Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: A density functional theory study

The selective hydrogenation of acetylene to ethylene on several Pd surfaces (Pd(111), Pd(100), Pd(211), and Pd(211)-defect) and Pd surfaces with subsurface species (carbon and hydrogen) as well as a number of Pd-based alloys (Pd-M/Pd(111) and Pd-M/Pd(211) (M = Cu, Ag and Au)) are investigated using density functional theory calculations to understand both the acetylene hydrogenation activity and the selectivity of ethylene formation. All the hydrogenation barriers are calculated, and the reaction rates on these surfaces are obtained using a two-step model. Pd(211) is found to have the highest activity for acetylene hydrogenation while Pd(100) gives rise to the lowest activity. In addition, more open surfaces result in over-hydrogenation to form ethane, while the close-packed surface (Pd(111)) is the most selective. However, we also find that the presence of subsurface carbon and hydrogen significantly changes the reactivity and selectivity of acetylene toward hydrogenation on Pd surfaces. On forming surface alloys of Pd with Cu, Ag and Au, the selectivity for ethylene is also found to be changed. A new energy decomposition method is used to quantitatively analyze the factors in determining the changes in selectivity. These surface modifiers are found to block low coordination unselective sites, leading to a decreased ethane production. (C) 2013 The Authors. Published by Elsevier Inc. All rights reserved.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

Evidence To Challenge the Universality of the Horiuti-Polanyi Mechanism for Hydrogenation in Heterogeneous Catalysis:Origin and Trend of the Preference of a Non-Horiuti-Polanyi Mechanism

The Horiuti-Polanyi mechanism has been considered to be universal for explaining the mechanisms of hydrogenation reactions in heterogeneous catalysis for several decades. In this work, we examine this mechanism for the hydrogenation of acrolein, the simplest alpha,beta-unsaturated aldehyde, in gold-based systems as well as some other metals using extensive first-principles calculations. It is found that a non-Horiuti-Polanyi mechanism is favored in some cases. Furthermore, the physical origin and trend of this mechanism are revealed and discussed regarding the geometrical and electronic effects, which will have a significant influence on current understandings on heterogeneous catalytic hydrogenation reactions and the future catalyst design for these reactions.

Selective hydrogenation of acetylene in ethylene rich feed streams at high pressure over ligand modified Pd/TiO2

The selective hydrogenation of acetylene from ethylene rich streams was conducted at high pressure and in the presence of CO over two 1 wt% loaded Pd/TiO2 catalysts with differing dispersions. Although, the more poorly dispersed sample did not result in high acetylene conversion only a small proportion of the total available ethylene was hydrogenated to ethane. The more highly dispersed sample was able to remove acetylene to a level below the detection limit but this was at the expense of significant proportion (ca. 30%) of the available ethylene. Modification of the catalysts by exposure to triphenyl phosphine or diphenyl sulfide and subsequent reduction at 393 K led to improved performance with increased conversion of acetylene and decreased propensity to hydrogenate ethylene resulting in an overall net gain in ethylene. The higher dispersed sample which had been ligand modified provided the best results overall and in particular for the diphenyl sulfide treated sample which was able to completely eliminate acetylene and still obtain a net gain in ethylene. The differences observed are thought to be due to the creation of appropriate active ensembles of Pd atoms which are able to accommodate acetylene but have limited ability to adsorb ethylene. Sub-surface hydrogen formation was suppressed, but not eliminated, by exposure to modifier.

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

Formulation of fermentation media from flour-rich waste streams for microbial lipid production by Lipomyces starkeyi

Flour-rich waste (FRW) and by-product streams generated by bakery, confectionery and wheat milling plants could be employed as the sole raw materials for generic fermentation media production, suitable for microbial oil synthesis. Wheat milling by-products were used in solid state fermentations (SSF) of Aspergillus awamori for the production of crude enzymes, mainly glucoamylase and protease. Enzyme-rich SSF solids were subsequently employed for hydrolysis of FRW streams into nutrient-rich fermentation media. Batch hydrolytic experiments using FRW concentrations up to 205 g/L resulted in higher than 90%(w/w) starch to glucose conversion yields and 40% (w/w) total Kjeldahl nitrogen to free amino nitro-gen conversion yields. Starch to glucose conversion yields of 98.2, 86.1 and 73.4% (w/w) were achieved when initial FRW concentrations of 235, 300 and 350 g/L were employed in fed-batch hydrolytic experiments, respectively. Crude hydrolysates were used as fermentation media in shake flask cultures with the oleaginous yeast Lipomyces starkeyi DSM 70296 reaching a total dry weight of 30.5 g/L with a microbial oil content of 40.4% (w/w), higher than that achieved in synthetic media. Fed-batch bioreactor cultures led to a total dry weight of 109.8 g/L with a microbial oil content of 57.8% (w/w) and productivity of 0.4 g/L/h.

