Reaction engineering studies in a polytropic fixed-bed reactor over a highly active and selective catalyst for oxidative methane coupling

The oxidative coupling of methane (OCM) was carried out in a polytropic fixed-bed reactor applying a Zr/La/Sr catalyst developed by the Neste company. Over this catalyst the OCM reaction follows a complex reaction scheme which includes primary parallel reaction steps to CO, CO₂ and C₂H₆ and consecutive reactions of ethane to ethylene or CO_x. Yield of higher hydrocarbons C₂₊ obtained with this catalyst strongly depended on reaction conditions, i.e. low partial pressures of methane and oxygen obtained by diluting the feed gas with nitrogen and high reaction temperatures promoted C₂₊ selectivity and yield. The maximum yield amounted to 21.4% (20 Vol.-% CH₄, 9 Vol.-% O₂, 71 Vol.-% N₂, T = 860°C; X_CH4 = 41.8%, S = 52.5%). This result belongs to the highest yields reported in the open literature.     

Synergism of enzymes in chemical pulp bleaching from an industrial point of view: A critical review

Enzymes are biological catalysts and are very specific, catalyzing either a single chemical reaction or a limited number of closely related reactions. For example, xylanases are enzymes that catalyze the cleavage of polymeric xylan and thereby break down this hemicellulose. The first xylanase enzyme preparations used in the bleaching process of chemical pulp also contained cellulase, which catalyzes the hydrolysis of cellulose. This obviously had an adverse effect on pulp yield and quality. Unfortunately, this setback gave enzyme-assisted pulp bleaching a negative reputation. At a later stage, enzyme producers managed to engineer enzyme production strains that generated cellulase-free xylanase preparations. However, due to the initial negative experiences with the earlier enzyme mixtures, only a limited number of companies in the pulp industry have seriously considered using these so-called second-generation enzymes in their bleach plants. It is apparent that these improved enzyme preparations would bring about significant benefits in terms of chemical cost savings and effluent quality. In addition to xylanase-aided bleaching, it is possible to improve the effectivity further by adding other enzymes, such as lipase and esterase, to create an enzyme cocktail. This may be particularly beneficial in the bleaching of hardwood pulp, such as white birch, which often encounters complex and troublesome problems with wood extractives. By adding different types of enzymes at more than one position in the fiberline, even further improvements are possible. The main objective of this review is to discuss the advantages of incorporating modern enzyme preparations in the bleaching of chemical pulp.     

Poly(propylene) composite with hybrid nanofiller: Dynamic properties

Mechanical, impact, and relaxation properties of in situ synthesized carbon nanotubes‐polyaniline (CNT‐PANi) hybrid nanoparticle‐filled poly(propylene) (PP) composites with or without an amphiphilic dispersing agent were investigated using tensile testing, notched Charpy impact testing, and dynamical mechanical testing methods. The reference material was MWCNT filled PP composite. Ethyl gallate (EG) was the dispersing agent which realizes high conductivity in PP composites with hybrid filler. Measured properties showed quite similar behavior of CNT‐PANi hybrid and neat CNT filled composites. Addition of 20% EG in PP did not cause essential differences compared to the neat PP. When the dispersing agent was added in filler containing PP composites, remarkable effects were observed, especially in PP‐hybrid composites. Mechanically, these materials had improved tensile properties, but they were brittle compared to the materials without dispersing agent. Dynamic mechanical analysis showed improvement in storage modulus, and in loss modulus the α transition was well observable. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Measurement of Particulate Carbon in Atmospheric Aerosol in Helsinki

By means of a simple optical apparatus the levels and variations of concentrations of elemental carbon in particles were measured. Additionally, relations between variations of elemental carbon, lead, sulfate, total suspended particle, and nitrate concentrations were studied. Calibration was performed on real samples analyzed by a wet chemical method.     

Kinetics of glucose decomposition in formic acid

Cellulose is abundantly available in the form of forestry and agricultural lignocellulosic residues. These residues offer the most potential source for the production of cellulosic glucose, which is a prerequisite for the sustainable production of glucose-based fuels and chemicals. Acid catalysis is one path to lignocellulosic glucose and further to its dehydration end products. Furthermore, many studied lignocellulose pretreatment methods for enzymatic hydrolysis are carried out in acidic conditions, in which the unwanted release of hemicellulose-based glucose and its further reactions to harmful end products are possible. Thus, in order to maximize glucose production from non-food cellulosic raw materials, data on the kinetics of cellulose decomposition and formation rates of end products are required. Glucose decomposition is a complex reaction system that has often been modelled with empirical, simplified models. In this study, a kinetic model was developed for glucose decomposition in formic acid solution. The experimentation was carried out in batch reactors at 180-220 °C in 5-20% (w/w) formic acid. The model developed relies on a mechanistic step through an unknown substance and gives excellent correspondence to the experimental data despite the pseudo-elementary nature of the model structure.     

