Kari Eränen

Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 °C/min) was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.

Imidazolium‐Based Poly(ionic liquid)s as New Alternatives for CO2 Capture

Solid imidazolium-based poly(ionic liquid)s with variable molecular weights that contain the poly[2-(1-butylimidazolium-3-yl)ethyl methacrylate] (BIEMA) cation and different counter anions were evaluated in terms of CO2 capture and compared with classical ionic liquids with similar counter anions. In addition to poly(ionic liquid)s with often-applied ions such as BF4 (-) , PF6 (-) , NTf2 (-) , trifluoromethanesulfonate (OTf(-) ) and Br(-) , for the first time [BIEMA][acetate] was synthesised, which revealed a remarkably high CO2 sorption performance that exceeded the poly(ionic liquid)s studied previously on average by a factor of four (12.46 mg gPIL (-1) ). This study provides an understanding of the factors that affect CO2 sorption and a comparison of the CO2 capture efficiency with the frequently used sorbents. Moreover, all the studied sorbents were reusable if regenerated under carefully selected conditions and can be considered as suitable candidates for CO2 sorption.

Pyrolysis of pine and gasification of pine chars - influence of organically bound metals.

Pyrolysis of pine and gasification of pine chars was studied in this work, focusing on the influence of organically bound metals. Selective leaching of the major ash-forming elements in pine wood was performed with different acids, namely, nitric, sulfuric, hydrochloric and oxalic acids. No other major changes in the chemical composition of the biomass were observed except the removal of the metals. The effect of organically bound sodium, potassium, magnesium and calcium was studied in both pyrolysis and gasification. Removal of the metals had a positive effect on the pyrolysis, resulting in higher bio-oil, lower char and gas yields.

Intensification of hemicellulose hot-water extraction from spruce wood in a batch extractor – Effects of wood particle size

The effect of five different wood particle size fractions between 0.5 and 12.5 mm on hot-water extraction of acetylated water-soluble hemicelluloses from spruce wood with a batch extraction setup at 170 °C was investigated. Extraction kinetics, with regard to particle size, was also studied. The purpose was to intensify the hemicellulose extraction for high molar mass hemicelluloses at high yield and purity. About 30% of the wood was dissolved and basically all the hemicelluloses could be extracted. The average molar masses of the extracted hemicelluloses decreased rapidly during the first 10 min of the extraction, but were not much affected by the difference in wood particle sizes. Smaller particles resulted in higher extraction rates. The reaction order was established to be of pseudo-first order for particles above 2mm and 1.5st order for particles smaller than 2mm. The effective diffusion coefficient was determined to be 9.11×10(-10) m(2)/s.

On the performance of Ag/Al2O3 as a HC-SCR catalyst – influence of silver loading, morphology and nature of the reductant

This study focuses on the performance of Ag/Al2O3 catalysts for hydrocarbon selective catalytic reduction (HC-SCR) of NOx under lean conditions, using complex hydrocarbons as reductants. The aim is to elucidate the correlation towards the silver loading and morphology, with respect to the nature of the reductant. Ag/Al2O3 samples with either 2 or 6 wt% silver loading were prepared, using a sol–gel method including freeze-drying. The catalytic performance of the samples was evaluated by flow reactor experiments, with paraffins, olefins and aromatics of different nature as reductants. The physiochemical properties of the samples were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, scanning transmission electron microscopy/high angle annular dark field imaging, X-ray photoelectron spectroscopy and N2-physisorption. The 2 wt% Ag/Al2O3 sample was found to be the most active catalyst in terms of NOx reduction. However, the results from the activity studies revealed that the decisive factor for high activity at low temperatures is not only connected to the silver loading per se. There is also a strong correlation between the silver loading and morphology (i.e. the ratio between low- and high-coordinated silver atoms) and the nature of the hydrocarbon, on the activity for NOx reduction. Calculated reaction rates over the low-coordinated step and high-coordinated terrace sites showed that the morphology of silver has a significant role in the HC-SCR reaction. For applications which include complex hydrocarbons as reductants (e.g. diesel), these issues need to be considered when designing highly active catalysts.

Comparative study of sulfur-free nickel and palladium catalysts in hydrodeoxygenation of different fatty acid feedstocks for production of biofuels

Catalytic hydrodeoxygenation (HDO) of fatty acids has been investigated using different feedstocks for renewable diesel production. Two types of catalysts were studied: sulfur-free nickel supported on H-Y zeolites, γ-Al2O3 and SiO2, and palladium supported on active carbon as a noble metal catalyst. Preliminary HDO experiments were carried out on these catalysts in a semi-batch reactor at 300 °C in H2 under a total pressure of 30 bar for 6 h with stearic acid as a model for fatty acids. An in-depth comparative study of Ni/H-Y and Pd/C was performed in HDO of fatty acid methyl ester (FAME) obtained from the Chlorella microalga, tall oil fatty acids (TOFA) and animal fat. HDO experiments revealed that Ni/H-Y was a better catalyst for this process providing higher activity for different fatty acids. Ni supported on γ-Al2O3 and SiO2 provided complete conversion upon testing in HDO of stearic acid while total HDO over Pd/C was not reached.

