Juha Ahola

Investigation of CO oxidation and NO reduction on three-way monolith catalysts with transient response techniques

The kinetics of CO oxidation and NO reduction reactions over alumina and alumina-ceria supported Pt, Rh and bimetallic Pt/Rh catalysts coated on metallic monoliths were investigated using the step response technique at atmospheric pressure and at temperatures 30–350°C. The feed step change experiments from an inert flow to a flow of a reagent (O2, CO, NO and H2) showed that the ceria promoted catalysts had higher adsorption capacities, higher reaction rates and promoting effects by preventing the inhibitory effects of reactants, than the alumina supported noble metal catalysts. The effect of ceria was explained with adsorbate spillover from the noble metal sites to ceria. The step change experiments CO/O2 and O2/CO also revealed the enhancing effect of ceria. The step change experiments NO/H2 and H2/NO gave nitrogen as a main reduction product and N2O as a by-product. Preadsorption of NO on the catalyst surface decreased the catalyst activity in the reduction of NO with H2. The CO oxidation transients were modeled with a mechanism which consistent of CO and O2 adsorption and a surface reaction step. The NO reduction experiments with H2 revealed the role of N2O as a surface intermediate in the formation of N2. The formation of NN bonding was assumed to take place prior to, partly prior to or totally following to the NO bond breakage. High NO coverage favors N2O formation. Pt was shown to be more efficient than Rh for NO reduction by H2.

Hydrolysis of organosolv wheat pulp in formic acid at high temperature for glucose production

Organosolv methods can be used to delignify lignocellulosic crop residues for pulp production or to pretreat them prior to enzymatic hydrolysis for bioethanol production. In this study, organic solvent was used as an acidic hydrolysis catalyst to produce glucose. Hydrolysis experiments were carried out in 5-20% formic acid at 180-220 °C. Wheat straw pulp delignified with a formicodeli™ method was used as a raw material. It was found that glucose yields from pulp are significantly higher than yields from microcrystalline cellulose, a model component for cellulose hydrolysis. The results indicate that cellulose hydrolysis of real fibers takes place more selectively to glucose than hydrolysis of microcrystalline cellulose particles does. The effect of the particle size on pulp hydrolysis was investigated, the crystallinity of hydrolyzed pulp was measured by XRD analysis, and the product distribution and its influence on the process was discussed.

Phosphonated nanocelluloses from sequential oxidative-reductive treatment-Physicochemical characteristics and thermal properties.

Nanocellulosic materials with good thermal stability are highly desirable for applications, such as reinforcement and filler agents in composites. In the present work, phosphonated cellulose was utilized to obtain nanocelluloses with good thermal stability and potential intumescent properties. Phosphonated cellulose was synthetized from birch pulp via sequential periodate oxidation and reductive amination using a bisphosphonate group-containing amine, sodium alendronate, as a phosphonating reagent. After high-pressure homogenization, bisphosphonate cellulose nanofibres or nanocrystals were obtained, depending on the initial oxidation degree. Nanofibres had a typical diameter of 3.8nm and length of several micrometers, whereas nanocrystals exhibited a width of about 6nm and an average length of 103-129nm. All nanocelluloses exhibited cellulose I crystalline structures and high transparency in water solutions. Phosphonated nanocelluloses exhibited good thermal stability and a greater amount of residual char was formed at 700°C compared to birch pulp and mechanically produced, non-chemically modified NFC.

Acid-catalysed xylose dehydration into furfural in the presence of kraft lignin.

In this study, the effects of kraft lignin (Indulin AT) on acid-catalysed xylose dehydration into furfural were studied in formic and sulphuric acids. The study was done using D-optimal design. Three variables in both acids were included in the design: time (20-80 min), temperature (160-180°C) and initial lignin concentration (0-20 g/l). The dependent variables were xylose conversion, furfural yield, furfural selectivity and pH change. The results showed that the xylose conversion and furfural yield decreased in sulphuric acid, while in formic acid the changes were minor. Additionally, it was showed that lignin has an acid-neutralising capacity, and the added lignin increased the pH of reactant solutions in both acids. The pH rise was considerably lower in formic acid than in sulphuric acid. However, the higher pH did not explain all the changes in conversion and yield, and thus lignin evidently inhibits the formation of furfural.

