Scientific rationale toward cupola design

Numerous improvements in cupola design and operation have been made in the past to increase productivity, spout temperature and fuel efficiency. However, these improvements have been based on practice and experience. The present work establishes a scientific rationale for cupola design and operation using a mathematical model. The improved performance of a divided-blast cupola over the conventional one has been successfully explained by the model. Performance of a cupola, as influenced by the important design parameter--the distance of separation between the two rows of tuyeres and operational parameters, such as size of coke and metallic charge, blast rate and charge level--was analyzed. For a divided-blast cupola, an optimum distance of 800-900 mm separation between the two rows of tuyeres was found to be ideal, irrespective of the size of cupola.

Production of syngas from steam reforming and CO removal with water gas shift reaction over nanosized Zr0.95Ru0.05O2-delta solid solution

This study presents the synthesis, characterization, and kinetics of steam reforming of methane and water gas shift (WGS) reactions over highly active and coke resistant Zr0.93Ru0.05O2-delta. The catalyst showed high activity at low temperatures for both the reactions. For WGS reaction, 99% conversion of CO with 100% H-2 selectivity was observed below 290 degrees C. The detailed kinetic studies including influence of gas phase product species, effect of temperature and catalyst loading on the reaction rates have been investigated. For the reforming reaction, the rate of reaction is first order in CH4 concentration and independent of CO and H2O concentration. This indicates that the adsorptive dissociation of CH4 is the rate determining step. The catalyst also showed excellent coke resistance even under a stoichiometric steam/carbon ratio. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic nature of Ru species. The associative mechanism involving the surface formate as an intermediate was used to correlate experimental data. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Catalytic performance of highly dispersed Ni/TiO2 for dry and steam reforming of methane

The present study reports a sonochemical-assisted synthesis of a highly active and coke resistant Ni/TiO2 catalyst for dry and steam reforming of methane. The catalyst was characterized using XRD, TEM, XPS, BET analyzer and TGA/DTA techniques. The TEM analysis showed that Ni nanoparticles were uniformly dispersed on TiO2 surface with a narrow size distribution. The catalyst prepared via this approach exhibited excellent activity and stability for both the reactions compared to the reference catalyst prepared from the conventional wet impregnation method. For dry reforming, 86% CH4 conversion and 84% CO2 conversion was obtained at 700 degrees C. Nearly 92% CH4 conversion and 77% CO selectivity was observed under a H2O/CH4 ratio of 1.2 at 700 degrees C for the steam reforming reaction. In particular, the present catalyst is extremely active and resistant to coke formation for steam reforming at low steam/carbon ratios. There is no significant modification of Ni particles size and no coke deposition, even after a long term reaction, demonstrating its potential applicability as an industrial reformate for hydrogen production. The detailed kinetic studies have been presented for steam reforming and the mechanism involving Langmuir-Hinshelwood kinetics with adsorptive dissociation of CH4 as a rate determining step has been used to correlate the experimental data.

Bajo Dios y bajo la ley : fundamentos de Derecho natural en el sistema del Common-law inglés

Resumen: El common-law inglés tiene una herencia cristiana increíblemente rica. Los juristas ingleses más prestigiosos –incluyendo a Blackstone, Coke y Fortescue– frecuentemente partían desde la fe cristiana a la hora de iluminar y desarrollar lo que ahora son ya principios bien establecidos de la doctrina del common-law. Por consiguiente, este sistema fue desarrollándose históricamente con una particular referencia a la tradición cristiana del derecho natural. Este artículo demuestra cómo el common-law inglés fue mayoritariamente inspirado y desarrollado por estos principios cristianos de la teoría del derecho natural y cómo estos principios todavía subsisten válidos para la interpretación del common-law aun en el presente.

Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N2O. HCl greatly increases CO and CH4 emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO2 system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K. (C) 2009 Elsevier Ltd. All rights reserved.

Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators.

In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt₃M alloys, where M is a transition metal. We found that only Pt₃Os and Pt₃Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt₃Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O₂ to form H₂O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the O_ad hydration reaction (O_ad + H₂O_ad -> OH_ad + OH_ad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt₃Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions.

We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt_2ML/Os core-shell) and H₂O formation steps (0.32 eV for Pt, 0.22 eV for Pt_2ML/Os core-shell). We found that Pt_2ML/Os has the highest activity (compared to pure Pt and to the Pt₃Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt_2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO₄ solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model.

In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni₄Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni₄Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni₄X (X=Fe, Co, Mn, and Mo), showed Ni₄Fe, Ni₄Co, and Fe₄Mn all have better coking resistance than pure Ni, but that only Ni₄Fe and Fe₄Mn have (slightly) improved activity compared to pure Ni.

In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba₈X₇M₁(OH)₁O₂₃ where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4⁺ X is replace by a 3⁺ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the O_donor-O_acceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.

Optimization of the pyrolysis process for the production of a biomass derived reducing agent and hydrogen-rich gases

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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

生物质煤气废水氨氮脱除的研究

生物质煤气废水是一种新出现的高浓度氨氮有机废水。作者采用化学沉淀法去除该废水中的氨氮，研究了不同沉淀剂、pH、温度和搅拌时间对氨氮去除效果的影响。结果表明，MgCl2＋Na3PO4·12H2O明显优于其他沉淀剂组合。当n（Mg^2＋）：n（NH4^＋）：n（PO4^3-）=1：1：1、pH10．0、温度30℃、搅拌时间30min时，废水中的氨氮质量浓度从处理前的222mg/L降到17mg／L，去除率为92.3％。

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O-2) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H-2+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 degrees C during 108 h lifetime test. However, no Coke deposition was detected for partial oxidation reforming process, which indicated that addition of O-2 can effectively prohibit the coke formation. O-2 Can also increase the CH4 conversion and H-2/CO ratio of the producer gas. The average conversion of CH4 in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H-2/CO ratio increased from 0.95 to 1.1 with the addition of O-2, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.

Study on the technology of thermal cracking of paraffin to alpha olefins

Alpha olefins are mainly produced from paraffin cracking in China, but their quality is not good because of bad quality of cracking feed and outdated technology. The technology of paraffin once-through cracking, paraffin recycle cracking of removing the heavy fraction after wax vaporizing and that of removing the heavy fraction before wax vaporizing were investigated in this paper. It was found that the technology of paraffin recycle cracking of removing the heavy fraction before wax vaporizing is new and better under the same operating conditions. Using hard paraffin (mp 54-56 degrees C) as feed, the high-quality alpha olefins products (C-5-C-21) containing more than 97 wt% of olefins and more than 88 wt% of alpha olefins are produced under optimum process conditions, which are a steam to paraffin ratio of 15 wt%, process temperature of 600 degrees C, low hydrocarbon partial pressure and residence time of 2 s. In addition, with the technology of the second injecting steam in ethylene cracking used in paraffin cracking, producing coke in paraffin cracking furnace has been markedly reduced.