experimented for reducing heat loss and enhancing flame stability. The combustor has the function of reducing wall heat loss, extending residence time and avoiding radical chemical quenching with a self-thermal insulation concept in which heat loss reduction is obtained by the opposite flow directions between thermal energy transfer and mass flow. The methane/air mixture flames formed in the chamber are blue and tubular in shape. Between the flames and the porous wall, there is a thin unburned film that plays a significant role in reducing the flames' heat loss and keeping the flames stable. The porous wall temperature was 150-400 degrees C when the temperatures of the flames and exhaust gas were more than 1200 degrees C. When the equivalence ratio phi < 1.0, the methane conversion ratio was above 95%; the combustion efficiency was near 90%; and the overall sidewall heat loss was less than 15% in the 1.53 cm(3) chamber. Moreover, its combustion efficiency is stable in a wider combustion load (input power) range.