Effect of the Load Size on the Efficiency of Microwave Heating Under Stop Flow and Continuous Flow Conditions

Abstract A novel heating efficiency analysis of the microwave heated stop-flow (i.e. stagnant liquid) and continuous-flow reactors has been presented. The thermal losses to the surrounding air by natural convection have been taken into account for heating efficiency calculation of the microwave heating process. The effect of the load diameter in the range of 4–29 mm on the heating efficiency of ethylene glycol was studied in a single mode microwave cavity under continuous flow and stop-flow conditions. The variation of the microwave absorbing properties of the load with temperature was estimated. Under stop-flow conditions, the heating efficiency depends on the load diameter. The highest heating efficiency has been observed at the load diameter close to the half wavelength of the electromagnetic field in the corresponding medium. Under continuous-flow conditions, the heating efficiency increased linearly. However, microwave leakage above the propagation diameter restricted further experimentation at higher load diameters. Contrary to the stop-flow conditions, the load temperature did not raise monotonously from the inlet to outlet under continuous-flow conditions. This was due to the combined effect of lagging convective heat fluxes in comparison to volumetric heating. This severely disturbs the uniformity of the electromagnetic field in the axial direction and creates areas of high and low field intensity along the load length decreasing the heating efficiency as compared to stop-flow conditions.

CO2 capture from biogas: absorbent selection

The development of proper biogas upgrading technology offers a viable means to utilize biogas in conventional power systems. In this paper, various molecular and ionic solvent systems were evaluated for CO2 removal from biogas in a loop reactor system. The performance of amine solutions, ionic liquids and their mixtures, amino acid salts and solutions blended with piperazine was compared in terms of their CO2 loading capacity. The experimental results revealed that addition of small amounts of piperazine can increase on average by 30 vol% the efficiency of above-mentioned solutions. The CO2 capturing capacity achieved for the most promising solvents was in the range of 50–60 L CO2/L absorbent. The regeneration of the solvent mixtures can be challenging since the solvents could loose 16–43 vol% of their initial efficiency upon CO2 release. The ionic liquid [C4mim][acetate] was found to be an efficient VOCs scrubbing media. Moreover, upon use of this ionic liquid, the amount of identified volatile organic compounds (VOCs) in the studied samples was reduced by 65 wt%, while the use of 15 wt% aqueous N-methyldiethanolamine (MDEA) resulted only in 32 wt% reduction in the amount of VOCs.

Zeolite-bentonite hybrid catalysts for the pyrolysis of woody biomass

Hybrid catalysts consisting of a zeolite (ZSM-5 or Beta) and bentonite as a binder were prepared and characterized by XRD, pyridine FTIR and nitrogen adsorption. The hybrid catalysts exhibited similar properties as the combined starting materials. Catalytic pyrolysis over pure ZSM-5 and Beta as well as hybrid catalysts has been successfully carried out in a dual-fluidized bed reactor. De-oxygenation of the produced bio-oil over the different zeolitic materials was increased compared to non-catalytic pyrolysis over quartz sand.

Acid hydrolysis of O-acetyl-galactoglucomannan in a continuous tube reactor: a new approach to sugar monomer production

Abstract Hemicellulose O-acetyl-galactoglucomannan (GGM) is the main noncellulosic water-soluble polysaccharide in the coniferous softwood Norway spruce, consisting of anhydro-galactose, -glucose, and -mannose. Acid hydrolysis of GGM has been studied in a continuous tube reactor to obtain these sugars under industrially relevant conditions. The reaction was performed under atmospheric pressure at 90°C and 95°C, and hydrochloric acid (HCl) served as catalyst. The influence of the reaction parameters, such as acid concentration (pH), temperature, concentration of the substrate, as well as catalyst and reactant flow rates, has been studied on the conversion efficiency and product distribution. Continuous production of monomeric sugars was achieved without formation of low-molecular by-products. The GGM conversion was high with HCl as catalyst, at 95°C, and a pH of 0.3. The main hydrolysis products were mannose, glucose, and galactose monomers. Minor amounts of sugar dimers were detected among the products. The experimental results are described with a laminar flow model for the continuous reactor.