Inventory of thermo-erosional valleys and streams in three ice-rich permafrost lowlands adjacent to the Laptev Sea, with links to maps in ArcGIS format

This dataset provides an inventory of thermo-erosional landforms and streams in three lowland areas underlain by ice-rich permafrost of the Yedoma-type Ice Complex at the Siberian Laptev Sea coast. It consists of two shapefiles per study region: one shapefile for the digitized thermo-erosional landforms and streams, one for the study area extent. Thermo-erosional landforms were manually digitized from topographic maps and satellite data as line features and subsequently analyzed in a Geographic Information System (GIS) using ArcGIS 10.0. The mapping included in particular thermo-erosional gullies and valleys as well as streams and rivers, since development of all of these features potentially involved thermo-erosional processes. For the Cape Mamontov Klyk site, data from Grosse et al. [2006], which had been digitized from 1:100000 topographic map sheets, were clipped to the Ice Complex extent of Cape Mamontov Klyk, which excludes the hill range in the southwest with outcropping bedrock and rocky slope debris, coastal barrens, and a large sandy floodplain area in the southeast. The mapped features (streams, intermittent streams) were then visually compared with panchromatic Landsat-7 ETM+ satellite data (4 August 2000, 15 m spatial resolution) and panchromatic Hexagon data (14 July 1975, 10 m spatial resolution). Smaller valleys and gullies not captured in the maps were subsequently digitized from the satellite data. The criterion for the mapping of linear features as thermo-erosional valleys and gullies was their clear incision into the surface with visible slopes. Thermo-erosional features of the Lena Delta site were mapped on the basis of a Landsat-7 ETM+ image mosaic (2000 and 2001, 30 m ground resolution) [Schneider et al., 2009] and a Hexagon satellite image mosaic (1975, 10 m ground resolution) [G. Grosse, unpublished data] of the Lena River Delta within the extent of the Lena Delta Ice Complex [Morgenstern et al., 2011]. For the Buor Khaya Peninsula, data from Arcos [2012], which had been digitized based on RapidEye satellite data (8 August 2010, 6.5 m ground resolution), were completed for smaller thermo-erosional features using the same RapidEye scene as a mapping basis. The spatial resolution, acquisition date, time of the day, and viewing geometry of the satellite data used may have influenced the identification of thermo-erosional landforms in the images. For Cape Mamontov Klyk and the Lena Delta, thermo-erosional features were digitized using both Hexagon and Landsat data; Hexagon provided higher resolution and Landsat provided the modern extent of features. Allowance of up to decameters was made for the lateral expansion of features between Hexagon and Landsat acquisitions (between 1975 and 2000).

A mathematical programming approach to optimal Markovian switching of Poisson arrival streams to queueing systems

Motivated by certain situations in manufacturing systems and communication networks, we look into the problem of maximizing the profit in a queueing system with linear reward and cost structure and having a choice of selecting the streams of Poisson arrivals according to an independent Markov chain. We view the system as a MMPP/GI/1 queue and seek to maximize the profits by optimally choosing the stationary probabilities of the modulating Markov chain. We consider two formulations of the optimization problem. The first one (which we call the PUT problem) seeks to maximize the profit per unit time whereas the second one considers the maximization of the profit per accepted customer (the PAC problem). In each of these formulations, we explore three separate problems. In the first one, the constraints come from bounding the utilization of an infinite capacity server; in the second one the constraints arise from bounding the mean queue length of the same queue; and in the third one the finite capacity of the buffer reflect as a set of constraints. In the problems bounding the utilization factor of the queue, the solutions are given by essentially linear programs, while the problems with mean queue length constraints are linear programs if the service is exponentially distributed. The problems modeling the finite capacity queue are non-convex programs for which global maxima can be found. There is a rich relationship between the solutions of the PUT and PAC problems. In particular, the PUT solutions always make the server work at a utilization factor that is no less than that of the PAC solutions.

Burning Low Volatile Fuel in Tangentially Fired Furnaces with Fuel Rich/Lean Burners

Pulverized coal combustion in tangentially fired furnaces with fuel rich/lean burners was investigated for three low volatile coals. The burners were operated under the conditions with varied value N-d, which means the ratio of coal concentration of the fuel rich stream to that of the fuel lean stream. The wall temperature distributions in various positions were measured and analyzed. The carbon content in the char and Nox emission were detected under various conditions. The new burners with fuel rich/lean streams were utilized in a thermal power station to burn low volatile coal. The results show that the N-d value has significant influences on the distributions of temperature and char burnout. There exists an optimal N-d value under which the carbon content in the char and the Nox emission is relatively low. The coal ignition and Nox emission in the utilized power station are improved after retrofitting the burners.