Kinetics of furfural destruction in a formic acid medium

Furfural is one of the key chemicals produced from hemicellulose pentosans in acidic conditions. In the same conditions, furfural also undergoes degradation reactions leading to yield loss. In this study, the kinetics of furfural degradation in a formic acid medium containing 2 to 30% (w/w) formic acid and 0.05 to 0.16 mol L−1 furfural was studied in small batch reactors. The reaction temperatures were 160, 180, and 200 °C. The results showed that the overall order of the reaction changes with the amount of formic acid catalyst: in high acid concentration (30%) the apparent order of reaction is over one and in low acid concentration (2%) the order of reaction is below one. The proposed kinetic model, which includes an uncatalysed and an acid-catalysed term, is capable of estimating this behaviour. The model and findings presented in this study can support the optimisation of furfural production conditions.

Formic acid aided hot water extraction of hemicellulose from European silver birch (Betula pendula) sawdust

Hemicellulose has been extracted from birch (Betula pendula) sawdust by formic acid aided hot water extraction. The maximum amount of hemicellulose extracted was about 70mol% of the total hemicellulose content at 170°C, measured as the combined yield of xylose and furfural. Lower temperatures (130 and 140°C) favored hemicellulose hydrolysis rather than cellulose hydrolysis, even though the total hemicellulose yield was less than at 170°C. It was found that formic acid greatly increased the hydrolysis of hemicellulose to xylose and furfural at the experimental temperatures. The amount of lignin in the extract remained below the detection limit of the analysis (3g/L) in all cases. Formic acid aided hot water extraction is a promising technique for extracting hemicellulose from woody biomass, while leaving a solid residue with low hemicellulose content, which can be delignified to culminate in the three main isolated lignocellulosic fractions: cellulose, hemicellulose, and lignin.

Pedagogical basis of DAS formalism in engineering education

The paper presents a new approach for a bachelor-level curriculum structure in engineering. The approach is called DAS formalism according to its three phases: description, analysis and synthesis. Although developed specifically for process and environmental engineering, DAS formalism has a generic nature and it could also be used in other engineering fields. The motivation for this new curriculum structure originates from the urge to solve the problems that engineering education has faced during the past decades, e.g. student recruitment problems and dissatisfactory learning outcomes. The focus of this paper is on the structure of the curriculum but the content is also discussed when it has an effect on the structure and its implementation. The presented structure, i.e. DAS formalism, builds upon the ideas of some classical pedagogical theories, which have regularly been applied at course level but seldom used to solve curriculum-level issues.

Object-oriented integration of macroscopic and microscopic characterization of matter

Abstract Molecular simulation is of growing importance in chemical engineering. The gap usually present in knowledge representations between disciplines is, however, a serious obstacle for efficient utilization of knowledge. The way of bridging the gap between macroscopic and microscopic characterization of matter presented in this paper is based on the view that the solution for integrating knowledge and for enhancing communication, in general, is possible by developing and adopting a unified concept system (PSSP language). The advantage of this system is that the same concepts can be used both in macroscopic and microscopic worlds, whereby the presentational gap is eliminated. Knowledge integration by the formal approach is illustrated by an example starting from an informal description of the example process which is represented as an object with its purpose and some features of its structure and state as specified. The structure of the process is then detailed hierarchically down to the molecular level. It is emphasized that structural detailing should be done in a manner which supports the subsequent state aggregation. The PSSP language can not eliminate discontinuities, which are in knowledge itself but precise location of the knowledge gap and its nature become more detectable by this kind of formal presentation

Optimisation of automotive catalytic converter warm-up: Tackling by guidance of reactor modelling

Abstract In this paper, the ability of the developed reactor model to predict converters performance has been evaluated against experimental data. The data is obtained from the full-scale tests and the performed European driving cycle vehicle tests., The focus is on the warm-up period of catalytic exhaust gas converters and especially on the prediction of catalyst light-off.