Long-chain fatty ammonium quaternaries in papermaking

A series of long-chain quaternary ammonium halogen esters (UKK-chemicals), quaternary dimethyl tallow epoxypropyl ammonium halogens (EPK1), quaternary ditallow methyl epoxypropyl ammonium halogens (EPK2), and EPK2 oligomers (EPK2P) were synthesized. At acidic, neutral, or slightly basic conditions, EPK1-, EPK2-, EPK2P-, and UKK-chemicals operate as cationic chemicals. They can be used, for example, as stock sizings, surface sizings, or fixatives. Stock sizing, surface sizing, and fixative experiments indicate that EPK1-, EPK2-, EPK2P-, and UKK-chemicals function at least as well as or better than the corresponding synthetic chemicals used in papermaking.     

Preparation and characterisation of α-methylstyrene–butadiene latexes for paper coating applications

The purpose of this work is to demonstrate how α-methylstyrene (AMS) can replace styrene in preparing styrene–butadiene (SB) type latexes and to compare the properties of the paper coating of the prepared α-methylstyrene–butadiene emulsion with the commercial styrene–butadiene latex reference sample. A lot of work is nowadays being conducted on different biorefinery concepts replacing fossil oil with biomass based raw materials due to the expected rise of the fossil oil cost. Aromatics can in principle be produced from renewable raw materials, such as lignin, sugars and terpenes for example. The potential methods include thermochemical conversions, catalytic fast pyrolysis, metabolic engineering, catalytic aromatisation and dehydrogenation among others. Terpenes, such as α-limonene and pinene, are possible sources of aromatics, and they can indeed be catalytically converted to p-cymene. Industrial hydrodealkylation and disproportionation processes developed by major petrochemical companies can further convert p-cymene to BTX aromatics or simultaneously dehydrogenate the alkyl chain of p-cymene to styrenic monomers such as α-methylstyrene. Based on the measured paper properties for uncalendered and calendered coated samples, AMS proved to be adequate to replace the oil based styrene in commercial reference SB latexes. Even though the emulsion polymerisation for the α-methylstyrene–butadiene latex was not optimised, almost all tested properties were at least equally good as in the commercial reference sample. α-Methylstyrene containing coating colours had slightly higher viscosity than the other coating colours. Coating colours containing α-methylstyrene seems to have an improved water retention compared to the commercial reference styrene–butadiene latex coating colour and the laboratory prepared styrene–butadiene coating colour. The paper coated with the commercial reference latex containing coating colour was less porous than the other coated papers. Despite of that, both dry and wet surface strength were at least equally good as in the case of the commercial reference latex. The results are promising when thinking of the future development of the bio-based latexes.     

Long-term sensor measurements of lung deposited surface area of particulate matter emitted from local vehicular and residential wood combustion sources

Abstract

Lung deposited surface area (LDSA) is a relatively new metric that has been argued to be more accurate at predicting health effects from aerosol exposure. For typical atmospheric aerosol, the LDSA concentration depends mainly on the concentration of ultrafine particles (e.g. vehicular exhaust emissions and residential wood combustion) and therefore optical methods cannot be used to measure and quantify it. The objective of this study was to investigate and describe typical characteristics of LDSA under different urban environments and evaluate how a diffusion charging-based Pegasor AQ Urban sensor (Pegasor Ltd., Finland) can be used as an alternative to optical sensors when assessing local combustion emissions and respective LDSA concentrations. Long-term (12?months) sensor measurements of LDSA were carried out at three distinctly different measurement sites (four sensor nodes) in the Helsinki metropolitan area, Finland. The sites were affected mainly by vehicular exhaust emission (street canyon and urban background stations) and by residential wood combustion (two detached housing area stations). The results showed that the accuracy of the AQ Urban was good (R² = 0.90) for the measurement of LDSA when compared to differential mobility particle sizer. The mean concentrations of LDSA were more than twice as high at the street canyon (mean 22 µm² cm^?3) site when compared to the urban background site (mean 9.4 µm² cm^?3). In the detached housing area, the mean concentrations were 12 µm² cm^?3, and wood combustion typically caused high LDSA peaks in the evenings. High correlations and similar diurnal cycles were observed for the LDSA and black carbon at street canyon and urban background stations. The utilization of a small-scale sensor network (four nodes) showed that the cross-station variability in hourly LDSA concentrations was significant in every site, even within the same detached housing area (distance between the two sites ～670?m).     

Gravure offset printing of polymer inks for conductors

A gravure offset printing process has been developed for Ag-filled polymer conductor ink. Pad printing and roller type printing have been used. Curing and electrical properties have been studied. A roller type of gravure offset printing has been used to evaluate the printing process and pad printing to print on the non-planar substrates. Based on differential scanning calorimetry (DSC) and resistivity measurements during ink curing, it was found that the ink had an optimum curing temperature of 140 °C. Square resistance of 300 and 150 μm wide lines can be as low as 20 and 28 mΩ/sq., respectively, for 7–8.5 μm thick line. The minimum line width was 70 μm. This minimum line width can be reduced with different ink solvents, but in this case the line thickness suffers and the square resistance increases, respectively.