The ionic composition of surface waters in the English Lake District, related to bedrock geology, with some singular facts and speculation on the existence of mineral-rich groundwaters

This article is based on a survey of tarns conducted mainly in the summers of 1983 to 1985, plus a survey made in the winter of 1985, in which streams were sampled on the wide variety of rock-types occurring on the fringes of the Lake District. Differences in composition of major ions and their concentrations in the surface waters of Cumbria reflect the complex geological structure of the region. At altitudes above 300 m, on Borrowdale Volcanics and Skiddaw Slates, surface waters are derived from atmospheric precipitation, with additional inputs of some ions - especially calcium and bicarbonate - from catchment rocks and soils. In some of the low-lying large lakes on the fringes of the central fells, water composition is also dominated by inputs from upper catchments; examples are Wastwater, Ullswater and Haweswater. However in other lakes there is evidence (Derwentwater and Bassenthwaite Lake) of inputs from saline groundwater.

Ranunculus calcareus and its role in lowland streams

Ranunculus calcareus , a species of water crowfoot which occurs in clear, nutrient-rich chalk streams, was studied. Seasonal changes in its biomass, its annual production and its fragmentation (leading to downstream movement of the plant) were investigated. From an understanding of the growth rate and requirements of plants such as these, an indirect method of management can be devised, which does not have the undesirable consequences of the direct methods (such as cutting).

Catchment and in-stream influences on metal concentration and ochre deposit density in upland streams, Northern Ireland

Metal concentrations from stream waters in two geological blocks in Northern Ireland were compared to determine the contributions of catchment characteristics and in-stream conditions. One block is composed of metamorphosed schist and unconsolidated glacial drift with peat or peaty podzol (mainly humic) soils, while the other block consists of tertiary basalt with brown earth and gley soils. Water samples were collected from 52 stream sites and analysed for Fe, Mn and Al as well as a range of other chemical determinands known to affect metal solubility. Densities of metal-rich ochre deposit were determined for stream bed stone samples. Higher conductivities and concentrations of bicarbonate, alkalinity, Ca and Mg occurred on basalt than on schist. Despite higher Fe and Mn oxide concentrations in basalt-derived non-humic soils, stream water concentrations were much lower and ochre deposit densities only one third of those on schist overlain by humic soils. Neither rock nor soil type predicted Al concentrations, but pH and dissolved oxygen did. Peat-generated acidity and the limited acid neutralising capacity of base-poor metamorphosed schist have resulted in elevated concentrations of metals and ochre deposit in surface waters.

Techno-Economic Feasibility of Selective CO2 Capture Processes from Biogas Streams using Ionic Liquids as Physical Absorbents

Biogas from anaerobic digestion of sewage sludge is a renewable resource with high energy content, which is formed mainly of CH4 (40-75 vol.%) and CO2 (15-60 vol.%) Other components such as water (H2O, 5-10 vol.%) and trace amounts of hydrogen sulfide and siloxanes can also be present. A CH4-rich stream can be produced by removing the CO2 and other impurities so that the upgraded bio-methane can be injected into the natural gas grid or used as a vehicle fuel. The main objective of this paper is to develop a new modeling methodology to assess the technical and economic performance of biogas upgrading processes using ionic liquids which physically absorb CO2. Three different ionic liquids, namely the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-hexyl-3-methylimidazoliumbis[(trifluoromethyl)sulfonyl]imide and trihexyl(tetradecyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide, are considered for CO2 capture in a pressure-swing regenerative absorption process. The simulation software Aspen Plus and Aspen Process Economic Analyzer is used to account for mass and energy balances as well as equipment cost. In all cases, the biogas upgrading plant consists of a multistage compressor for biogas compression, a packed absorption column for CO2 absorption, a flash evaporator for solvent regeneration, a centrifugal pump for solvent recirculation, a pre-absorber solvent cooler and a gas turbine for electricity recovery. The evaluated processes are compared in terms of energy efficiency, capital investment and bio-methane production costs. The overall plant efficiency ranges from 71-86 % whereas the bio-methane production cost ranges from £6.26-7.76 per GJ (LHV). A sensitivity analysis is also performed to determine how several technical and economic parameters affect the bio-methane production costs. The results of this study show that the simulation methodology developed can predict plant efficiencies and production costs of large scale CO2 capture processes using ionic liquids without having to rely on gas solubility experimental data.